Synergistic effects of the hybridization between boron-doped carbon quantum dots and n/n-type g-C3N4 homojunction for boosted visible-light photocatalytic activity

Dye wastewater has raised a prevalent environmental concern due to its ability to prevent the penetration of sunlight through water, thereby causing a disruption to the aquatic ecosystem. Carbon quantum dots (CQDs) are particularly sought after for their highly tailorable photoelectrochemical and optical properties. Simultaneously, graphitic carbon nitride (g-C3N4) has gained widespread attention due to its suitable band gap energy as well as excellent chemical and thermal stabilities. Herein, a novel boron-doped CQD (BCQD)-hybridized g-C3N4 homojunction (CN) nanocomposite was fabricated via a facile hydrothermal route. The optimal photocatalyst sample, 1-BCQD/CN (with a 1:3 mass ratio of boron to CQD) accomplished a Rhodamine B (RhB, 10 mg/L) degradation efficiency of 96.8% within 4 h under an 18 W LED light irradiation. The kinetic rate constant of 1.39 × 10–2 min−1 achieved by the optimum sample was found to be 3.6- and 2.8-folds higher than that of pristine CN and un-doped CQD/CN, respectively. The surface morphology, crystalline structure, chemical composition and optical properties of photocatalyst samples were characterized via TEM, FESEM-EDX, XRD, FTIR, UV–Vis DRS and FL spectrometer. Based on the scavenging tests, it was revealed that the photogenerated holes (h+), superoxide anions (∙O2–) and hydroxyl radicals (∙OH) were the primary reactive species responsible for the photodegradation process. Overall, the highly efficient 1-BCQD/CN composite with excellent photocatalytic activity could provide a cost-effective and robust means to address the increasing concerns over global environmental pollution.


Introduction
In the recent years, the dramatic growth in global population calls for immediate measures to protect the environment and natural resources. While the rapid industrialization has indeed promoted the blooming of various sectors including food and beverage, paper and textile, irrigation and drainage, medical and pharmaceutical, etc., these industries are accountable for several major environmental issues. In this regard, the discharge of effluents by these production and manufacturing plants is detrimental to Mother Nature, resulting in the pollution of water resources and diminished water quality. Notably, the level of dissolved contaminants in the vast majority of water bodies is above the acceptable standard for human consumption, leading to the scarcity of clean water in many communities around the world. Based on data from the World Health Organization, an annual estimation of 485,000 diarrheal deaths occurs due to the consumption of contaminated drinking water while waterborne diseases such as cholera, polio and typhoid remain as serious threats to the public health (Organization 2019). Specifically for wastewater containing azo dyes, it induces mutagenic and carcinogenic effects with the presence of complex aromatic compounds (da Silva et al. 2014). The high color intensity displayed by organic dyes also jeopardizes the aquatic ecology as it impedes the sunlight from entering Responsible Editor: Sami Rtimi. the water, resulting in reduced photosynthesis and consequently eutrophication. Therefore, an effective, sustainable and environmentally-benign method to treat dye-containing wastewater is of utmost importance.
Photocatalysis has garnered widespread attention among researchers as this cutting-edge technology is highly green and sustainable. The advanced oxidation processes (AOPs) offered by heterogeneous photocatalysis is especially promising because of its ability to oxidize a wide spectrum of complex organic compounds, attributing to highly reactive oxidants as well as reactive species with relatively low selectivity such as the hydroxyl radicals Muraro et al. 2020). Photocatalyst is broadly recognized for its robustness and versatile applicability across different fields including mineralization of organic pollutants, CO 2 reduction, hydrogen generation via water splitting and others (Moreno et al. 2021;Zhen et al. 2021). While water treatment by means of photo-driven reactions is undoubtedly environmentally friendly, the performances of the existing photocatalytic systems are greatly hampered by several setbacks. Among the prominent issues include the ineffective utilization of solar energy and the rapid recombination rate of electron-holes pairs (Weon et al. 2019;Jiao et al. 2020). As visible light makes up an approximately 42% of the solar energy, the design of a visible-light-responsive photocatalyst is greatly desired due to its relatively high photonic energy (Wang et al. 2017c). Hitherto, most of the existing photocatalytic systems are only active under high energy ultraviolet (UV) light which constitutes merely 6% of the entire solar spectrum . A number of strategies such as functionalization, elemental doping and size tuning have been proposed to boost the apparent quantum efficiency of the existing photocatalysts and concurrently diminish the aforementioned limitations (Nassar and Abdelrahman 2017;Ma et al. 2018;Li et al. 2020b). A plethora of nanomaterials have also been identified as promising photocatalytic materials. These include metallic titanium oxide (TiO 2 ), tungsten oxide (WO 3 ), MXenes as well as non-metallic CQDs, graphitic carbon nitride (g-C 3 N 4 ), phosphorus (P), graphene and combinations hereof (Cushing et al. 2017;Cao et al. 2018;Jeevitha et al. 2018;Hu et al. 2019;Kooshki et al. 2019;Mishra et al. 2019).
Ascribing to its suitable electronic band structure, facile synthesis and readily tunable features, two-dimensional (2D) g-C 3 N 4 has thrust into the limelight within the field of photocatalysis (Che et al. 2019). As compared to its metal-based counterparts, the metal-free g-C 3 N 4 has also alleviated the risk of metal-leaching, which is known to be a process where toxic metal components dissolve into liquid medium, inflicting detrimental damage to the environment (Zhang et al. 2016b;Sahu et al. 2020). The vast untapped potential of g-C 3 N 4 has prompted much research interests in studying its structural framework, optoelectronic and physicochemical properties. Among the more effective strategies in enhancing the photocatalytic performance of g-C 3 N 4 is through the formation of a homojunction system, where the difference in conduction band (CB) and valence band (VB) levels between precursors could facilitate the separation of photoinduced charge carriers (Phang et al. 2020b). Several research articles on g-C 3 N 4 homojunction with enhanced photocatalytic performance have been published in the literature (Ye et al. 2017;Phang et al. 2020a). For instance, Tan et al. successfully fabricated a mesoporous g-C 3 N 4 nanosheet-laminated homojunction, which displayed a 12.5-and 6.5-fold improvement in performance as compared to pristine g-C 3 N 4 derived from melamine and amino cyanamide, respectively . Similarly, Yang's group constructed a triazine-/heptazine-based g-C 3 N 4 homojunction via the overgrowth of triazine-based g-C 3 N 4 nanoparticles embedded on the inner wall of the heptazine-based g-C 3 N 4 hollow tubes (Yang et al. 2020a). The efficiency for photocatalytic H 2 generation was drastically improved, with a H 2 evolution rate 12-times higher in relative to bulk g-C 3 N 4 . On the whole, the ameliorated photoactivities in different applications are primarily credited to the enhanced photo-response toward visible light, rapid charge transfer and separation in addition to excellent photo-stability upon the formation of homojunction structures.
To further improve the photoactivity of g-C 3 N 4 , the doping of a co-catalyst onto the fundamental framework is regarded as one of the most effective strategies (Ran et al. 2015;Chen et al. 2017;Hasija et al. 2019). Carbon quantum dots (CQDs) are widely known as a novel class of nanomaterials with ultrafine dimensions of less than 10 nm (Phang and Tan 2019). CQDs have become the focus of attention among material scientists and researchers in the recent years owing to their prominent optical and physicochemical properties. Furthermore, CQDs are also highly sought after for its up-converted photoluminescence (UCPL) properties, extended range of sensitivity toward visible light as well as its inexpensive synthesis cost (Wang et al. 2019a;Molaei 2020). The readily tunable features of CQDs, chemically and physically, render their robustness and allow them to be tailored precisely for a variety of applications. Recently, there has been a surge in publications on the modification strategies of CQDs to further enhance their photocatalytic effectiveness. These strategies include size tuning for quantum confinement effect (Li and Zhao 2014), surface passivation and functionalization (Luo et al. 2013;Lim et al. 2015;Yang et al. 2016;Pan et al. 2017), heteroatom doping and the formation of hybridized nanocomposites Zhang et al. 2017a). Among the common doping elements for CQDs are nitrogen (N), boron (B), sulfur (S) and phosphorus (P), which are typically derived from urea, boric acid, ʟ-cysteine and phosphoric acid, respectively (Bhati et al. 2019;Lin et al. 2019;Wang et al. 2019b;Zhang et al. 2020b). Each element has its distinctive advantages over the other elements in improving the photoactivity of CQDs. For instance, N-doped CQDs were reported to increase the aqueous dispersibility and fluorescence emission of the composite while B-doped CQDs displayed enhanced visible light absorption and quantum yield (Ma et al. 2012;Guo et al. 2018;Song et al. 2020). On the other hand, doping of heteroatom S was shown to improve the electrical conductivity of CQDs whereas the introduction of P dopants accelerated the electron transfer to impede charge carrier recombination (Wang et al. 2019b;Zhang et al. 2020c). Collectively, it is apparent that the doping of CQDs with different heteroatoms is promising to drastically enhance various extrinsic properties and structural features advantageous for photocatalysis. For instance, Peng et al. successfully fabricated the B-doped carbon dots via a simple hydrothermal route. Based on the photoactivity test over RhB and methylene blue (MB) degradation, the synthesized B-doped carbon dots demonstrated an outstanding performance in which a 100% degradation of both dyes were attained within a short span of 170 min (Peng et al. 2020).
In this work, we report the smart engineering of zerodimensional (0D) B-doped CQD (BCQD) on 2D g-C 3 N 4 /g-C 3 N 4 homojunction (CN) to form a highly robust hybrid BCQD/CN. To the best of our knowledge, the fabrication of this novel and efficient nanocomposite system for RhB degradation has not been reported in the literature thus far. Herein, BCQDs were doped onto CN via a facile hydrothermal method. The CQDs were derived from citric acid with boric acid as the B-dopant, while g-C 3 N 4 homojunctions were fabricated with urea and thiourea as the precursors. The mass loadings of boric acid were varied to determine the optimum amount of B-dopant over the n/n-junctioned g-C 3 N 4 . The photocatalytic efficiency of the as-developed photocatalyst samples was evaluated via the degradation of RhB dye. It is noteworthy that the present work employs the use of a low-powered 18 W LED light as the irradiation source, rendering the overall photocatalytic process both environmentally benign and economically feasible. All in all, this study aims to provoke novel research ideas in the field of photocatalysis with the development of BCQDs incorporated g-C 3 N 4 /g-C 3 N 4 homojunction nanocomposites.

Synthesis of BCQD
Three (3) grams of citric acid and x-amount of boric acid were mixed in 15 ml of distilled water followed by mild stirring for 10 min. The symbol 'x' denotes the amount of boron-dopant employed (0.5, 1, 2 and 3 g) in the synthesis of BCQDs with respect to a fixed amount of CQDs. The homogeneous mixture was then transferred into a Teflonlined autoclave reactor for hydrothermal treatment at 180 °C for 14 h, after which the solution was cooled naturally to ambient temperature. Subsequently, the resultant brown suspension was subjected to centrifugation at 12,000 rpm for 20 min to remove larger particles and impurities. The supernatant containing purified BCQD was obtained and dried in an oven at 90 °C overnight before further use. The prepared samples with 0.5, 1, 2 and 3 g of boric acid were denoted as 0.5-BCQD, 1-BCQD, 2-BCQD and 3-BCQD, respectively. Pristine CQD samples were also synthesized following a similar procedure without the addition of boric acid.

Synthesis of g-C 3 N 4 /g-C 3 N homojunction (CN)
g-C 3 N 4 /g-C 3 N 4 homojunction was prepared by a facile thermal polymerization route following a reported work with slight modifications (Phang et al. 2020a). Typically, 6 g of each precursor (urea and thiourea) were mixed in 30 ml of distilled water with gentle stirring to obtain a well-mixed solution. Subsequently, the resultant mixture was placed in the oven at 90 °C overnight to construct the nanocomposite photocatalyst. The molecular composite was transferred into a porcelain crucible and subjected to calcination at 550 °C with a ramping rate of 2 °C/min for 2 h. The resultant yellow-colored solid was cooled to ambient temperature overnight and then ground to fine powders before further use.

Synthesis of BCQD/CN nanocomposite
One (1) gram of the as-synthesized CN and 0.01 g (1 wt %) of pristine CQD or x-BCQD were mixed in 90 ml and 10 ml of distilled water, respectively. The two solutions undergone ultrasonication in separate beakers for 30 min to minimize agglomeration and exfoliate the layers of g-C 3 N 4 nanosheets. Next, both solutions were mixed and stirred for 30 min. The resultant beige-colored solution was transferred into a Teflon-lined autoclave reactor and heated at 120 °C for 4 h. The sample was collected via filtration and washed with distilled water several times. Finally, the nanocomposite photocatalyst was obtained after oven-drying at 70 °C overnight. The final photocatalyst samples were labelled as CQD/CN, 0.5-BCQD/CN, 1-BCQD/CN, 2-BCQD/CN and 3-BCQD/CN. The synthesis route of BCQD/CN nanocomposites is depicted in Fig. 1.

Characterization of materials
The surface morphology of CQD/CN and the optimized photocatalyst sample, 1-BCQD/CN were analyzed with transmission electron microscopy (TEM) (FEI Tecnai G2 20 S-TWIN, USA) by applying 200 kV of accelerating voltage. Field emission scanning electron microscope (FE-SEM) (ultra-high-resolution Hitachi SU8010, Japan) coupled with energy-dispersive X-ray analyzer (EDX) was carried out to study the surface morphology, elemental compositions and framework of CN, CQD/CN and 1-BCQD/CN. For TEM and FESEM analysis, a small amount of the photocatalyst samples were dispersed in ethanol solution and subjected to 1 min of ultra-sonication, the suspension was then dropped on a lacey carbon film and silicon wafer, respectively. The lacey carbon film and silicon wafer were subsequently ovendried prior to TEM and FESEM characterization. EDX analysis was performed quantitatively for spatial variations in elemental compositions through spot scans. The crystal structures of CN, CQD/CN and 1-BQD/CN were characterized via high-resolution X-ray diffraction (XRD) with X-ray diffractometer (Bruker D8 Discover, Germany) in the presence of Ni-filtered Cu Kα operated at 40 kV and 40 mA, with 0.02°/s as scanning rate. XRD peaks are developed by constructive interference of a monochromatic beam of X-rays and described by Bragg's Law: nλ = 2d sin θ, where order of reflection, wavelength of incident X-rays, interplanar spacing of crystal and incident angle are denoted by n, λ, d and θ, respectively. Fourier transform infrared (FTIR) spectra of CN, CQD/CN and 1-BCQD/CN were measured with FTIR spectrometer (Perkin Elmer Frontier) based on percent transmittance (% T) value in the wavenumber range of 4000-400 cm −1 and resolution of 1 cm −1 . Ultraviolet-visible diffuse reflectance spectra (UV-vis DRS) of the as-developed photocatalyst samples were analyzed using Cary 100 UV-Vis (Agilent Technologies, USA). All optical evaluations were obtained at room temperature and pressure with a wavelength range of 300-800 nm. Photoluminescence (PL) spectra of the samples were recorded with fluorescence spectrometer (Perkin Elmer LS-55, USA) with 420 nm as measurement wavelength.

Photocatalytic activity evaluation
The photoactivity of as-prepared samples were assessed via the degradation of a cationic dye, Rhodamine B (RhB). The photocatalytic experiments were conducted in a photoreactor under ambient conditions. Typically, 0.15 g of photocatalyst sample was uniformly distributed in a glass beaker containing 100 mL of 10 mg/L RhB solution. The resultant mixture was stirred without light for 30 min to establish adsorption-desorption equilibrium. Before switching on the light source, a 5 ml aliquot of the equilibrated RhB solution was collected and used as the blank sample. The LED lamp (4410R-18 W) was then switched on as the source of irradiation and samples were obtained at every 60-min interval for a total duration of 240 min. The range of wavelength and intensity of LED light source employed are 400-700 nm and 0.237 W/m 2 , respectively. All solution samples were subjected to centrifugation at 12,000 rpm for 3 min for removal of suspended powdered photocatalyst. The supernatant was then obtained and measured using a UV-Vis spectrophotometer (Hach DR 6000) and a wavelength scan ranging from 300-800 nm was obtained. The characteristic peak of the absorption band for RhB dye (552 nm) was also recorded with respect to time. Pseudo first rate constant, k of the photo-reaction was determined following the Langmuir-Hinshelwood model as presented in Eq. 1, where C 0 (mg/L), C (mg/L), k (min −1 ) and t (min) denote the RhB concentration at time t, initial concentration, kinetic rate constant and irradiation time, respectively.
The efficiency of the photocatalyst samples was evaluated in accordance with Eq. 2: A standard equilibrium curve was constructed to establish a correlation between the absorbance and the concentration of RhB dye conforming to the Beer-Lambert Law, which proclaims that the concentration and absorption of a species in the solution are proportional to one another.

Photoelectrochemical measurement
Photoelectrochemical characterizations of the photocatalysts were analyzed with an electrochemical workstation (CHI 6005E, Chenhua Instruments, China) in a quartz cell equipped with a standard three-electrode system. Each sample was coated on a titanium electrode and employed as the working electrode. Meanwhile, a Pt plate and saturated Ag/ AgCl electrode were employed as the counter and reference electrode, respectively. 0.003 mg of photocatalyst sample was distributed in C 2 H 5 OH and ultrasonicated for 10 min prior to drop-casting the catalyst onto a 1 cm 2 fluorinedoped tin oxide (FTO) substrate. The film was subsequently oven-dried and the thin-film electrodes of CN, CQD/CN and 1-BCQD/CN were obtained. A 1.0 M Na 2 SO 4 was employed as the electrolyte. The evaluation of transient photocurrent response was carried out with the light being switched on and off by applying a bias of 0.35 V. The electrochemical impedance spectra (EIS) were evaluated over a frequency of 0.1-10 5 Hz and applied potential of 0.35 V vs. Ag/AgCl with an alternating current (AC) perturbation signal of 0.01 V under the irradiation of visible light (λ > 400 nm). The Mott-Schottky plot of photocatalyst samples was obtained over a potential range of -1.0 to 1.0 V vs. Ag/AgCl.

Free radical scavenging tests
To investigate the photocatalytic mechanisms underlying BCQD/CN nanocomposites, a series of scavenging tests were conducted. 2-propanol (IPA), triethanolamine (TEOA) and p-benzoquinone (BZQ) were utilized to capture hydroxyl (•OH), holes (h + ) and superoxide anion (•O 2 ─ ) radicals, respectively. The concentrations of IPA and TEOA used in the scavenging tests were fixed at 1.2 vol %; while 0.6 vol % of BZQ was employed. The experimental setup for the scavenging analysis was identical to the procedure of photocatalytic activity evaluation as presented in Sect. 2.4.

Point of zero charge (pH pzc ) measurement
The pH pzc of the photocatalyst sample was determined using the pH drift method at room temperature with 0.15 g of photocatalyst dispersed in 100 mL of NaCl solution (0.01 M) ). The initial pH values were adjusted between the range of 3-11 with HCl (0.01 M) and NaOH (0.01 M). The photocatalyst-NaCl suspensions were placed in a shaker for 24 h to equilibrate the process of proton adsorption-desorption. The equilibrium/final pH value was then measured and plotted against the initial pH value. The pH pzc of the corresponding photocatalyst was determined as the intersection point of initial and equilibrium pH.

Process optimization of RhB photodegradation by Response Surface Methodology (RSM)
RSM is an established technique applied in the process optimization of a multivariable system (Vaez et al. 2012). The optimal conditions for photodegradation of RhB were determined using Minitab 19 statistical software. In this study, the three independent parameters of interest are pH value (x 1 ), initial concentration of dye (x 2 ) and dosage of photocatalyst (x 3 ), corresponding to the degradation efficiency of RhB as the response. The set level and range of the independent variables are tabulated in Table 1. The form of RSM used in this study is Box-Behnken designs (BBD) to evaluate the effect of three independent variables in 13 sets of experimental runs according to the following equation: where K and Ɵ are the number of factors and points in the center, respectively.

Characterization of CN, CQD/CN and 1-BCQD/CN
The surface structure and morphology of CN, CQD/CN and 1-BCQD/CN were analyzed using FESEM and TEM. The successful fabrication of an n/n-type g-C 3 N 4 homojunction (CN) was reported in our previous work (Phang et al. 2020a). As shown in Fig. 2(a), the FESEM image of CN features two-dimensional (2D) nanosheets with wide lateral dimensions. The formation of macro-scale g-C 3 N 4 (3) N = 2 × K(K − 1) + was due to the stacking of 2D polymer molecules while the lamellar structure of g-C 3 N 4 was eventually produced as the planar structure of the molecules undergone distortion. Such distortion was reported to be a result of the enlarged space between g-C 3 N 4 polymer molecules developed during the release of ammonia gas during the calcination step ). In addition, the platelet-like structures were also observed to be highly porous with large spatial networks. Figure 2(b) and (c) illustrate the FESEM images of CQD/CN and 1-BCQD/CN. From the microscopy images, it is evident that the 2D nanosheet framework of g-C 3 N 4 was generally well-retained. This indicated that the introduction of CQDs and BCQDs had no substantial effects on the surface morphology of g-C 3 N 4 , which was consistent with previously reported studies (Liu et al. 2020;Seng et al. 2020).
EDX analysis was also conducted to investigate the elemental composition of each nanocomposite sample.  CQDs. The presence of C in the EDX spectra could be due to the amorphous carbon of g-C 3 N 4 nanosheets and co-catalyst CQDs. Meanwhile, the existence of N in the spectra could be ascribed to the construction of g-C 3 N 4 using heptazine (C 6 H 3 N 7 ) as the fundamental building block of the graphitic carbon framework. Finally, the minor composition of O could be due to the formation of carboxyl groups (─COOH) during the synthesis of BCQDs as well as possible adsorption of water molecules on the photocatalyst surface. Figure 3(a)-(c) presents the TEM images of CN, CQD/ CN and 1-BCQD/CN. Similar to the FESEM image, the TEM image of CN depicted in Fig. 3(a) features a highly porous 2D planar sheet with pores of estimated diameters ranging from 22-39 nm. Upon the incorporation of CQD and BCQD, no distinguishable changes were observed with regard to the surface morphology and structure of g-C 3 N 4 . The TEM images of CQD/CN and 1-BCQD/CN are depicted in Fig. 3(b) and (c), respectively. Monodispersed quasispherical dark spots with an average diameter range of 6.076 and 6.024 nm (see Fig. 3(d)) were observed on the CN sheets for CQD and 1-BCQD, respectively. This indicated the successful formation of CQDs and BCQDs on the surface CN. The co-existence of BCQDs and CN with such close contact between them reaffirmed the successful preparation of the heterostructure nanocomposites. This unique 0D/2D layout is perceived to be beneficial for the effective transfer of photogenerated charge carriers, which will in turn lead to a reduction in electron-hole recombination rate.
The crystalline frameworks of CN, CQD/CN and 1-BCQD/CN were analyzed with XRD, a non-destructive test method for the identification of plane spacing and crystal structure based on monochromatic beam of X-rays.
Figure 4(a) presents the XRD patterns of CN, CQD/CN and 1-BCQD/CN. Two distinctive diffraction peaks were displayed by all the as-prepared photocatalytic samples, which validated the construction of stacked graphitic layers of g-C 3 N 4 (JCPDS, No. 87-1526) (Ran et al. 2019;Orooji et al. 2020). The peak observed at a lower diffraction angle of 13.4° (d = 0.67 nm) corresponded to the (100) plane associated with the in-plane structural packing motif of heptazine units (Tyborski et al. 2013). On the other hand, a moreapparent peak located at approximately 27.4° (d = 0.325 nm) could be indexed to the (002) plane, corresponding to the typical interplanar stacking layers of conjugated aromatic compounds (Elshafie et al. 2020). It should be noted that all samples (CN, CQD/CN and 1-BCQD/CN) exhibited identical XRD trends. This indicated that the hybridization of CN with CQD or BCQD did not alter its fundamental crystalline layout, which was consistent with the microscopy images in Fig. 2 and 3. Interestingly, the characteristic peaks associated with CQD or BCQD were not observed in the XRD profiles. This may ascribe to the low quantity of quantum dots employed in the nanocomposite samples. Another possible reason for this observation could be the overshadowing of amorphous CQD by highly crystalline g-C 3 N 4 polymers. Similar findings were also reported in several published work, where the hybridization of CQDs with different semiconducting materials (e.g., CQD/Fe 2 O 3 and NCQD/TiO 2 ) was studied Martins et al. 2016). Figure 4(b) shows the magnified XRD profiles of CN, CQD/CN and 1-BCQD/CN between 26 and 29°, where the (002) peaks were, respectively, located at 27.34°, 27.32° and 27.37°, respectively. Generally, a slight right-shift in the XRD peak is an implication of narrower interlayer and The molecular structure and chemical composition of CN, CQD/CN and 1-BCQD/CN were also analyzed via FTIR as shown in Fig. 4(c). For CQD/CN and 1-BCQD/CN nanocomposites, the broad band at 3260 cm −1 was ascribed to the stretching of -OH groups with the presence of CQD and BCQD (Zhang et al. 2017b). Apart from that, there were no observable changes to the transmittance peaks of the samples. This once again affirmed the well-preserved chemical framework of CN with the coupling of CQD and BCQD. The sharp peaks located in the range of 1200-1650 cm −1 could be attributed to the stretching modes of -C-N heterocycles, displaying peaks located at 1646 cm −1 , 1578 cm −1 , 1411 cm −1 , 1329 cm −1 and 1235 cm −1 (Kumru et al. 2019;Seng et al. 2020). On the other hand, the peak at 1081 cm −1 could be associated to the oxygenated functional group C-O (Wang et al. 2017b). The typical breathing mode of tri-striazine unit of g-C 3 N 4 homojunction was represented by the intense peak at 808 cm −1 (Zhang et al. 2020a).
To gain a deeper understanding of the chemical interactions, XPS analysis was carried out to identify the elemental composition and bonding on the surface of the photocatalysts. As shown in Fig. 5(a), the survey spectra of CN, CQD/ CN and 1-BCQD/CN show that the samples were primarily composed of C, N and O. The atomic concentrations and weight percentages of each element are summarized in Fig. 5(e). Intriguingly, the B element was not detected in the 1-BCQD/CN sample, which could be due to the low quantity of dopant used on the hybrid nanocomposite.
Nevertheless, the successful integration of the B dopant was verified through EDX analysis as discussed earlier (see Fig. 2(f)). Figure 5(b) presents the deconvoluted C 1 s spectra of 1-BCQD/CN, where four prominent peaks at 288.85, 288.15, 285.70 and 284.72 eV were observed. These peaks corresponded to the C-N-C bonds, sp 2 -hybridized atomic carbon in N-C = N of the aromatic systems, C-O/C = O and C-C/C = C coordination, respectively Qiao et al. 2015;Tan et al. 2015;Qin and Zeng 2017). Besides that, the N 1 s core level spectrum as depicted in Fig. 5(c) displayed a dominant peak centered at 398.57 eV, which could be associated to the pyridine N atom of the s-triazine rings (Sun et al. 2015;Cao et al. 2018). The N peak at 399.64 eV could be attributed to the pyrrolic N atom as part of the π-bonding system while the peak at 400.95 eV was ascribable to the graphitic N atom bonded to three carbon atoms within the aromatic rings (Kundu et al. 2010;Qiao et al. 2015;Fontelles-Carceller et al. 2016). The O 1 s spectra, as shown in Fig. 5(d) was deconvoluted to two fitted peaks: 533.09 eV and 531.71 eV, which corresponded to -OH and C-O/C = O bonds, respectively. These represented the oxygenic components of the B-doped CQDs which was similarly reported in the literature (Qin and Zeng 2017;Kesarla et al. 2019).
The optical properties of the as-developed photocatalysts were studied using UV-Vis DRS. As presented in Fig. 6(a), the adsorption bands of CN, CQD/CN and 1-BCQD/CN were categorized under the violet-blue regime of the visible spectrum. As observed from Fig. 6(a), the samples presented similar optical absorbances with absorption edges of CN, CQD/CN and 1-BCQD/CN at ca. 460, 453 and 452 nm, respectively. As the changes in the absorption edge of bulk and CQDs-based CN were relatively insignificant, it is reasonable to infer that CQDs primarily served as electron transfer conduits to enhance the transportation of photoinduced charge carriers (Seng et al. 2020). The measurements obtained were similar to the typical optical absorption of g-C 3 N 4 published in the previous studies Yan et al. 2020). The optical band gap energy (E g ) of a semiconductor is defined as the energy difference between the highest occupied state in the VB and the lowest unoccupied state in the CB. The E g can be determined via the construction of a Tauc plot, i.e., a graph of [F(R).hv] n vs. photon energy (hv) (Viezbicke et al. 2015). The absorption coefficient, Planck constant and optical frequency are denoted as F(R), h and v, respectively, whereas the value of exponent n depends on the transition nature of the material (Xu and Gao 2012;Kumar et al. 2017). As presented in Fig. 6(b), the E g values of CN, CQD/CN and 1-BCQD/CN were approximately 2.70, 2.76 and 2.78 eV, respectively. The widening of E g upon CQD or

Evaluation of photocatalytic activity
The photocatalytic activities of CN, CQD/CN and BCQD/ CN (with varying mass loadings of the B dopant) were assessed via the photodegradation of organic dye RhB. Prior to light illumination, the suspension of photocatalyst and dye solution was stirred for 30 min without light to establish an adsorption-desorption equilibrium. The almost-complete saturation at the solid-liquid interface minimizes the effect of physical interaction on the changes in RhB concentration as photocatalytic reaction occurs (Zhang et al. 2016a).
The photocatalytic experiments were carried out under the irradiation of an 18 W LED light for a total duration of 4 h. The primary objectives of this study are: (i) to analyze the effect of incorporating B-dopant on CQDs-decorated n/n junctioned g-C 3 N 4 ; and (ii) to investigate the optimum mass loading of B on the hybrid sample. Control experiments were also conducted following the procedures outlined in Sect. 2.4, but without (i) the photocatalyst sample; and (ii) light source (see Supplementary Information-Sect. 1.0). In both conditions, no significant discoloration of RhB was observed, which confirmed the indispensable roles of the photocatalyst and excitation source for the photodegradation process. Figure 7(a) shows the graph of ln (C 0 /C) against irradiation time of each photocatalyst sample for the evaluation of the k value according to the Langmuir-Hinshelwood model. The best-fitted lines signified the linear relationship between ln (C 0 /C) and irradiation time, thereby confirming that the photocatalytic degradation of RhB dye was in accord with the first-order kinetics. Figure 7(b) depicts an overview of the photodegradation efficiencies and kinetic rate constants of CN, CQD/ CN and BCQD/CN with varying mass loadings of B (0.5-BCQD/CN, 1-BCQD/CN, 2-BCQD/CN and 3-BCQD/ CN). As observed, the photocatalytic performances were in the order of: 1-BCQD/CN > 2-BCQD/CN > 3-BCQD/ CN > 0.5-BCQD/CN > CQD/CN > CN. In comparison with pure CN and CQD/CN, all B-modified CQD/ CN photocatalysts displayed a pronounced improvement in photoactivities. The optimum 1-BCQD/CN sample achieved a remarkable 96.8% removal of RhB dye in 4 h under LED light illumination with an associated k value of 1.39 × 10 -2 min −1 . This translated to an improvement factor of 3.6 and 2.8 over pure CN and CQD/CN, which validated the significance of heteroatom B doping on CQDs for photocatalytic activity enhancement. The discoloration process of RhB in the presence of 1-BCQD/CN is shown in inset of Fig. 7(d). Interestingly, the color of the organic dye was observed to change progressively from its characteristic pink shade to orange and yellow, before turning colorless eventually.
As demonstrated in Fig. 7(b), the mass loading of B on CQD/CN did not impose prominent effects on the photodegradation efficiency of the hybrid material. However, its profound impact on the apparent rate constant was evident. Based on Fig. 7(b), the evaluated rate constant demonstrated an appreciable surge from 1.09 × 10 -2 min −1 (0.5-BCQD/CN) to 1.46 × 10 -2 min −1 (1-BCQD/CN). This observation highlighted the significance of precise mass loading of the B-dopant on CQD/CN in terms of expediting interfacial charge transfer and hindering electron-hole recombination. Figure 7(c) shows the absorbance trend exhibited by the RhB solution catalyzed over 1-BCQD/CN sample under visible light irradiation. For a RhB dye, the characteristic peak of the absorbance curve was noted at a wavelength of 554 nm prior to photodegradation. Apart from the gradual decrease in absorbance intensity with time, the peaks shifted gradually toward the blue region (left) of the visible spectrum as the illumination time lengthened. This was in congruent with the reported studies on the photodegradation of RhB catalyzed by g-C 3 N 4 / g-C 3 N 4 homojunction systems, Ag 3 PO 4 nanoparticles and Ag 3 VO 4 /β-Ag 3 VO 4 nanocomposites Xu et al. 2017;Phang et al. 2020a). Besides, the left-shifted peaks signified the generation of de-ethylated intermediates as the chromophores and aromatic rings of the RhB dye undergone deconstruction (Li et al. 2008;Chiu et al. 2019).
In comparison with several previously published studies, the optimum photocatalytic nanocomposite sample 1-BCQD/CN performed fairly well among its counterparts. Table S1 in Supplementary Information-Sect. 2.0 presents the photodegradation performance of different photocatalytic nanocomposites as reported in the literature (da Silva et al. 2014Silva et al. , 2016Silva et al. , 2021Liu et al. 2017;Muraro et al., 2020;Sahu et al. 2020;Zhu and Zhou 2020).

Photoelectrochemical and PL analysis
To further study the charge migration behavior and separation of photo-generated electron-hole pairs across the interface of BCQD/CN photocatalyst, transient photocurrent response and Mott-Schottky plots were also Fig. 7 (a) RhB degradation profile with respect to time, b) linear graph of ln (C o /C) against irradiation time for all photocatalyst samples, (c) RhB degradation efficiency and kinetic rate constant of each photocatalyst under the irradiation of LED light and (d) absorbance curves of 1-BCQD/CN at wavelengths between 300 and 800 nm for 240 min with 60-min intervals (Inset: gradual decolorization of the RhB dye as a result of photodegradation in the presence of 1-BCQD/ CN) ◂ constructed. As presented in Fig. 8(a), the transient photocurrent measured were plotted with respect to time for CN, CQ/CN and 1-BCQD/CN with alternate cycles of on-off visible light irradiation to study their photoelectronic properties. The electric current generated by the photo-excited charge carriers were measured via transient photocurrent as the visible light pulse was turned on and decayed promptly with the light shut off (Xiang et al. 2011;Phang et al. 2020a). It is observed that there was a significant improvement in the transient photocurrent response exhibited by 1-BCQD/CN. The relatively high current density of 1-BCQD/CN is an implication of the boosted effectiveness in electron-hole pairs separation which may be ascribed to the presence of BCQDs. The doping of BCQDs on CN played a significant role as the channels for electron transport (as discussed previously in Sect. 3.2) and this inference was further supported by the generally low Fermi level of CQDs (-0.3 eV) relative to that of CN (-0.61 eV) (Tian et al. 2017;Wang et al. 2017a). Thus, the photoinduced electrons were prompted to shuttle from CN to BCQDs, in which the BCQDs served as electron traps, to effectively retard the recombination of electron-hole pairs Di et al. 2020).
Moreover, Mott-Schottky analysis was performed as an effort to analyze the interrelation between applied potential and capacitance space charge region. Figure 8(b) presents the Mott-Schottky plots of the photocatalyst samples and the flat band potential (E fb ) was evaluated via the extrapolation of tangent lines at the x-axis intercept whereby C −2 = 0. From the Mott-Schottky plot, the E fb of CN, CQD/ CN and 1-BCQD/CN were determined as -0.70, -0.74 and -0.77 V vs. Ag/AgCl, respectively. The E fb was marginally lowered with the incorporation of CQD and BCQD, indicating a depletion in photo-generated holes on the surface of the hybrid photocatalysts (Rangaraju et al. 2009;Liu et al. 2014). On top of that, Mott-Schottky plots of the samples displayed positive slopes which is the typical characteristic of an n-type semiconductor (Guan et al. 2020). Hence, this verified the successful construction of photocatalytic nanocomposites featuring n/n homojunction via coupling of g-C 3 N 4 derived from urea and thiourea. The measured flat band potentials are with respect to NHE using the conversion equation as expressed in Eq. (3) whereby pH value was approximately 7.0 and E AgCl = 0.197 V at ambient temperature (Babu et al. 2018;Li et al. 2020a): Upon conversion, the E fb (vs. NHE) of CN, CQD/CN and 1-BCQD/CN were evaluated as -0.09, -0.13 and -0.16 V, respectively. It is well-entrenched that the E cb of an n-type semiconductor is generally 0.1-0.3 V more negative than its E fb , as governed by the electron effective mass and carrier concentration (Tian et al. 2015). In this case, the difference in voltage between E fb and E cb was set at 0.3 V. Therefore, the E cb were calculated as -0.39, -0.43 and -0.46 V for CN, CQD/CN and 1-BCQD/CN, respectively. Subsequently, the valence band potential, E vb were evaluated according to the equation as follows: The E vb of CN, CQD/CN and 1-BCQD/CN were obtained as 2.31, 2.33 and 2.32 V, respectively.
The PL spectra exhibited by CN, CQD/CN and 1-BCQD/ CN were also presented in Fig. 8(c). Hitherto, the governing factor of PL mechanism has yet to be thoroughly elucidated and remains highly debatable as there are multiple argumentations regarding this subject matter. The proposed concepts include quantum confinement effect, functional groups, structural defect, surface passivation and functionalization, etc. (Wang et al. 2014;Choi et al. 2016;Das et al. 2017). Nonetheless, it has been widely perceived that the intensity of PL emission is closely associated with the recombination of photo-excited charge carriers. Thus, PL spectra are commonly utilized to interpret the migration behavior, separation and transfer mechanism of electron-hole pairs (Zhu et al. 2019). Based on Fig. 8(c), the PL emission spectra of CN, CQD/CN and 1-BCQD/CN featured a prominent luminescence peak ranging from 420-520 nm. As it is well known, intense fluorescence (FL) emission implies a high rate of electron-hole recombination, whereby photogenerated holes from the lower energy states and electrons from the higher energy states recombine to release energy (4) E fb (vs.NHE) = E fb (vs.Ag∕AgCl) + E (AgCl) + 0.059pH (5) E vb = E cb + E g in the form of light . It is observed from Fig. 8(c) that CN exhibited the strongest PL emission spectra. On the contrary, relatively low PL emission peaks were demonstrated by CQD/CN and 1-BCQD/CN, reflecting the suppressed electron-hole recombination in the presence of pristine or B-doped CQDs. This also reaffirmed the role of CQDs in the hybridized photocatalytic nanocomposites as an electron transport conduit, considerably boosting the effectiveness of charge carrier transport and separation. Fundamentally, a low charge carriers recombination rate is highly beneficial toward the photocatalytic efficiency of a semiconductor nanomaterial.

Free radical scavenging test and plausible photocatalytic charge transfer mechanism
A series of scavenging tests were performed to identify the role of each reactive species in the photocatalytic mineralization of RhB and to propose a plausible photocatalytic mechanism over BCQD/CN. The declined photocatalytic performance in the presence of each scavenger implied the importance of the associated reactive species. The scavenging chemicals, TEOA, BZQ and IPA were applied to capture the relevant reactive species, h + , •O 2 − and •OH, respectively. The changes in concentration of RhB and degradation efficiency of BCQD-CN are summarized in Fig. 9(a). As observed in Fig. 9(b), it is evident that there was a drastic decrease in photoactivity upon the addition of TEOA (scavenger of h + ), indicating that h + species were indispensable for RhB photodegradation. Precisely, h + reactive species held a crucial role in the generation of radicals including •OH and OH − , which actively took part in the mineralization of RhB ions (RhB + ) into photodegraded products. In the absence of h + species, the generation of •OH radicals is not viable as the oxidation potential of water (H 2 O/•OH = + 2.73 eV) is more positive than the VB potential of the photocatalyst sample ). Nevertheless, •OH radicals could also be generated via a different pathway whereby the reduction of elementary oxygen leads to the formation of •O 2 − species, which are then further reduced to •OH radicals through multiple-electron reduction reactions. In addition, the VB potential of BCQD/ CN was more positive than the standard redox potential of waterborne hydroxyl radicals (•OH/OH − = + 1.99 eV), rendering the oxidation of OH − feasible (Wu et al. 2015). In short, these reactive species are crucial in the degradation and mineralization of RhB + under light irradiation.
Based on the scavenging test, a plausible step-by-step charge transfer mechanism for RhB photodegradation is presented in Fig. 10. The entire photo-reaction is initiated by the irradiation of visible light, where the electrons from VB are excited and directed toward CB. Upon the departure of electrons, holes are generated at the VB concurrently. Due to the difference in CB and VB levels of g-C 3 N 4 homojunction derived from urea and thiourea, the photo-generated electrons and holes are separated more effectively in comparison with the charge transfer within a pristine g-C 3 N 4 . Specifically, the flow of photogenerated electrons (e − ) is directed from the higher CB level of thiourea to that of urea while majority of the photogenerated holes (h + ) are prompted to flow from the lower VB level of urea to that of thiourea. The opposite direction in flow of charge carriers minimizes the recombination possibility for electrons and holes. Furthermore, the doping of CQDs with heteroatoms B enriched the presence of structural defects on the functionalized surface of BCQDs, effectively trapping more photo-excited charge carriers and hampered the recombination of electrons and holes (Peng et al. 2020). Consequently, the photoinduced electrons from VB of CN are readily transferred to the BCQDs due to their lower energy levels . The electrons are also captured and accumulated in the BCQDs attributed to their excellent conductivity and large capacity for electron storage (Ong et al. 2017). The electrons accumulated in the BCQDs and remnant of electrons in CN are primarily responsible for the reduction of O 2 to generate superoxide anion radicals (•O 2 − ). The reduction process is feasible as the CB levels of the nanocomposite are more negative than the redox potential of O 2 /•O 2 − at -0.16 V (Krumova and Cosa 2016). The •O 2 − radicals are indispensable for the mineralization of RhB dye as evidenced by the scavenging test. On the other hand, the photoinduced holes in VB are gradually transported to the surface and participate in the oxidation process of hydroxyl species into hydroxyl radicals (•OH) as the VB level of BCQD/CN is more positive as compared to the redox potential of OH − /•OH at + 1.89 V (Armstrong et al. 2015). It is also worth mentioning that the change in redox potential ability upon hybridization is negligible as ratiocinated from the evaluated VB and CB energy levels of pristine CN, CQD-and BCQD-based CN. Therefore, it is reasonable to deduce that the BCQD and/or CQD mainly acted as channels to facilitate electron transport and storage for the photocatalytic enhancement. Another factor that should be taken into consideration for RhB photodegradation is the challenge of possible colloidal instability, competition over active sites and susceptible hole scavenging posed by the inorganic chloride anions (Cl − ) (Chong et al. 2010). Nonetheless, the presence of π-π interactions on the exterior of the nanocomposite photocatalyst enhanced the adsorption of organic pollutants, resulting in a boosted photocatalytic efficiency. Ultimately, the mineralization process of RhB pollutants was expedited by reactive species including •OH, •O 2 − and h + in the formation of photo-degraded products.

Recyclability test
In addition to the initial photocatalytic performance, the reusability of photocatalysts is also critical for practical and long-term applications. For the evaluation of its photostability, the optimal sample, 1-BCQD/CN, was assessed and recycled for three consecutive cycles under identical conditions. The photocatalyst sample was separated from the dye solution via vacuum filtration and washed copiously with distilled water prior to oven-drying for the subsequent cycle. To account for the weight loss in the recovered photocatalyst sample, the amount lost was compensated by a decreased volume of dye solution following a fixed ratio of 0.15 g photocatalyst to 100 mL RhB solution (10 mg/L). The recyclability test of 1-BCQD/CN is presented in Fig. 11(a). It is apparent that the photoactivity of 1-BCQD/CN was successfully retained even after three successive cycles without any observable regression in its photocatalytic performance. Precisely, the 1-BCQD/CN photocatalyst sample maintained 98.6% of its original activity after three consecutive runs. Furthermore, there were no significant changes to the molecular structure and chemical composition of the recycled 1-BCQD/CN with reference to its fresh counterpart as evidenced by their respective FTIR spectra presented in Fig. 11(b). This suggests that 1-BCQD/CN is superior in terms of its stability and durability, which are highly advantageous from the economic and sustainability perspectives for probable industrial applications in the future.

Process optimization of RhB photodegradation underlying 1-BCQD/CN
Regression analysis was performed and a second-order polynomial equation was determined that best demonstrates the empirical relationship between photodegradation efficiency of RhB and the independent variables: Based on Eq. 6, the pH value and initial dye concentration had negative effects on the response (RhB degradation), whereby the photoactivity increases as the pH and initial RhB concentration decrease. On the other hand, dosage of photocatalyst had a positive effect on the photodegradation process as a higher rate of RhB removal was observed with an increase in the photocatalyst amount. Table 2 presents the model summary of regression equation for photocatalytic degradation of RhB. From the results displayed in Table 2, the coefficient of determination (R 2 ) calculated is close to 1 and the adjusted value is also comparable to the corresponding R 2 , which indicates the adequacy of the regression model. Furthermore, the relatively low prediction error sum of squares (PRESS) reflected in a high predicted R 2 .
Based on the analysis of variance (ANOVA) results, it is further verified that the regression model is a good fit to the experimental data as p-values of all coefficients are less (6) RhBdegradation(%) = 124.6 − 26.53x 1 − 1.680x 2 + 456.3x 3 + 1.2596x 2 1 + 0.2256x 1 x 2 − 16.26x 1 x 3 − 9.73x 2 x 3 Fig. 11 (a) Recyclability test of 1-BCQD/CN for three consecutive cycles and (b) FTIR spectra of 1-BCQD/CN in fresh and recycled conditions than 0.05. The analysis results also showed that all three independent variables are influential to the removal of RhB to a certain degree, with pH value, initial concentration and photocatalyst dosage contributing 57.49, 18.77 and 4.23% to the overall RhB photodegradation process, respectively. The model was further validated by comparing the experimental and predicted responses for each run, it was observed that the difference between these values is marginal as tabulated in Table 3. On top of that, Fig. 12(a) shows that the predicted values are linearly proportional to that of experimental with slight deviation.

Effect of pH value
The solution pH is one of the primary factors that affect the process of RhB photodegradation and pH value of effluents differ considerably across various industrial sectors (Ghosh and Pal 2020). Herein, the pH value of RhB solution was varied from 3 to 11 and it was observed that 1-BCQD/CN displayed relatively high degradation effectiveness in the acidic environment as compared to the alkaline region. It is well known that RhB dye has an acid dissociation constant, pKa of approximately 3.1 (Huy et al. 2017;Tho et al. 2018). In the case of pH > pKa, the carboxyl groups of RhB are deprotonated with the formation of negatively charged ions. In conjunction with the study of pH value effect on RhB photodegradation performance of the optimum photocatalyst, the pH pzc of 1-BCQD/CN was also evaluated. Based on the pH drift method, the pH pzc of 1-BCQD/CN was determined as 7.0 ( Fig. 12(b)). This implied that the surface of the photocatalyst is positively charged when the pH of the solution is less than pH pzc and vice versa (Yang et al. 2020b). The value of pH pzc evaluated is comparable to several other g-C 3 N 4 -based semiconductors as reported previously Fronczak et al. 2018). Therefore, the dye adsorption on 1-BCD/CN was enhanced due to its positively charged surface being in contact with deprotonated RhB ions. In contrast, the drastic decline in the photodegradation of RhB as pH value increases may be ascribed to the zwiterionic form of RhB whereby the carboxyl and xanthene groups of RhB monomers combine  . 12 (a) Graph of predicted against experimental data for each run, (b) plot for determination of pH pzc of 1-BCQD/CN and (c) optimum conditions to form dimers, impeding the contact between RhB and 1-BCQD/CN (Huy et al. 2017). Nevertheless, the correlation between pH value, pKa and pH pzc is not the sole governing factor that determines the RhB photodegradation efficiency, there are other influences such as hydrogen bonding and hydrophobic interactions Kooh et al. 2016;Madjene et al. 2021).

Effect of photocatalyst dosage
The rate of RhB photocatalytic degradation is strongly dependent on the amount of photocatalyst involved. The dosage of the photocatalyst 1-BCQD/CN was varied from 0.10 to 0.20 g. It was observed that the percentage of RhB photodegradation was improved with increasing dosage of photocatalyst, this is attributed to the growing number of photogenerated electron-hole pairs and availability of active sites (Ramanathan et al. 2019;Saher et al. 2021).

Effect of initial RhB concentration
Another influential factor on the photocatalyst degradation of RhB is the initial dye concentration, which was studied by varying the initial concentration of RhB from 10 to 30 mg/L. Based on the optimization results, it can be deduced that the rate of RhB photodegradation decreased with an increase in initial RhB concentration. The drop in RhB photodegradation performance with relatively high concentration is mainly due to the limited amount of light penetration through the dye solution. Besides that, the large amount of dye molecules that were absorbed onto the surface of the photocatalyst may obscure the active sites from receiving the photons which are essential for photocatalytic activity to occur (Zhao et al. 2012;Maruthamani et al. 2015). Based on the boundaries and independent variables set for the optimization study, the optimum conditions for maximum photocatalytic degradation of RhB were identified as pH 3.7, initial dye concentration of 10 mg/L, and photocatalyst dosage of 0.20 g (Fig. 12(c) and Fig. S2). A further experimental investigation was conducted based on the generated ideal conditions, and a relatively high conformity between the experimental data and model predicted value was observed.

Conclusion
In summary, novel metal-free composite photocatalysts (BCQD/CN) were successfully fabricated by hybridizing B-doped CQDs and n/n-type g-C 3 N 4 homojunction derived from equal proportion of urea and thiourea. Different amounts of B dopant were applied to determine the appropriate dosage in optimizing the photocatalytic efficiency of BCQD/CN nanocomposite. The successful incorporation of BCQDs and CQDs into g-C 3 N 4 /g-C 3 N 4 homojunction was verified via a series of characterization analyses including FESEM, TEM, EDX, XRD, FTIR and XPS. These tests have successfully proven the co-existence of BCQDs and CN which were bonded together securely as distinguished through the changes in their surface morphologies, crystalline structures, chemical compositions, etc. PL and UV-Vis DRS were also carried out to study the optical properties of the as-synthesized photocatalyst samples by evaluating their band gap structures and charge transfer behaviors. The optimized photocatalytic nanocomposite, 1-BCQD/CN with a mass ratio of boric acid to citric acid at 1:3, displayed a marginally higher photocatalytic performance relative to other BCQD/CN samples with a RhB photodegradation efficiency 31% and 40% higher than that of CQD/CN and CN, respectively. There are several contributing factors to the boosted photoactivity of BCQD/CN nanocomposites, including the synergistic effects of (1) promoted electron charge transport from CN to BCQDs, (2) suppressed recombination rate of electron-hole pairs and (3) improved charge density in facilitating charge migration. The photoactivity evaluation of RhB degradation was conducted under the illumination of an 18 W LED light. The remarkable photoefficiency displayed by BCQD/CN toward RhB degradation despite the relatively low-powered light source highlights the various benefits from the environmental and economic perspectives. This offers an optimistic outlook to the possible industrial-scale operation for wastewater treatment by means of photocatalysis in the near future. On top of that, the durability of 1-BCQD/CN was also validated by subjecting it to three consecutive cycles of RhB photodegradation under identical conditions, where no observable regression in photoactivity was observed. A plausible photocatalytic mechanism for RhB degradation in the presence of BCQD/ CN was also proposed by identifying the roles of specific reactive species through a series of scavenging tests. An optimization study was performed for the process of RhB photodegradation and a quadratic regression model was developed to identify the optimum conditions for maximum removal of RhB as pH 3.37, initial RhB concentration of 10 mg/L and 0.20 g of 1-BCQD/CN photocatalyst. On the whole, this research work is expected to provoke more pioneering research ideas in the development of photocatalytic semiconductors as a robust approach to various pressing global challenges, particularly the environmentaland energy-related matters.