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TD Bank Retools Branch Network While Beefing Up Digital Investments
'America's Most Convenient Bank' still believes in branches but has been optimizing its network in the wake of Covid's digital wake-up call. Changes include flexible floor plans that can shift from a transaction-heavy setup to a more advice-friendly arrangement.
By Steve Cocheo, Executive Editor at The Financial Brand
For TD Bank convenience has long been considered a core 'product.' The emphasis goes back to its acquisition of Commerce Bank, which coined the tagline, "America's Most Convenient Bank."
In the quest for convenience, there never was a channel TD didn't like, because it was all about serving the consumer however they wanted, whenever they wanted, and nearly wherever they wanted. Emblematic of that strategy was the company's extensive and closely spaced branch system in the eastern U.S. Even today in some TD Bank communities you can't go north, east, south or west without hitting a TD Bank office.
As the meaning of convenience changes, TD Bank is changing its branching approach — in number, purpose and style.
Like many financial institutions, TD Bank, the eighth-largest U.S. bank and a subsidiary of Canada's TD Bank Group, saw a massive increase in usage of digital channels during the pandemic. In 2020 alone, in both the U.S. and Canada, TD saw a 57% increase in adoption of digital services. It has four million active mobile users in the U.S., counting both consumers and small businesses, and 50% of customers are active online, on mobile or both.
This all begs the question, is the company's extensive U.S. branch system still the competitive advantage it was for years?
The short answer appears to be, "Yes, but differently."
Factors Driving TD's Revised Branch Thinking
In the wake of Covid shutdowns and periods of drive-through service only, TD Bank has learned some lessons, and sees the need for some changes, but it has also seen reaffirmation of the desire for branches (which it calls "stores").
"We believe that the branch is essential to our distribution strategy," says Ernie Diaz, Head of Consumer Distribution, Wealth and TD Auto Finance, in an interview with The Financial Brand. "There is a need for it and the consumer wants the option to bank with TD in whatever channel they want at pretty much any time they want."
In other words, in spite of what digital gurus say, "the branch is not dead," he declares.
Early on during the pandemic TD Bank consumers fell back on digital channels and drive-through service, but they wanted more, says Diaz.
"We have found that there is a strong relationship between the physical and the digital. The customer isn't saying they want to do all one or all the other. They have gone between one channel and another, especially during difficult times."
— Ernie Diaz, TD Bank
"For some needs, people were willing to make an appointment to come in, because they wanted to have a conversation," says Diaz. Even as more use was being made of digital channels, the bank quickly put a digital booking service called Virtual Queue in place for both consumer and business customers. There were many thousands of check-ins daily before branches completely reopened.
One lesson taken away from the Covid period that may stand the bank in good stead — particularly given the flare-up in cases in the summer of 2021 — is the ability to quickly shift branch modes depending on what is going on with consumers and with the health of bank staff, according to Diaz.
"Every day you're getting some Covid cases and with that you have to adjust when it impacts staffing in a particular store," says Diaz. "What we have done is set up an approach where we adjust the operating model in the store temporarily. We may go to a drive-through-only model until we've restabilized staffing. Or we may have to go back to the Virtual Queue appointment-setting service to make sure we've got enough people in the store to handle the traffic and the social distancing."
Why Citi Won't Dump Its Skinny Branch Network and Go All Digital
Future of Branches Debated in a Transformed Digital Ecosystem
Do Shared Branches Have a Role in the Digital Age?
5 Points to Keep Your Branch Strategy on Track
As younger consumers expect a flawless, frictionless digital experience, traditional financial institutions need to adapt to meet them where they are.
wednesday, february 9th at 2:00pm est
Reallocating Resources without Losing the Classic TD Appeal
Having seen digital channels proven out during a time when many consumers wanted to avoid human contact, TD Bank has been approaching efforts to "optimize" its branch system carefully.
Banks and credit unions that lean heavily on physical presence pay for the advantage in real estate, maintenance and staff costs, and that's just for starters. McKinsey estimates that one-third to one-half of the operating costs of a retail bank come from the branch system and associated employees. There's a balancing act between spending for the traditional network and spending to build and improve digital channels.
Milestones Versus Millstones
A FitchRatings paper on U.S. bank branch optimization warns against getting stuck in 'brick and mortar traps.' The costs of maintaining branch networks can keep funds from going into investments in self-serve technologies.
On the other hand, studies indicate that as much as half of attrition among retail customers comes from unhappiness with service, according to FitchRatings. The perception that a financial institution lacks sufficient branches to serve consumers can cause consumers to leave for another institution. And while younger consumers like digital channels by nature, many studies indicate that they still want to have branches in easy reach.
In February 2021 during an earnings call TD Bank Group management revealed that it planned to close 82 stores in the U.S. By summer that had been completed, so that between that large closure and a handful of others, TD's U.S. network had dropped 7% from 1,232 at yearend 2020 to 1,142 in August 2021.
The intent is to put the savings back into the business in the form of digital platform investment, among other items, according to Gregory Braca, Group Head, U.S. Retail, and CEO of TD Bank.
"One thing that Covid has taught us is that our customers want access to us, but they want it all ways," said Braca in February. "They do want physical and we're seeing many of our customers return into the store. And we're bullish on that. And you'll see markets in future years where we continue to invest in new stores. But what you're also seeing is the need for investment in digital and digital capabilities, and we're doing just that."
How frequently consumers use a specific store may determine its continued existence in the TD Bank network, according to Diaz. Something else that will play a part in decisions is the travel time to the next-closest office should a store be closed. Diaz says there's no satisfactory overall standard, and that drive time in different locales and states may mean more or less than in others.
"I don't want to inconvenience our customer base," says Diaz. "That would go against our 'Unexpectedly Human' approach to our markets." But he says in most areas five to ten additional minutes driving should be acceptable.
Rethinking Branch Networks Without Killing Sales or Jeopardizing Growth
Branch Staff Unprepared as Offices Become 'Advisory Centers'
Chatbots and Cafés: How Capital One Balances Digital, Physical Banking
The Coming Convergence of Neobanks and Traditional Players
Out of Sight, Out of Mind: Why Branches Still Matter
Bringing Flexibility to the Floors of TD Bank Stores
Diaz says the rapidly building participation in self-service channels is causing more of the business that comes into stores to be of an advisory nature. This suggests that stores be migrated to a model that allows them to actually adapt to days when more traffic will be people seeking advice from bankers and, conversely, to layouts favoring transactional business when demand for those services is heavier.
The bank is experimenting with modular furniture, including mobile teller station "pods," that will permit locations to be adapted based on the nature of anticipated traffic. One such location is at a new store at the University of Central Florida in Orlando. The UCF store features a flexible layout with sit/stand workstations (pictured below) designed to serve as traditional teller counters (standing) or desks for more in-depth conversations (seated), according to the bank.
TD Bank's new flagship store, to be located in the retail section of the "supertall" One Vanderbilt tower in Manhattan, will also be flexible, but in a slightly different way, the bank states. Branch employees will be "untethered" from workstations and equipped with tablets to allow them to have advice, service or sales conversations from anywhere in the facility.
Going forward, branch locations may consist of smaller formats, says Diaz, "but they will have tremendous flexibility built into them."
This article was originally published on August 17, 2021 . All content © 2022 by The Financial Brand and may not be reproduced by any means without permission.


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Turkey demands extradition of Fethullah Gulen from US
Erdogan wants businessman Fethullah Gulen sent back from the US, accusing him of being behind failed coup.
17 Jul 2016 09:22 GMT
US-Turkish tensions have grown after government forces put down an attempted coup on Friday night.
Turkish President Recep Tayyip Erdogan has accused exiled Turkish businessman and cleric Fethullah Gulen of orchestrating the violence and is demanding that the US extradite him.
Gulen, who lives in Pennsylvania, denied any involvement and condemned the coup attempt.
US-based cleric Fethullah Gulen lives in Saylorsburg, Pennsylvania [Greg Savoy/Reuters]
Secretary of State John Kerry told his Turkish counterpart in a phone call that Turkey needs to respect due process as it investigates those it believes were involved in the plot.
At least one senior Turkish official has directly blamed the US for the attempt to topple Erdogan. That prompted Kerry to tell Turkey's foreign minister that "public insinuations" about a US role are "utterly false" and harmful to US-Turkish relations.
The exchange comes against the backdrop of Turkey closing its air space, effectively grounding US fighter jets that have been targeting Islamic State of Iraq and the Levant (ISIL, also known as ISIS) forces in neighbouring Syria and Iraq.
Purge launched
Turkey has begun a purge of soldiers and judiciary officials allegedly connected to the plot.
By Saturday evening, the government had detained 2,839 military personnel, with the number of arrests expected to rise, according to Prime Minister Binali Yildirim.
Turkey's top judicial body, the HSYK, dismissed 2,745 judges on Saturday, according to Turkey's Anadolu news agency.
Additionally, a senior Turkish official told Al Jazeera that at least two judges from the constitutional court and 10 judges from the HSYK had been detained.
Speaking on condition of anonymity, the official said that the judges were detained based on "financial transactions and communications between the individuals in question and the putschists", but added that detention did not necessarily mean conviction.
Another senior official, also speaking anonymously, told Al Jazeera that a top army general was also detained over his alleged involvement.
"General Erdal Ozturk, commander of the Third Army, has been detained," he said.
"Our sense is that the would-be junta had made preparations for some time. They had determined which military officers would take over as governors, heads of government agencies ... but they were forced to rush due to the upcoming Supreme Military Council meeting," he added.
The coup attempt began at around 19:30 GMT on Friday with the partial closure by troops of two major bridges over the Bosphorus in Istanbul.
"Their immediate goal was to seize control of key areas like the Bosphorus Bridge or Taksim Square," the same official told Al Jazeera.
"In Ankara, they tried to storm the Presidential Palace, the Prime Minister's office, the National Intelligence Organization and the Parliament. They also attempted to take down the satellite infrastructure and, in some areas, seized control of telecommunications hubs," he added.
An official described Ozturk as one of the "masterminds of the coup".
Turkey attempted coup

redpajama_set_name: RedPajamaCommonCrawl


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IV. León bizánci császár (750–780)
IV. Leó pápa (790–855)
IV. Leó örmény király (1308/9–1341)
IV. Leó mingréliai fejedelem (?–1694 /után/)

redpajama_set_name: RedPajamaWikipedia


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Malaria Test/ MP - QBC Method
Also known as : Malaria Test/ MP - QBC Method
No specific preparation required
Details of Malaria Test/ MP - QBC Method
What Is Mp Test?
There are diseases that sweep into the society, once in a while, that create havoc and are potentially destructive to the race. Malaria is one of those diseases that pose a significant threat to human life. If estimations are to be believed, hundreds of millions die due to Malaria. Quite alarmingly, World Health Organization (WHO) has compiled the list of countries that are vulnerable to this disease.
India, according to the list, is ranked 4th spot for malaria cases and deaths in 2017. The list further went on clear the fact that approximately 7% of the deaths are because of this grim disease in India. To make it even worse, children under the age of 5 are said to be the ones that are highly vulnerable to the parasites that cause them.
Hence it would be considered cautious and relevant on one's part to understand the primary underlying mechanism that shapes up this fatal disease. Malaria is a deadly disease caused by the Plasmodium parasite. This is transmitted through the bites of infected female Anopheles mosquitoes. It should be known that malaria, as a disease that can have serious implications similar to a virus and bacterial infection, is actually not caused by these.
It is through a parasite, which is single-celled, that can potentially multiply in the red blood cells rapidly and even in the intestines of the mosquitoes. The parasite grows in the liver, and then infects red blood cells (RBCs). The exact series of events that can result in getting injected by such parasites are not particularly easy to explain. The details are maybe convoluted from a layman's perspective.
Initially, a mosquito can get affected by feeding on a person who already houses the parasite. when this infected mosquito bites onto another person, the parasites will be shared with this new individual. Once these parasites grow haphazardly, they affect the liver and red blood cells. The cycle continues to become vicious and never-ending.
The person, infected with the parasites, will not be able to sense the infusion right away. The parasites, over a period of time, multiply in the liver, which is when the symptoms start to surface. The chills, high-fever could be benevolent of all symptoms, as they are possibilities of catching jaundice or anemia during this time. If ill-fated, the brain can be severely affected resulting in other neurological problems.
This parasite could also be transmitted through other media like blood transfusion, use of infected needles or syringes contaminated with blood, vertical transmission, or organ transplant.
When Do You Expect Results?
Why Get Tested?
Individuals infected with malaria are generally very ill with high fevers, shaking chills, and flu-like symptoms and malaise. The most commonly used tests to detect the malaria parasite are:
Malarial Parasite by Smear Examination (Blood)
Rapid Diagnostic Test (RDT) such as
Malaria detection by Quantitative Blood Count (QBC), Blood
Malarial Antibody-IgG, SerumMalarial Antigen (Vivax & Falciparum), Blood
Reason To Take Mp Test
Apart from the possibility of getting infected through female mosquitoes, and a blood transfusion from a priorly affected patient, it can also be transmitted from the mother to the foetus during pregnancy.
A variety of symptoms are generally observed in infected persons, ranging from absent, very mild symptoms to severe disease and even death. These symptoms begin to show up about 1-3 weeks after the infection. But there is also a rare possibility of housing an inactive parasite inside the body for up to a year.
More commonly an infected individual is observed to have a combination of symptoms like:
General malaise
Enlarged spleen
Anaemia; One of the most common and understandable symptoms of malaria, as the red blood cells of the blood are severely affected by malarial parasites.
Mild jaundice
Enlargement of the liver; Liver happens to be the first organ that is affected by the plasmodia parasite. Because of the excessive work the liver and spleen have to take up to combat malarial infection by constantly releasing antibodies through white blood cells, they enlarge.
Increased respiratory rate
Cerebral malaria: If the flow of small blood cells to the brain is blocked by other blood cells, filled with parasites, it can result in swelling of the brain. In the worst-case scenario, it may also result in a coma.
People from regions that are easily prone to Malarial parasites can have an altered immune system. Because of the frequency at which they can be exposed to the diseases, they will be able to acquire partial immunity for the symptoms.
But the acquired partial immunity can wear off, eventually, when an individual moves away to a different country where the frequency of exposure to the parasite will be lessened.
Preparations Needed For Mp Test
Preparatory instructions before the test *:
No Fasting Required.
No other special preparations are required.
Sample Required?
Specimen type: Serum (Blood Sample),
Specimen collection procedure: Venipuncture (Collection of blood from a vein, usually from the arm)


What is Bitcoin Cash and Where did it come from?
Enter The Crypto > Alt Coin > What is Bitcoin Cash and Where did it come from?
Bitcoin Cash (BCH) came about as a result of a fork from Bitcoin on 1 August 2017.
Why did the fork happen?
Why did Bitcoin's Blocksize matter?
The supporters of Bitcoin Cash were concerned about the 1MB limit as it meant that transactions were slow. The network could not handle the amount of transactions that were taking place at the required pace. This led to an increase in fees, as users paid miners more in order to add their transaction to the first available 'block.' Users were discouraged from sending small tranactions due to the fees payable.
Supporters of Bitcoin Cash found this unacceptable, they were concerned that this would lead to people no longer using Bitcoin.
In 2017, capacity hit the 'invisible wall'. Fees skyrocketed, and Bitcoin became unreliable, with some users unable to get their transactions confirmed, even after days of waiting.
Bitcoin stopped growing. Many users, merchants, businesses and investors abandoned Bitcoin. Its marketshare among other cryptocurrencies quickly plummeted from 95% to 40%. (BitcoinCash.org).
What did Bitcoin Cash do to fix this apparent problem?
The increase in the blockchain's size means that BCH allows for more transactions to take place per day, at a faster and cheaper rate.
Bitcoin Cash immediately raised the block size limit to 8MB as part of a massive on-chain scaling approach. There is ample capacity for everyone's transactions.
It is extremely difficult to predict the future, especially in the Crypto world. A week ago the Crypto world was preparing for the 'Segwit2x' hard fork, which did not happen. We are very much still at an early stage. Cryptocurrencies and blockchain technology have yet to really take off (despite what some may think).
We have been following Bitcoin Cash for a while. On 5th November we posted on Bitcoin Cash whilst the price was $620. It has since risen to over $2,500 before falling to a current price of $1,230.
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The role of oxygen and water on molybdenum nanoclusters for electro catalytic ammonia production
Jakob G. Howalt1,2 and
Tejs Vegge1
Jakob G. Howalt
Department of Energy Conversion and Storage, Technical University of Denmark, DK-4000 Roskilde, Denmark
Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark
Tejs Vegge
1Department of Energy Conversion and Storage, Technical University of Denmark, DK-4000 Roskilde, Denmark
2Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark
Received 30 Sep 2013, Accepted 17 Jan 2014, Published 31 Jan 2014
The presence of water often gives rise to oxygen adsorption on catalyst surfaces through decomposition of water and the adsorbed oxygen or hydroxide species often occupy important surfaces sites, resulting in a decrease or a total hindrance of other chemical reactions taking place at that site. In this study, we present theoretical investigations of the influence of oxygen adsorption and reduction on pure and nitrogen covered molybdenum nanocluster electro catalysts for electrochemical reduction of N2 to NH3 with the purpose of understanding oxygen and water poisoning of the catalyst. Density functional theory calculations are used in combination with the computational hydrogen electrode approach to calculate the free energy profile for electrochemical protonation of O and N2 species on cuboctahedral Mo13 nanoclusters. The calculations show that the molybdenum nanocluster will preferentially bind oxygen over nitrogen and hydrogen at neutral bias, but under electrochemical reaction conditions needed for nitrogen reduction, oxygen adsorption is severely weakened and the adsorption energy is comparable to hydrogen and nitrogen adsorption. The potentials required to reduce oxygen off the surface are −0.72 V or lower for all oxygen coverages studied, and it is thus possible to (re)activate (partially) oxidized nanoclusters for electrochemical ammonia production, e.g., using a dry proton conductor or an aqueous electrolyte. At lower oxygen coverages, nitrogen molecules can adsorb to the surface and electrochemical ammonia production via the associative mechanism is possible at potentials as low as −0.45 V to −0.7 V.
Keywords: ammonia; density functional theory; electrocatalysis; nanoparticles; oxygen poisoning
Molybdenum nanoclusters have been identified as a prime candidate for electrochemical ammonia production with seemingly low Faradaic losses to hydrogen evolution [1,2]. To produce ammonia electrochemically, one can either use a liquid or a solid electrolyte, but these effectively require wet conditions to obtain sufficient protonic conduction [3,4]. The presence of water may give rise to oxygen or hydroxide adsorption on the surface, which can occupy or block important surfaces sites. The adsorbed oxygen species can either decrease or totally hinder other chemical reactions taking place at that site. Oxygen poisoning of the surface is indeed a main inhibitor for ammonia production [5,6]. In this paper, the presence of oxygen species, e.g., resulting from a dehydrogenation reaction of residual water from a solid electrolyte or an aqueous electrolyte, will be investigated to understand the implications it has on the catalytic properties for electrochemical ammonia production. In addition, the blocking of active sites by oxygen species has been explored; together with a determination of reduction pathways to electrochemically reduce the blocking oxygen off the surface.
Computational Method
DFT calculations
The calculations were carried out with density functional theory (DFT) calculations [7,8] using the RPBE exchange correlation functional [9] along with the projector augmented wave method [10,11] as implemented in the GPAW code [12-14]. A grid of (3,3) for the finite difference stencils have been used together with a grid spacing of 0.18 Å and a minimum of 20 free bands above the Fermi level. Periodic boundary conditions with a Monkhorst–Pack [15] k-point sampling of 2 × 2 × 2 were used to perform a methodological consistent comparison with previously obtained results on stepped and flat surfaces [1,16]. A 7 Å vacuum layer on all sides of the nanocluster is applied, giving a separation of 14 Å between the clusters. When solving the electronic density self-consistently, the convergence criteria have been chosen such that the changes were ≤10−5 eV for the energy and 10−4 electrons per valence electron for the density. In all calculations, a Fermi smearing of 10−4 eV has been used. The atomic simulation environment ASE [17] was used to set up the atomic structure of these systems. All calculations were performed without spin polarization in order to enable full structural (and atomic) relaxation of the full Mo13 nanocluster together with the adsorbates (N, H, O, NH, etc.); these were carried out using the BFGS and FIRE [18] optimizers within ASE.
Electrochemical modelling
The procedure for electrochemical reduction of nitrogen molecules through the associative mechanism is outlined in [2,16]. It was shown that the associative mechanism is the preferred route for electrochemical ammonia production, where the protonation of the nitrogen molecules give rise to a weakened N–N bond and subsequent splitting at the third or fourth protonation step. The dissociative mechanism, the other route for electrochemical ammonia production, is due to high dissociation barriers (1.8 eV) of N2 not taking place at the surface.
For the purposes of analyzing the reduction of oxygen, a two-step electron-transfer process was assumed and simulated using the Heyrovsky-type [19] reaction. In an acidic environment, the reaction comprises of these elementary reaction steps:
where e− is an electron in the electrode, H+ is a proton in the electrolyte and * is a surface site. The reference potential is set to that of the standard hydrogen electrode, and through the computational hydrogen electrode approach the electrons and protons are introduced into the analysis, where 1/2 H2 H+ + e−. Hereby, a description of the effects of an external applied potential U on the electrons and the concentration of protons in the electrolyte [20-24] are implemented.
The adsorption energy of O* under electrochemical reaction conditions under an applied potential U are calculated as where Esurface/O and Esurface are the total energies of the molybdenum nanocluster with and without the specific oxygen atom adsorbed, and is the gas phase energy of water and are the energy of protons and electrons with an applied potential defined by the computational hydrogen electrode approach. Molecular O2 is not expected to be present under operating conditions and the sole contributor of O atoms is water. At standard ambient temperature and pressure the adsorption energies are corrected with zero-point energy, EZPE, and entropy, TS, contributions at room temperatures.
In this paper the pH value is set to 0 and the values of the free energy corrections for all the oxygen containing species were found in literature [25], were the ΔEZPE –TΔS corrections for O is 0.05 eV, for OH is 0.35 eV and for H2O is 0.67 eV. A pH of, e.g., 7 would change the energy by 0.41 eV for all the reduction mechanisms, leaving the relative activity unchanged.
Oxygen adsorbed in nitrogen vacancies
We have previously shown that partially reduced nitrogen covered molybdenum nanoclusters are promising catalysts for electrochemical production of ammonia [2]. N2 adsorption is preferred over H in nitrogen vacancy sites at lower nitrogen coverages at the potential of U = −0.6 V needed for electrochemical ammonia production through the associative mechanism [2]. Adsorption of oxygen atoms at nitrogen vacancy sites is presented in Figure 1, where they have been adsorbed at the vacant bridge site.
Figure 1: (a) Adsorption of oxygen at a nitrogen vacancy site on Mo13N10, and (b) adsorption of oxygen at a nitrogen vacancy site on Mo13N12. Oxygen is adsorbed in the bridge site in both cases.
Figure 1: (a) Adsorption of oxygen at a nitrogen vacancy site on Mo13N10, and (b) adsorption of oxygen at a n...
The free energies for oxygen absorption are shown in Table 1 for neutral bias and the potential needed for ammonia production, and listed together with the energies for nitrogen and hydrogen (from [2]). At neutral bias, oxygen is the preferred adsorbate with adsorption energies of −1.58 eV increasing to −2.15 eV. Under these conditions, the vacancy sites will be filled with oxygen and block nitrogen molecules from adsorbing to the active sites and stop the electrochemical formation of ammonia.
Table 1: Stability of nitrogen, hydrogen and oxygen with (U = −0.6 V) and without (U = 0 V) an applied potential at nitrogen vacancy sites on Mo13Nx nanoclusters. The potential required to produce ammonia electrochemically at partially nitrogen covered molybdenum nanoclusters was shown to be U = −0.6 V [2]. The energies are given with respect to H2O (g), H2 (g) and N2 (g). (The values for ΔGN2, ΔGH (U = 0 V) and ΔGH (U = −0.6 V) are taken from [2]).
ΔGN2 [eV]
ΔGH [eV] (U = 0 V)
ΔGO [eV] (U = 0 V)
ΔGH [eV] (U = −0.6 V)
ΔGO [eV] (U = −0.6 V)
Mo13N12 −0.06 −0.66 −1.58 −1.26 −0.38
Mo13N10 −1.2 −0.73 −2.33 −1.33 −1.13
Mo13N9 −1.13 −0.59 −2.15 −1.19 −0.95
At the potentials needed for ammonia production (−0.6 V), the adsorption of oxygen is weakened by 1.2 eV, due to the change in energy from oxidation of water at the applied potential, i.e., −2U. Under these conditions, the adsorption of oxygen has a comparable stability to nitrogen and hydrogen.
The strong preference for oxidation at neutral bias means that the particles will often be (partially) oxidized during synthesis or sample transfer [24]. To free the active sites for N2 adsorption and subsequent electrochemical ammonia production, the adsorbed oxygen atoms needs to be removed from the surface sites. One way of re-activating the molybdenum nanocluster for electrochemical ammonia production is therefore to reduce the oxygen electrochemically to water, which will be less strongly bound to the active site and make it possible to bind N2 preferentially.
In the case of oxygen adsorption on the more nitrogen rich molybdenum nanoclusters, Table 2 shows the required potentials for the two-proton transfer steps in the reduction of oxygen.
Table 2: Reduction of oxygen adsorbed on the Mo13Nx nanocluster.
UO→OH [V]
UOH→H2O [V]
Mo13N12O −0.35 −1.62
Mo13N9O −0.72 −1.41
The potentials range from −1.28 to −1.62 V for the second protonation step, where the formation of H2O is hindered by the adsorbed nitrogen atoms in the three fold hollow sites, surrounding the adsorption site of O, OH and H2O. The high potential needed for the formation of H2O is due to the repositioning of the adsorption site of OH (bridge site) to the adsorption site of H2O (ontop site), which is structurally hindered by the nearby adsorbed nitrogen atoms. The removal of oxygen from the partially nitrogen covered molybdenum surface and oxygen will therefore constitute a strong blocking of the active sites and subsequently limit the ammonia production rate through the associative mechanism on partially oxidized nitrogen covered molybdenum nanoclusters.
Direct reduction of the residual nitrogen skin will, however, still be possible and the potential will not be influenced by the presence of oxygen and the nitrogen skin will be reduced electrochemically at −0.6 V as shown in [2].
An oxygen skin
The electrochemical production of ammonia will not only occur on nitrogen covered molybdenum clusters, but could also take place at very low or no nitrogen coverage [2]. A clean molybdenum nanocluster in contact with nitrogen, hydrogen and water at neutral bias will also adsorb oxygen from water on the surface, see Figure 2. The figure shows the total adsorption free energies of oxygen, nitrogen and hydrogen as the coverage evolves and until saturation of oxygen and nitrogen is obtained on the surface. This oxygen skin is approximate 1–2 eV more energetically favoured than a nitrogen skin at low coverage. At higher coverage, the oxygen skin becomes even more energetically favoured. However, an applied potential of U = −0.6 V, destabilizes oxygen (dashed blue line) significantly with respect to nitrogen and hydrogen (dashed red line), such that an overlayer of oxygen arising from electrochemical splitting of water should not be expected.
Figure 2: The total free energy for covering the Mo13 nanocluster with nitrogen, oxygen or hydrogen. The filled black line shows the filling of the nitrogen skin, while the filled blue line shows the evolution of oxygen coverage at neutral bias. The red coloured line shows the adsorption of hydrogen, while the dashed red coloured line shows adsorption of hydrogen and the dashed blue line shows the adsorption of oxygen at an external applied potential of −0.6 V, which is the potential needed for electrochemically ammonia production previously determined for the clean and nitrogen covered molybdenum nanocluster [2].
Figure 2: The total free energy for covering the Mo13 nanocluster with nitrogen, oxygen or hydrogen. The fill...
A cyclic pattern is seen in the binding energy for both nitrogen and oxygen adatoms, and the distance between the cycles correspond roughly to an addition of 10 electrons, corresponding to the filling of a d-shell. Figure S1 in Supporting Information File 1 shows the d-band of the molybdenum nanocluster as the oxygen coverage increases and it is observed that the d-band broadens and the energetically lower lying d-orbitals are filled additionally as the coverage of oxygen is increased.
The preferred adsorption sites for the oxygen atoms are the three fold hollow sites, see Figure 3a. When all the three fold sites are filled, the oxygen atoms will adsorb in the four fold hollow sites, see Figure 3c, where additional adsorption of a few oxygen atoms greatly distorts the surface; this restructuring allows a higher filling of oxygen on the surface, see Figure 3d. The maximum filling of the surface increases to 16 oxygen atoms and further additions of oxygen atoms are energetically unfavourable. Close to a full overlayer, the binding sites of oxygen becomes asymmetrically and the oxygen atoms now binds in a mix of a three fold hollow site and a bridge site.
Figure 3: (a) The Mo13O6 nanocluster, (b) the Mo13O9 nanocluster with N2 adsorbed, (c) the Mo13O12 with an almost filled oxygen skin, (d) the Mo13O16 with a filled oxygen skin. At the Mo13O16, the oxygen adsorption sites are a mix of three fold hollow sites and bridge sites.
Figure 3: (a) The Mo13O6 nanocluster, (b) the Mo13O9 nanocluster with N2 adsorbed, (c) the Mo13O12 with an al...
Reduction of the oxygen overlayer
For a fully oxygen covered molybdenum nanocluster, nitrogen molecules cannot adsorb to the surface. Therefore, a full oxygen skin eliminates electrochemical ammonia production. It is therefore necessary to reduce the surface, in order to create active sites for nitrogen adsorption. To investigate the reduction of oxygen on a partially or fully oxygen covered molybdenum nanocluster, the reduction of all adsorbed oxygen atoms should, in principle, be analysed. This is, however, not computationally feasible and instead up to three representative adsorbed oxygen atoms are reduced at each investigated oxygen coverage. Each of the selected oxygen atoms represents a unique oxygen adsorption position and the coverage ranges from 16 oxygen atoms to only one oxygen atom. The potentials needed for the two proton transfer processes are presented in Table 3. For other proton transfer processes (not shown), the local geometries around the adsorption site can hinder both protonation steps, but most often the second protonation is hindered. One such hindrance can be the movements from the adsorption site of the OH species to an on top site, where the H2O species is energetically most stable. Such movement requires a restructuring of the local environment, and hence the protonation step can become strongly endothermic. The largest variation is therefore seen for the second protonation step. For the presented reduction steps of OH to H2O, the required potentials are in the range of −0.2 to −0.7 V. The formation of OH from O will require a negative potential to stabilize the OH specie compared to the O atom, and in most cases the potential required are in the range of −0.3 V to −0.7 V.
Table 3: Reduction of an oxygen overlayer on molybdenum nanoparticles. Multiple adsorbed oxygen atoms have been reduced at the studied oxygen coverage. This is done to probe the reduction of all the unique adsorption sites at the studied oxygen coverage.
Mo13O16 −0.49 −0.44
Mo13O14 0.04 −0.47
Mo13O9 −0.27 −0.67
Mo13O −0.67 −0.72
For most of the studied coverages, the reaction free energies for desorption of H2O off the surface are either low or exergonic. In general, desorption energies are lower than 0.4 eV, but for a single adsorbed H2O molecule, it is as high as 1.2 eV. Water should therefore desorb thermally from the surface, except at very low oxygen coverages.
The study of oxygen reduction produces adsorption energies for O, OH, H2O at different coverages. No apparent correlation is found between the adsorption energies of EO, EOH and EH2O on the cluster, see Figure S2 and Figure S3 in Supporting Information File 1, in contrast to what has previously been observed on metal surfaces, where scaling relations are applicable for OH species on close-packed and stepped surfaces for low coverages [26]. The close packed and stepped surfaces typically have less restructuring during the adsorption of O, OH and H2O.
On the molybdenum nanocluster surface, larger local restructuring takes place when either O is added or removed and when either O or OH is protonated. The restructuring of the molybdenum cluster involves all atoms in the nanocluster. This is an effect of the small size of the nanocluster, where the local impact from an adsorption or a reduction step influences the whole nanocluster.
The lowest required potential for water formation at the different coverages is in the range of −0.3 V to −0.7 V. These values are lower or comparable to the required potential needed to form ammonia on the molybdenum nanocluster [2]. Overall, it seems that it is possible to reduce oxygen of the surface at moderate potential of −0.72 V. The potential required for reduction of a surface oxygen atom indicates that the nanoclusters can be reactivated after exposure to water from the electrolyte or the fabrication process.
Formation of ammonia at relative high oxygen coverage
Nitrogen molecules are not able to adsorb to neither an oxygen vacancy site nor ontop of an oxygen atom at high oxygen coverages. Once the oxygen skin has been partially reduced, the nitrogen molecules adsorb onto the surface at the oxygen vacancy sites, see Figure 3b. The adsorption of nitrogen become stable at a coverage of less than 10 oxygen atoms, see Table 4. The adsorption energies of N2 range from −1.0 eV to −1.8 eV depending on the oxygen coverage. The corresponding hydrogen adsorption energies are lower, ranging from −0.65 eV to −0.86 eV, and nitrogen molecules are therefore preferred over hydrogen on the surface at neutral bias. At an applied potential of −0.6 V, which is the potential shown to electrochemically produce ammonia on the clean molybdenum nanocluster, the reaction free energy of adsorbing either a hydrogen atom (coming from H+ and e−) or a nitrogen molecule will at certain coverages be in favour of H (Mo13O8 and Mo13O6) and others of N2 (Mo13O9 and Mo13O7).
Table 4: The adsorption free energies of nitrogen and hydrogen with and without an applied potential on a partly oxygen covered Mo13 nanocluster.
∆GN2 [eV]
∆GH [eV] (U = 0 V)
∆GH [eV] (U = −0.6 V)
Mo13O12 No binding −0.23 −0.83
Mo13O10 0.33 −0.84 −1.44
Mo13O9 −1.82 −0.72 −1.32
For nitrogen molecules adsorbed at a vacancy site on either Mo13O9 or Mo13O6, the potential for driving the electrochemical production of ammonia has been determined. These nanoclusters were selected to describe the two regimes with either strong or weak N2 adsorption compared to hydrogen adsorption, respectively. On the Mo13O9 nanocluster, N2 is bound most strongly at an applied potential of −0.6 V, while hydrogen is bound stronger on the Mo13O6 nanocluster. Investigations of the associative pathway on the Mo13O9 nanocluster, shows the first protonation step to require an onset potential of −0.7 V similar to that needed to reduce oxygen (see Table 3). The onset potentials are shown in Figure 4 for the following electrochemical reaction steps:
The x-axis show the adsorbed reaction intermediate for each protonation step and NH2N denotes a doubly protonated nitrogen molecule with the N–N backbone intact, while NH3–NH denotes NH3 and NH adsorbed on the surface and the N–N backbone has been dissociated. Five pathways were studied, and all of them had the first initial protonation step to be the potential limiting step with identical required onset potentials.
Figure 4: Diagram of the required applied potential to make each reaction step exergonic for electrochemical ammonia production on the Mo13O9 through the associative mechanism. For all five studied reaction pathways, the highest required potential is −0.7 V for the first protonation step.
Figure 4: Diagram of the required applied potential to make each reaction step exergonic for electrochemical ...
For a more reduced oxygen skin, e.g., the Mo13O6 nanocluster, the energetics of the electrochemical production of ammonia are much more diverse. Here, two routes are very favourably, demanding only potentials of around −0.45 V, to drive the electrochemical production of ammonia, see Figure 5. The routes not shown require potentials of −0.85 V to −1.3 V. The reaction intermediates for the preferred ammonia formation route have been used as the bottom x-axis. The blue filled line on Figure 5 shows that the rate-limiting step is the last protonation; while for the alternative route, marked with the green dashed line and the corresponding reaction intermediates have been used as the top x-axis in Figure 5, the rate-limiting steps are found to be both the third and the last protonation step. The limiting step for this reaction path is the formation of the NH2–NH intermediate on the surface. The reaction is then followed by a very exergonic reaction step, where the N–N bond breaks. In both pathways, the N–N bond breaking in the associative process is very exergonic and no apparent activation barrier is observed for the N–N cleavage at either the third or fourth protonation step. The onset potential presented here for electrochemical ammonia production is similar to those obtained in previous studies on both clean and nitrogen covered molybdenum nanoclusters [2].
Figure 5: Diagram of the required applied potential to make each reaction step exergonic for electrochemical ammonia production on the Mo13O6 through the associative mechanism. The limiting reaction is the last protonation to form the second ammonia on the surface requiring a potential of −0.45 V to become exergonic.
Instead of protonating the adsorbed nitrogen molecule, the potential could drive the reduction of oxygen. In Table 5, the potentials for driving the oxygen reduction processes are presented. Here, a potential of −0.77 V is required for the high oxygen coverage case, while the last reduction step for the lower oxygen coverage requires significantly larger potentials, i.e., −1.3 V to −1.75 V, to make the reaction exergonic, H2O is found to be unstable on Mo13O6, while Mo13O9 has a stable adsorption of water.
Table 5: The required potentials for reducing oxygen at two oxygen coverages, when nitrogen molecules are present on the partly covered oxygen surfaces.
Mo13O9-N2 −0.53 −0.77
Competing reaction mechanisms
Here, a possible reaction pathway is presented for electrochemical ammonia production on the Mo13O9 nanocluster with adsorbed N2 at an applied potential U = −0.7 V. Three possible mechanisms must be considered: the reduction of N2 to ammonia, hydrogen adsorption and evolution, and last the reduction of oxygen and subsequently formation of water. Here, we assume that the adsorption of H with N2 present on the surface will be equal to adsorption of H on a surface without N2 present.
The reaction free energies of forming H, OH, and N2H at U = −0.7 V are: ∆G[N2* + (H+ + e−) → N2H*] = 0 eV, ∆G[(H+ + e−) → H*] = −1.42 eV, ∆G[O* + (H+ + e−) → OH*] = −0.17 eV, respectively. The reaction step with the lowest reaction free energy is hydrogen adsorption on the surface. For adsorbed hydrogen, the next step will be formation of H2(g) with a reaction free energies of ∆G[H* + (H+ + e−) → H2(g)] = 0.02 eV. The next reaction to occur on the surface will therefore be the reduction of O to OH at −0.17 V. For this reaction intermediate, the next step will produce H2O with a reaction free energy of ∆G[OH* + (H+ + e- ) → H2O*] = 0.08 eV. Small energy differences exist for the next protonation step, but N2H will be formed on the surface.
The subsequent reaction intermediates for ammonia formation are exergonic at U = −0.7 V. The initial production of an overlayer of H is followed by reduction of O into OH, until the electrochemical reduction of N2 becomes possible. When the ammonia molecules have desorbed from the surface, adsorption of N2 is 0.4 eV more stable than H, which would make the adsorption of nitrogen at a vacancy site energetically favourable. At higher pH-values this difference would increase in favour of N2 adsorption because a pH relatively destabilizes the adsorption of H, see Equation 1. Because of the very small difference between the formation of N2H, H2O and H2(g) a Faradaic loss due to hydrogen evolution should be expected and a reduction of the oxygen skin on the surface would also be expected at this oxygen coverage and potential.
For the Mo13O6 nanocluster with N2 adsorbed at an applied potential of U = −0.45 V, the preferred mechanism is the following. First hydrogen is bound to the surface, then O is reduced to OH and then finally the reduction of N2 can take place. Here, the reaction free energy for production of gas phase hydrogen is ∆G[H* + (H+ + e−) → H2(g)] = 0.20 eV and for water formation is ∆G[OH + (H+ + e−) → H2O*] = 0.59 eV, while ∆G for all electrochemical reaction steps for ammonia production, see Figure 5, are zero or lower as in the previous example on the Mo13O9 nanocluster.
In the discussion of the preferential reactions on the Mo13O9 and Mo13O6 nanoclusters, all possible adsorbate–adsorbate interactions are not included due to the large computational cost associated with a comprehensive investigation. This is a potentially significant assumption, since the adsorption energies may decrease with higher coverage of certain species [27]. For hydrogen evolution on the Mo13O6 nanocluster, this could, e.g., have the consequence that the free energy barrier for producing gas phase hydrogen molecules is lowered.
The results for ammonia production on a partially oxidized molybdenum nanocluster indicates that the formation of ammonia on the molybdenum nanocluster is possible at a low onset potential, but with a low Faradaic efficiency due to the parasitic formation of both adsorbed H or OH on Mo13O9 and Mo13O6. Adsorption of nitrogen seems to hinder the further reduction of OH at lower oxygen coverages. This indicates that the nanocluster should be fully reduced, i.e., no oxygen present on the surface, before nitrogen is able to reach the catalyst surface. Small amounts of oxygen present at the molybdenum nanocluster surface, arising from either the electrolyte or from the preparation of the electrocatalyst, should therefore not affect the electrochemical production of ammonia.
Density functional theory calculations have been employed to investigate the adsorption and reduction of oxygen on molybdenum nanoclusters. The computational hydrogen electrode was used to determine potentials for reduction of nitrogen and oxygen and the hydrogen evolution reaction.
First, a partially nitrogen covered molybdenum nanocluster was exposed to gaseous water, showing preferential adsorption of oxygen atoms compared to both hydrogen atoms and nitrogen molecules at neutral bias (U = 0 V), while the adsorption energies are comparable at the potential needed to produce ammonia (U = −0.6 V). The consequence is that the presence of water will lead to preferential oxygen adsorption at the nitrogen vacancy sites unless a negative bias is applied. The reduction of the oxygen atoms at the nitrogen rich molybdenum nanocluster was studied, and potentials more negative than −1.25 V is required to reduce the oxygen atoms into water. The main challenge is the second protonation step, where the reaction step is very dependent on the local environment. The oxygen atom will bind to the vacancy site blocking the adsorption of nitrogen molecules and thereby greatly reduce the efficiency of the nitrogen rich molybdenum nanocluster as an electro catalyst for ammonia production through the associative mechanism. A direct reduction of the nitrogen skin will, however, still be possible at U = −0.6 V [2].
A clean molybdenum nanocluster in contact with oxygen, hydrogen and nitrogen will preferentially form an oxygen skin at neutral bias and nitrogen adsorption on an oxygen covered molybdenum nanocluster is found to be impossible. The reduction of an oxygen overlayer was therefore studied and it was found that the reduction requires potentials of −0.29 V to −0.72 V to successfully produce water from adsorbed oxygen atoms.
For oxygen coverages of nine or less oxygen atoms, adsorption of nitrogen and hydrogen becomes possible. The electrochemical production of ammonia for adsorbed nitrogen molecules at partial oxygen coverage will only require potentials of −0.45 V to −0.7 V to make the reaction exergonic. These onset potentials are similar to values reported in earlier studies of electrochemical ammonia production on molybdenum nanocluster with or without a nitrogen skin [2]. At the potentials needed to make the ammonia production exergonic, hydrogen is found to be present on the surface, and a reduction of oxygen to OH is observed, before electrochemical production of ammonia is possible.
On the basis of the work presented here, we propose that (partially) oxidized and nitrided molybdenum nanoclusters can be re-activated for ammonia production by electrochemical reduction of the adsorbed oxygen resulting from, e.g., the catalyst synthesis procedure or the presence of water in the electrolyte, at a potential of approximate −0.7 V. This makes molybdenum nanoclusters a highly promising catalyst for electrochemical ammonia production via the associative mechanism.
Supporting Information File 1: Additional Figures.
The authors would like to acknowledge the the Danish Center for Scientific Computing, the Catalysis for Sustainable Energy (CASE) initiative, the Center of Atomic-Scale Materials Design (CAMD) and the National Danish Advanced Technology Foundation. CASE is funded by the Danish Ministry of Science, Technology and Innovation, and CAMD is funded by the Lundbeck Foundation.
Howalt, J. G.; Bligaard, T.; Rossmeisl, J.; Vegge, T. Phys. Chem. Chem. Phys. 2013, 15, 7785–7795. doi:10.1039/c3cp44641g
Howalt, J. G.; Vegge, T. Phys. Chem. Chem. Phys. 2013, 15, 20957–20965. doi:10.1039/c3cp53160k
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2. Howalt, J. G.; Vegge, T. Phys. Chem. Chem. Phys. 2013, 15, 20957–20965. doi:10.1039/c3cp53160k
1. Howalt, J. G.; Bligaard, T.; Rossmeisl, J.; Vegge, T. Phys. Chem. Chem. Phys. 2013, 15, 7785–7795. doi:10.1039/c3cp44641g
9. Hammer, B.; Hansen, L. B.; Nørskov, J. K. Phys. Rev. B 1999, 59, 7413–7421. doi:10.1103/PhysRevB.59.7413
25. Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H. J. Phys. Chem. B 2004, 108, 17886–17892. doi:10.1021/jp047349j
7. Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864–B871. doi:10.1103/PhysRev.136.B864
8. Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133–A1138. doi:10.1103/PhysRev.140.A1133
5. Fastrup, B.; Nygård Nielsen, H. Catal. Lett. 1992, 14, 233–239. doi:10.1007/BF00765236
6. Kuchaev, V. L.; Shapatina, E. N.; Avetisov, A. K. Russ. J. Electrochem. 2009, 45, 983–995. doi:10.1134/S1023193509090031
19. Heyrovský, J. Recl. Trav. Chim. Pays-Bas 1927, 46, 582–585. doi:10.1002/recl.19270460805
3. Sone, Y.; Ekdunge, P.; Simonsson, D. J. Electrochem. Soc. 1996, 143, 1254–1259. doi:10.1149/1.1836625
4. Kreuer, K.-D.; Paddison, S.; Spohr, E.; Schuster, M. Chem. Rev. 2004, 104, 4637–4678. doi:10.1021/cr020715f
20. Rossmeisl, J.; Logadottir, A.; Nørskov, J. K. J. Chem. Phys. 2005, 319, 178–184. doi:10.1016/j.chemphys.2005.05.038
21. Rossmeisl, J.; Qu, Z.-W.; Kroes, G.-J.; Nørskov, J. K. J. Electroanal. Chem. 2007, 607, 83–89. doi:10.1016/j.jelechem.2006.11.008
22. Hummelshøj, J. S.; Blomquist, J.; Datta, S.; Vegge, T.; Rossmeisl, J.; Thygesen, K. S.; Luntz, A. C.; Jacobsen, K. W.; Nørskov, J. K. J. Chem. Phys. 2010, 132, 071101. doi:10.1063/1.3298994
23. Reuter, K.; Scheffler, M. Phys. Rev. B 2001, 65, 035406. doi:10.1103/PhysRevB.65.035406
24. Rossmeisl, J.; Nørskov, J. K.; Taylor, C. D.; Janik, M. J.; Neurock, M. J. Phys. Chem. B 2006, 110, 21833–21839. doi:10.1021/jp0631735
16. Skúlason, E.; Bligaard, T.; Gudmundsdóttir, S.; Studt, F.; Rossmeisl, J.; Abild-Pedersen, F.; Vegge, T.; Jónsson, H.; Nørskov, J. K. Phys. Chem. Chem. Phys. 2012, 14, 1235–1245. doi:10.1039/c1cp22271f
18. Bitzek, E.; Koskinen, P.; Gähler, F.; Moseler, M.; Gumbsch, P. Phys. Rev. Lett. 2006, 97, 170201. doi:10.1103/PhysRevLett.97.170201
15. Monkhorst, H.; Pack, J. D. Phys. Rev. B 1976, 13, 5188–5192. doi:10.1103/PhysRevB.13.5188
12. Mortensen, J. J.; Hansen, L. B.; Jacobsen, K. W. Phys. Rev. B 2005, 71, 035109. doi:10.1103/PhysRevB.71.035109
13. Enkovaara, J.; Rostgaard, C.; Mortensen, J. J.; Chen, J.; Dułak, M.; Ferrighi, L.; Gavnholt, J.; Glinsvad, C.; Haikola, V.; Hansen, H. A.; Kristoffersen, H. H.; Kuisma, M.; Larsen, A. H.; Lehtovaara, L.; Ljungberg, M.; Lopez-Acevedo, O.; Moses, P. G.; Ojanen, J.; Olsen, T.; Petzold, V.; Romero, N. A.; Stausholm-Møller, J.; Strange, M.; Tritsaris, G. A.; Vanin, M.; Walter, M.; Hammer, B.; Häkkinen, H.; Madsen, G. K. H.; Nieminen, R. M.; Nørskov, J. K.; Puska, M.; Rantala, T. T.; Schiøtz, J.; Thygesen, K. S.; Jacobsen, K. W. J. Phys.: Condens. Matter 2010, 22, 253202. doi:10.1088/0953-8984/22/25/253202
14. The GPAW code is available as a part of the CAMPOS software: http://wiki.fysik.dtu.dk/gpaw/
10. Blöchl, P. E. Phys. Rev. B 1994, 50, 17953–17979. doi:10.1103/PhysRevB.50.17953
11. Blöchl, P. E.; Först, C. J.; Schimpl, J. Bull. Mater. Sci. 2003, 26, 33–41. doi:10.1007/BF02712785
17. The ASE code is available as a part of the CAMPOS software: http://wiki.fysik.dtu.dk/ase/
26. Abild-Petersen, F.; Greeley, J.; Studt, F.; Rossmeisl, J.; Munter, T. R.; Moses, P. G.; Skúlason, E.; Bligaard, T.; Nørskov, J. K. Phys. Rev. Lett. 2007, 99, 016105. doi:10.1103/PhysRevLett.99.016105
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© 2014 Howalt and Vegge; licensee Beilstein-Institut.
Howalt, J. G.; Vegge, T. Beilstein J. Nanotechnol. 2014, 5, 111–120. doi:10.3762/bjnano.5.11


New Delhi: BSF Director General Rajni Kant Mishra on Friday said the Kartarpur road corridor between India and Pakistan will not be a security challenge for the force as it has already been handling Wagah-Attari International Border (IB) that witnesses cross over of lots of people.
"As a border guarding force, we will handle the responsibilities we are given. Opening of Kartarpur corridor is not a challenge… This is not a difficult thing as we handle a large number of people who keep coming and going from Wagah-Attari border," he told the media during an annual conference of the Border Security Force (BSF).
The DG's assertion came in a reply to a question if the force would face a security challenge after the building of the corridor from Dera Baba Nanak in Punjab's Gurdaspur district to the IB to facilitate Indian pilgrims to visit Gurdwara Darbar Sahib in Kartarpur in Pakistan.
The foundation stones for developing the four-kilometre corridor on either side of the border were laid by India and Pakistan earlier this week.
Mishra said his force had given befitting reply to Pakistan after the killing of BSF head constable Narender Kumar in a Border Action Team (BAT) attack on a patrol party in September and that strategy will be adopted for all such attacks in the future.
Over the functioning of pilot projects of Comprehensive Integrated Border Management System (CIBMS) in Jammu along the IB between India and Pakistan to track infiltration, Mishra said the BSF is satisfied with the results since its installation.
The DG said the BSF is also constructing some unique bunkers with in-house mechanism so that the personnel can physically keep an eye on the border, respond as per the need and keep them protected at the same time.
About the viral video released last year by BSF trooper Tej Bahadur Yadav complaining about the quality of food being served to soldiers, the DG said his force does not supply food to the place related to the incident.
On the illegal Rohingya migration issue, Mishra said they are not a big issue for the force and that in course of monitoring, the BSF has intercepted 54 incoming and 176 outgoing movements of the community in one year.


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Спурій Фурій Медуллін () — преномен, номен і когномен діячів Стародавнього Риму, часів Римської республіки з патриціанського роду Фуріїв, його гілки Медуллінів:
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 Спурій Фурій Медуллін Фуз — консул 464 року до н. е.
 Спурій Фурій Медуллін — військовий трибун з консульською владою 400 року до н. е.
 Спурій Фурій Медуллін — військовий трибун з консульською владою 378 року до н. е.

Див. також
 Фурії


text:
Hire your car
DIRECT RENTAL, NOT A BROKER!
Malaga airport history
The history from Malaga airport dates back to 1919, during this year a strong rain caused the plane piloted by Pierre George Latécoère to search for an alternative landing piste as the area where he planned to land near the Misericordia beach was flooded, he finally landed on the area where the airport is situated actually.
Pierre George Latécoère was a pilot and a co-owner from an airline, he was trying to link France with its colonies in North Africa through Spain and finally linked Tangier and Casablanca with Toulouse through Malaga, Alicante and Barcelona airports.
Malaga airport was initially a small dirt track of about 500 meters lenght on a rented land, the waiting room was a small cottage situated nearby as by that time the flights demand was still low.
In 1932 the airport was acquired by the government and in 1937 during the Civil War in Spain it became an airbase where planes from both sides actively participated in the battle skirmishes. Shortly after the conflict it would become an international civil airport.
From 1939 in advance the airport continued expanding and actually it already has two runways.
Airport development
Growth of flights also brought a growth in development with a new terminal called Pablo Ruiz Picasso inaugurated in 1968, a parking area inaugurated in 1995, a hangar and a cargo terminal.
Today Malaga airport is among the first airports in Spain in importance and it receives the most flights in Andalusia.
Recent reforms have provided better access to the airport by road and train, the Terminal T3 built in 2010 and a new parking building.
Malaga airport guide
Malaga airport map
Arrivals guide
General aviation terminal
Aeronautical Museum
Airlines baggage guide
Car hire reviews
Malaga airport taxi
Departures guide
Buses from the airport
Malaga airport train station
Customs restrictions


Ansell Court is a fantastic new Extra Care scheme, developed by Barnet Homes on behalf of Barnet Council.
Ansell Court provides tenants with the very best in independent living and the peace of mind that onsite care and support is available, day and night.
The scheme which is wheelchair accessible, consists of 50 one bedroom and 3 two-bedroom apartments. All the apartments are spacious and include a fitted kitchen, lounge and walk-in shower room.
PA Choices matches people who are in receipt of direct payments with personal assistants who are able to support them on a day to day basis.


text:
Michelle Obama Is Not Running for President
The former first lady put to rest a rumored White House bid and discussed diversity in higher education at the Simmons Leadership Conference in Boston.
By Hayley Glatter·	 4/6/2018, 8:59 a.m.
Photo via AP/Pablo Martinez Monsivais
It's simple, really: Michelle Obama does not want to be president, and so she is not running for president.
During a moderated conversation at Simmons College's 39th annual leadership conference on Thursday, the former first lady discussed a litany of topics ranging from diversity to the state of American democracy—and put to rest any notion that her name will be on the ballot in 2020.
"I have never had the passion for politics," Obama said. "I just happened to be married to somebody who has the passion for politics, and he drug me kicking and screaming into this arena. Just because I gave a good speech, and I'm smart and intelligent, doesn't mean that I should be the next president."
Obama emphasized the need to encourage qualified women with political drive to pursue higher office, rather than homing in on inspiring people like herself and Oprah who may have other aspirations.
The former first lady also discussed equity in higher education during the Q&A, which was moderated by Simmons president Helen Drinan. Obama, who graduated from Princeton University and Harvard Law School, said she sometimes "felt like an affirmative action kid," on campus. She noted that the term "affirmative action" has been twisted to take on negative connotations in some circles despite the broader ubiquity of the practice.
"When affirmative action means color, it's deemed to be problematic," Obama said. "I have a problem with that, because affirmative action exists everywhere throughout society. It's called privilege."
Obama, whose forthcoming memoir Becoming will be released in November, also emphasized the need to view diversity at the university level in a more holistic way. Simply admitting a few students of color and calling it a day isn't enough.
"The few sprinkles are going to get lost, because it's hard being the only one when you're sitting in a majority class and you're the only one fighting for your perspective," Obama said. "Universities have a responsibility to create a diverse life. They understand that a healthy, thriving community looks like everything—not just great grades and perfect SAT scores."
This year's conference, which carried the theme "Disrupt the Ordinary," also featured Gretchen Carlson. Previous Simmons Leadership Conference speakers include Madeleine Albright, Hillary Clinton, Toni Morrison, and Oprah Winfrey.
Go for the Goals
The Power of Giving Back


Abraham's first son, Ishmael, is important in the religion of Islam. The Qur'an says that he was a prophet and an apostle (see Qur'an Sura 19:54). Arabic Muslims trace a lot of their lineage back to Ishmael. When we go back to Genesis and the conversation that the Angel of the Lord had with Hagar, Ishmael's mother, we see an important word for Muslims. The Angel told her, "Return to your mistress, and submit yourself under her hand" (Genesis 16:9). The key word is "submit." The word Muslim means "one who submits," and Muslims believe that Abraham coined the term. According to Islamic tradition, Abraham and Ishmael traveled to Mecca and there they built the Kaaba. The Kaaba is the holy shrine in Mecca where every Muslim is supposed to make a pilgrimage at least once during their lifetime. They believe that Abraham and Ishmael are buried in Mecca, even though the Bible says Abraham is buried in Hebron, in the cave of Machpelah in Israel.
Here is an interesting note: The sacred shrine, the Kaaba, was once a shrine that housed 360 different idols, representing 360 gods worshiped by the various Arab tribes in the region. Allah was one of those gods, a moon god, until Muhammad claimed that Allah was the one true god. In his fervor to unify all of the tribes, he squelched the worship of all other gods, killed anyone who did not submit to his perspective, and established Islam. Fascinating, isn't it, that what today is called one of the three great monotheistic religions actually began as a polytheistic religion?
This is also interesting prophetically because Muhammad himself is called the prophet of the sword and traced his lineage back to Ishmael, of whom it was foretold, "His hand shall be against every man, and every man's hand against him" (Genesis 16:12). This is especially interesting, considering that Islam itself divides the entire world into two and only two camps. The first camp is the house of Islam, the house of those who submit. The other one, if you're not Muslim, is the house of war. You're either Muslim and of the house of Islam, or you're of the house of war. The Qur'an has 109 verses called war verses. One out of every fifty-five verses in the Qur'an is about making war or feuding against others—either in an inclusive statement or a call to arms. In light of Ishmael's origins and the prediction made about him and those who would follow him, it's helpful to understand Islamic history, traditions, and views.
Skip Heitzig, author of The Bible from 30,000 Feet, is pastor-teacher of Calvary Church, ministering to more than 15,000 people weekly. He holds a DD and PhD from Trinity Southwest University and has a popular multimedia teaching ministry that includes print, audio, and online resources. Skip and his wife, Lenya, reside in New Mexico and have one son and two grandchildren.


The Damien High School football team won its first game in nearly two years yesterday, rolling past Kaimuki, 42-15, in the opening game of the 39th Annual Father Bray Classic at Aloha Stadium.
Damien running back Ranson DeCosta eluded the Kaimukii defense and found some running room during yesterday's game.
The Monarchs' previous victory — 11 games ago — was a 7-6 win over Pac-Five on Oct. 21, 2000.
Damien's Ranson DeCosta scored touchdowns on a 10-yard run and 93-yard kickoff return, and teammate Andrew Canoy found the end zone on a 79-yard run and 82-yard kickoff return. The Monarchs also scored on Daniel Chaves' 36-yard interception return for a touchdown.
"We had a bunch of big plays, and everybody fulfilled their role nicely," said Damien co-coach Dean Nakagawa. "Our special teams were special; actually all of our teams put it together. That's what we're trying to develop here — a team concept. We want everybody to believe in themselves."
Nakagawa, a former Iolani standout and University of Hawai'i cornerback, was the Monarchs' defensive coordinator last year. He and co-coach Rudy Alejo took over the program after former head coach Chris Bisho resigned earlier this summer.
Damien lost only 11 players to graduation, and even this year's team has only nine seniors.
"We're still very young," Alejo said. "But the veterans have responded well and the rookies have carried their load. Even the coaches all pulled together. We've been behind the rest of the league for awhile, but we feel the kids are focusing on what's at hand and not on the past."
DeCosta's touchdown run and Chaves' interception gave the Monarchs a 14-0 first-quarter lead, but Kaimuki's Sheldon Sarcedo cut it to 14-6 with his 67-yard touchdown run. The extra point attempt was blocked.
Canoy's touchdown run helped give Damien a 21-6 lead in the second quarter. Kaimuki's Ji Min Kim connected on a 31-yard field goal to make it 21-9, but Canoy returned the ensuing kickoff for a touchdown to help give the Monarchs a 28-9 halftime advantage.
In the third quarter, Sarcedo returned a fumble 63 yards for a touchdown to make it 28-15, but DeCosta answered with a 93-yard kickoff return to help put Damien up 35-15.
In addition to his two touchdowns, DeCosta also converted five extra points, played safety and punted. He played quarterback as a sophomore on last year's team.
"We're going to use his athletic ability as much as we can," Alejo said.
Nakagawa and Alejo said the Monarchs also received strong performances from quarterback Tevita Williams, defensive lineman Soane Sevelo, offensive lineman Chris Meheula, center Garyk Ontai and linebacker Brennan Delacruz.
Quarterback Royce Machado passed for two touchdowns, and Matt Bell and Samson Milo each scored on touchdown runs as the Governors scored 28 unanswered points against the Wolfpack.
Pac-Five took a 7-0 second-quarter lead after McShane Dator's 19-yard touchdown pass to Travis Tyler. Alwin Faumui caught a 15-yard touchdown pass from Machado to make it 7-6 just before halftime. The extra point attempt failed.
Bell's third-quarter touchdown run from three yards out helped Farrington take a 13-7 lead, and Dionte Noma'aea caught a 26-yard touchdown pass from Machado to help the Govs go up, 21-7, with 9:12 remaining in the game. Milo's 2-yard touchdown run sealed it later in the fourth quarter.
The game marked the coaching debut of Farrington's Randall Okimoto, a former standout for the Governors and letterman at UH.
Raynold Stowers rushed for 184 yards and three touchdowns on 13 carries, and Kelly Teramoto ran for 129 yards and three touchdowns on 17 carries to lead the Raiders past the Rams.
Stowers and Teramoto, both juniors, combined for five first-half touchdowns as Iolani led 27-0 after one quarter and 34-0 at intermission. Stowers scored on runs of 2, 35 and 66 yards and Teramoto scored on runs of 4, 1 and 40 yards.
The Raiders' defense, led by linebacker Kala Ka'aihue, limited Radford to 69 total yards in the first half. Rams quarterback Stephen Bauglin finished with 11 completions in 20 attempts for 150 yards and one touchdown.


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text:
28th May 2021 21:03:46 Hours
GENERAL SHAVENDRA SILVA, GUEST OF HONOUR IN PAKISTAN NATIONAL DAY CELEBRATIONS
The annual national Pakistan Day (23 March) Military Parade also known as the National Day Joint Services Parade that commemorates the resolution for creation of Pakistan honoured Sri Lanka 's Chief of Defence Staff and Commander of the Army, General Shavendra Silva inviting him to be the Guest of Honour at the spectacular commemorative celebration, graced by the President of Pakistan, Chairman of Joint Chiefs of Staff Committee, Chief of Army Staff, Chief of Navy Staff, Chief of Air Force Staff and a host of other foreign and local dignitaries in Islamabad.
A colourful and spectacular parade showcasing military prowess of the Pakistan Army, its short and long range missiles, tanks, jets, drones and other hardware, accompanied by simultaneous demonstrations of aerial manoeuvres and excellent aerobatics for audiences featured distinctively in the day 's spectacle.
A team of Sri Lanka Army 's Special Force (SF) parachutists alongside Pakistan 's armed forces, attaching greater importance to the day 's event in Pakistan, displayed their skills falling from a height of about 12,000 feet amid roars of applause as the main features of the celebration got underway. On practical grounds, this year 's celebrations were held on 25 March in the presence of a huge gathering of participants.
Next to Pakistan 's regular Army, Navy and Air Force units with paramilitary forces filed past the Chief Guest, President Dr Arif Alvi, Guest of Honour, General Shavendra Silva, Pakistan 's Army Chief and other dignitaries, attired in colourful regalia as the climax of the day 's event.
During the same ceremony, the President of Pakistan conferred national awards and Presidency medals. Before the day 's proceedings, wreaths were also laid at the mausoleums in Lahore and Karachi to recall the memories of Pakistan 's founding fathers.
Mrs Sujeewa Nelson, President, Army Seva Vanitha Unit, Major General Sanjeewa Wanasinghe, Adjutant General and a few senior officers of the Sri Lanka Army were in the Commander 's retinue.
Pakistan Day is observed as a public holiday in all over the country where the early morning military and civilian parades with gun salutes are held while all state and private sector buildings remain decorated with national flags and colourful bunting.


text:
SearchSubmit ContentClass NotesArchives
Francisco Moreno
An artist whose work bridges then and now
Courtesy of the artist and Erin Cluley Gallery, Dallas. Photos by Kevin Todora.
Journeys are important to Francisco Moreno ('10 BFA, Painting). Whether it's a journey from place to place or past to present, he is interested in creating art that explores those transitions—and how they can come to define who we are. "As a Mexican-born American citizen, I pull from an archive that references ideas that traverse borders, an abstract allegory for my identity," he says. With Chapel, which debuted at the Erin Cluley Gallery in Dallas, Moreno created an entire structure that brings these ideas together.
Moreno's Chapel was specifically inspired by a visit to the 12th-century mural paintings of the Hermitage of the Vera Cruz de Maderuelo. In 1947, the mural fresco paintings were transferred from their original location in the municipality of Maderuelo to canvas and reconstructed at the Prado Museum in Madrid.
"As a Mexican-born American citizen, I pull from an archive that references ideas that traverse borders, an abstract allegory for my identity."
"The experience of the thoughtfully handpainted beauty was overwhelming," he says. "The fact that the murals are displaced from their original location felt peculiarly familiar, as I have been perplexed by notions of identity since my family left Mexico City in order to relocate to Arlington."
For Chapel, Moreno designed, constructed, and painted the interior of an all-encompassing 16-by-12-by-13-foot barrel-vaulted structure, which was inspired by Spanish Romanesque chapels. His focus was engaging the past while making a new mark, so the interior is filled not with religious iconography, but layered sketches that he described to The Dallas Morning News as a "giant drawing, a stream-of-consciousness collage."
The artist's journey
For Moreno, becoming an artist was also a journey largely shaped by his travels. As an undergraduate student in architecture at another Texas university, he was looking for a career path he could be passionate about. But architecture didn't fit. He took an industrial design course at the Tec de Monterrey campus in Queretaro, Mexico, but that wasn't quite right, either. He eventually transferred to UTA, where he took an intermediate painting class—and he never looked back.
"The faculty at UTA were very generous with their time, and the art studios are fantastic," he says. "I'm glad I was able to find my way at UTA. It showed me I could really pursue the arts."
Looking to the future, Moreno is willing to go wherever his creative pursuits may lead.
"Right now, I'm just painting and drawing, thinking of new, crazy ideas," he says. "Creativity is like anything else—you just have to put in the work."
Take a look at Moreno's latest work on his Instagram account, @morencisco.
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text:
package irc

import (
	"errors"
	"net"

	"github.com/ergochat/ergo/irc/flatip"
	"github.com/ergochat/ergo/irc/modes"
	"github.com/ergochat/ergo/irc/utils"
)

var (
	errBadGatewayAddress = errors.New("PROXY/WEBIRC commands are not accepted from this IP address")
	errBadProxyLine      = errors.New("Invalid PROXY/WEBIRC command")
)

const (
	// https://www.haproxy.org/download/1.8/doc/proxy-protocol.txt
	// "a 108-byte buffer is always enough to store all the line and a trailing zero
	// for string processing."
	maxProxyLineLen = 107
)

type webircConfig struct {
	PasswordString string  `yaml:"password"`
	Password       []byte  `yaml:"password-bytes"`
	Fingerprint    *string // legacy name for certfp, #1050
	Certfp         string
	Hosts          []string
	allowedNets    []net.IPNet
}

// Populate fills out our password or fingerprint.
func (wc *webircConfig) Populate() (err error) {
	if wc.PasswordString != "" {
		wc.Password, err = decodeLegacyPasswordHash(wc.PasswordString)
		if err != nil {
			return
		}
	}

	certfp := wc.Certfp
	if certfp == "" && wc.Fingerprint != nil {
		certfp = *wc.Fingerprint
	}
	if certfp != "" {
		wc.Certfp, err = utils.NormalizeCertfp(certfp)
	}
	if err != nil {
		return
	}

	if wc.Certfp == "" && wc.PasswordString == "" {
		return errors.New("webirc block has no certfp or password specified")
	}

	wc.allowedNets, err = utils.ParseNetList(wc.Hosts)
	return err
}

// ApplyProxiedIP applies the given IP to the client.
func (client *Client) ApplyProxiedIP(session *Session, proxiedIP net.IP, tls bool) (err error, quitMsg string) {
	// PROXY and WEBIRC are never accepted from a Tor listener, even if the address itself
	// is whitelisted. Furthermore, don't accept PROXY or WEBIRC if we already accepted
	// a proxied IP from any source (PROXY, WEBIRC, or X-Forwarded-For):
	if session.isTor || session.proxiedIP != nil {
		return errBadProxyLine, ""
	}

	// ensure IP is sane
	if proxiedIP == nil {
		return errBadProxyLine, "proxied IP is not valid"
	}
	proxiedIP = proxiedIP.To16()

	isBanned, requireSASL, banMsg := client.server.checkBans(client.server.Config(), proxiedIP, true)
	if isBanned {
		return errBanned, banMsg
	}
	client.requireSASL = requireSASL
	if requireSASL {
		client.requireSASLMessage = banMsg
	}
	// successfully added a limiter entry for the proxied IP;
	// remove the entry for the real IP if applicable (#197)
	client.server.connectionLimiter.RemoveClient(flatip.FromNetIP(session.realIP))

	// given IP is sane! override the client's current IP
	client.server.logger.Info("connect-ip", "Accepted proxy IP for client", proxiedIP.String())

	client.stateMutex.Lock()
	defer client.stateMutex.Unlock()
	client.proxiedIP = proxiedIP
	session.proxiedIP = proxiedIP
	// nickmask will be updated when the client completes registration
	// set tls info
	session.certfp = ""
	session.peerCerts = nil
	client.SetMode(modes.TLS, tls)

	return nil, ""
}

// handle the PROXY command: http://www.haproxy.org/download/1.8/doc/proxy-protocol.txt
// PROXY must be sent as the first message in the session and has the syntax:
// PROXY TCP[46] SOURCEIP DESTIP SOURCEPORT DESTPORT\r\n
// unfortunately, an ipv6 SOURCEIP can start with a double colon; in this case,
// the message is invalid IRC and can't be parsed normally, hence the special handling.
func handleProxyCommand(server *Server, client *Client, session *Session, line string) (err error) {
	var quitMsg string
	defer func() {
		if err != nil {
			if quitMsg == "" {
				quitMsg = client.t("Bad or unauthorized PROXY command")
			}
			client.Quit(quitMsg, session)
		}
	}()

	ip, err := utils.ParseProxyLineV1(line)
	if err != nil {
		return err
	} else if ip == nil {
		return nil
	}

	if utils.IPInNets(client.realIP, server.Config().Server.proxyAllowedFromNets) {
		// assume PROXY connections are always secure
		err, quitMsg = client.ApplyProxiedIP(session, ip, true)
		return
	} else {
		// real source IP is not authorized to issue PROXY:
		return errBadGatewayAddress
	}
}

redpajama_set_name: RedPajamaGithub


text:
Hoya sp. aff. burtoniae
Hoya species affinis burtoniae (meaning it's potentially a new, yet-to-be-described species that is very similar, but not identical, to a named species) is sometimes sold under the name Hoya DS-70 which is the accession number given by David Silver to the plant in his collection.
Hoya burtoniae is part of the Apocynaceae family and its native range is Philippines (Luzon). Leaves are ovate and covered with a velvety pubescence. Variegation on this plant ranges from a creamy yellow to pink.
Genus name is new Latin, named after Thomas Hoy ( c. 1750– c. 1821), English gardener.
Light: Bright indirect light, meaning the plant sees the sun for 0-4 hours per day - this could be through trees or a translucent curtain, it's important for the plant to see the sky in order to thrive.
Water: Given adequate light, keep the potting mix evenly moist, the potting mix is traditionally quite chunky, water will usually flow through quite easily. Pour water slowly over the top of the substrate and allow the water to pass through the drainage holes.
Potting mix: A chunky well-draining mix composed of coco coir, perlite or vermiculite, orchid bark, worm castings and some horticultural charcoal.
Temperature: 15-35˚C.
Maranta leuconeura var erythroneura 'Lemon Lime'
Scindapsus treubii 'Moonlight'


text:
Q: ORA-01843: not a valid month error when inserting input from html to oracle database I am having trouble trying to insert a timestamp input into my Oracle SQL Developer database. I have a table named userappt and the column called appt_date is a timestamp value. Then, I have a stored procedure called insertapptpro that will be called in my php file named insertappt.php as the action for a html form file named userappt.html. I tried inserting a new appointment but the error Warning: oci_execute(): ORA-01843: not a valid month ORA-06512 appears and returns nothing to my database.
Here is my table and stored procedure code:
create table appt
(
appt_id varchar(15) primary key,
pet_name varchar(100),
purpose varchar(50),
appt_date timestamp
);

create or replace procedure insertapptPro(
p_name appt.pet_name%type, p_purpose appt.purpose%type, p_date appt.appt_date%type)
is
begin
insert into appt(pet_name, purpose, appt_date)
values (p_name, p_purpose, p_date);
end;
/

declare
a varchar(100);
b varchar(50);
c timestamp;
begin
a := 'Jack Jack';
b := 'Rear bleeding';
c := '15-Dec-2019 09:00';
insertapptpro(a,b,c);
end;
/

And this is my php code for the file insertappt.php:
$name = $_POST['PET_NAME'];
$purp = $_POST['PURPOSE'];
$date = $_POST['APPT_DATE'];

    $query1 = 'BEGIN INSERTAPPTPRO(:PET_NAME, :PURPOSE, :APPT_DATE);END;';
    $result = oci_parse($connection, $query1);

    oci_bind_by_name($result, ':PET_NAME', $name);
    oci_bind_by_name($result, ':PURPOSE', $purp);
    oci_bind_by_name($result, ':APPT_DATE', $date);

    oci_execute($result);

    if (oci_fetch($result)==0)
    {
        echo "<script type=\"text/javascript\">window.alert('Booked Successfully!')";window.location.href='/system/userappt.php';</script>";
    }

    else
    {
        echo "<script type=\"text/javascript\">window.alert('Register Failed');</script>";
    }
?>

And lastly, my html form code for the file userappt.html:
<form class="" action="insertappt.php" method="post">
          <p>
        Pet Name: <input type="text" name="PET_NAME" placeholder="Patient Name" class="inputtxt" required>
        Purpose: <input type="text" name="PURPOSE" placeholder="Purpose" class="inputtxt" required>
        Appointment date and time: <input type="datetime-local"  name="APPT_DATE" placeholder="Appointment date and time" class="inputtxt" required>
        <input type="submit" value="Book" class="subbtn">
        </form>

I'm fairly new to using datetime-local in html and timestamp in oracle, so I hope I'll learn something from you guys.

redpajama_set_name: RedPajamaStackExchange