Preparation of Novel Mesoporous LaFeO3-SBA-15-CTA Support for Syngas Formation of Dry Reforming

A nanocomposite NiPt/5LSBA-160 catalyst comprised of highly dispersed Ni nanoparticles contacting intimately with Pt over novel mesoporous LaFeO3-SBA-15-CTA support with a high specific surface area (SSA) was successfully developed for the dry reforming of methane. Results revealed that the high SSA mesoporous LaFeO3-SBA-15-CTA materials could first be synthesized by an in situ growth hydrothermal process and used as an excellent carrier candidate of Ni-based catalysts to achieve enhanced catalytic activity due to the strong interaction between LaFeO3 and Ni species. Moreover, the introduction of Pt over a Ni/5LSBA-160 catalyst would further promote the interaction between Ni and support, improve the dispersion of active Ni centers and obtain a higher syngas formation rate as well as tolerance to carbon coking than that of a Pt-free Ni/5LSBA-160 catalyst sample. This finding uncovers a promising prospect for high SSA mesoporous perovskite preparation and utilization in catalysis such as oxidation, hydrogenation, photocatalysis, energy conversion and so on.


Introduction
The catalytic dry reforming of methane (DRM) process can convert both CH 4 and CO 2 into synthesis gas (syngas, CO and H 2 ), which is a classical building feed to produce sulfur-free diesel fuels, oxygenated chemicals and other important high value-added chemicals [1][2][3]. However, the DRM reaction usually needs to be performed at a high reaction temperature due to its intrinsic endothermic property (Equation (1)), which inevitably generates some side reactions, such as Equations (2) and (3), and causes carbon deposition, covering the active site of the catalysts [4][5][6]. On the other hand, the catalysts (e.g., Ni-based catalysts) universally exhibit low thermal stability under harsh reaction conditions which leads to sintering [7]. Therefore, to realize the industrialization of the DRM reaction with a long lifetime and high efficiency, two major manipulators for catalysts must first be solved, namely active phase (Ni) sintering and carbon deposition [8,9].
It is accepted that the strong metal-support interaction can serve as an alternative effective strategy to improve the dispersion of active phase nanoparticles and promote their resistance to sintering and carbon deposition [10,11]. The key issue is to develop carriers or additives with high thermal stability that can strongly interact with the active phase. Various materials such as Al 2 O 3 , ZrO 2 , MgO, CeO 2 , mesoporous silica and molecular sieve are used as catalyst supports or additives and can enhance the catalytic activity of active species such as Ni particles in DRM [12]. Recently, perovskite oxides (ABO 3 ) aroused much attention due to their outstanding virtues of abundant lattice defects, readily heteroatomic substitution and high thermal stability for the DRM reaction [13,14]. Catherine et al. reported that an LaNiO 3 catalyst prepared using the auto-ignition process showed high activity, stability and good tolerance to anti-coke for dry reforming [15]. Moradi et al. studied the partial substitution of Mg, Sr and Ba on the A site and evaluated the catalytic activity for DRM. It was found that the substitution of Ba showed higher activity than that of Mg and Sr, and the optimized La 0.9 Ba 0.1 NiO 3 catalyst possessed the highest conversion of CH 4 and CO 2 . Moreover, LaFeO 3 -based catalysts also performed high catalytic activity and the selectivity of synthesis gas (CO and H 2 ) [16,17]. Liao et al. reported that the Ni nanoparticles were served as catalytically active sites self-generated from nanoparticles/LaFeO 3 heterogeneous structure, and can exhibit superior performance for both methane conversion and the activation of C-O bonds [18].
Nevertheless, the preparation of perovskites should be performed under relatively stringent conditions such as high temperature and long calcinations time; this would cause the agglomeration of grain size and decrease of specific surface area, which would discourage the exposure of active sites or loading center for heterogeneous catalysis [19]. To deal with this problem, some porous silica materials such as ordered cubic mesopores (KIT-6) and ordered hexagonal mesoporous silica structures (SBA-15) were added during the synthesis process as hard templates [20]. Mesoporous LaFeO 3 catalyst was successfully formed using KIT-6 as a hard template, and the specific surface area was up to138 m 2 /g, which exhibited a higher adsorbed oxygen concentration and better low-temperature reducibility as well as excellent oxidation activity [21]. Ruan et al. employed SBA-15 as a templating agent to prepare a mesoporous LaAl 0.25 Ni 0.75 O 3 perovskite catalyst, and the catalyst process had higher activity and stability than that of the catalyst synthesized by the commercial silica template, where the conversion for both CH 4 and CO 2 can be maintained at more than 75% after 36 h of DRM reaction [20]. However, the subsequent removal process of the templating agent is complicated as well as the discharge of wastewater. Therefore, it is urgent to develop a new synthesis process to prepare perovskites-based catalysts with large specific surface area and multiple active catalytic sites for DRM reaction.
In our previous study, high-quality SBA-15-CTA (CTA stands for citric acid) materials were tailored under moderate polycarboxylic acid (citric acid), and the obtained SBA-15-CTA-loaded Ni catalysts showed good potential for the dry reforming of methane (DRM) reaction with much less coke formation at 700 • C [22]. Moreover, citric acid is widely used as a complexing agent to promote intermetallic dispersion and reduce the crystallization temperature in the preparation of the tunable perovskite materials [23]. The bridging connection of citric acid spurs us to develop an SBA-15-CTA supported perovskites catalyst with a large specific surface area using one-pot hydrothermal technology. In this contribution, a one-step in situ growth hydrothermal process was firstly employed to effectively prepare a series of LaFeO 3 /SBA-15-CTA hybrid materials with a large specific surface area, and these mesoporous perovskites were used as the carriers to synthesize Ni(Pt)/LaFeO 3 -SBA hybrid catalysts for the DRM reaction. The obtained composite catalysts displayed high activity and resistance to carbon deposition for the dry reforming process. It should be noted that the preliminary study for the addition of Pt aims at investigating the interaction among the metals and the support, and further investigations are needed.

Materials
All the reagents, including anhydrous citric acid, tetraethyl orthosilicate (≥98%, TEOS), poly (ethylene glycol)-block-poly (propylene glycol)-block-poly (ethylene glycol) ( The preparation of LaFeO 3 -SBA-15-CTA supports was carried out using a one-pot in situ growth hydrothermal process. The precursor solution was produced by mixing stoichiometric amounts of La(NO 3 ) 3 ·6H 2 O and Fe(NO 3 ) 3 ·9H 2 O into citric acid-deionized water solution (citric/(La + Fe) molar ratio = 1.1) at room temperature (RT), and then the surfactant of P 123 was added to the solution and stirred to form a homogeneous solution. After that, TEOS was slowly added to the above mixture. Subsequently, the mixture was loaded into a PTFE-lined stainless-steel autoclave and heated at various temperatures (120 • C, 140 • C, 160 • C) for 24 h (please refer to Table 1 for the detailed experimental factors). After cooling down to room temperature, the crystallized product was filtered, washed and dried at 100 • C for 24 h. Finally, the powder product was calcined at 750 • C for 6 h to achieve mesoporous xLaFeO 3 -SBA-15-CTA support, which was labeled as xLSBA-T (x means the content of LaFeO 3 , T stands for the hydrothermal temperature).  [24]. It was noted that the Ni and Pt components were settled at 5 wt.% and 0.5 wt.%, respectively.

Catalysts Characterization
X-ray diffraction (XRD, 2θ = 5-80 • ) and small-angle XRD (2θ = 0-6 • ) were carried out on an X-ray diffractometer (Bruker D8 Advance) using Cu Kα1 irradiation (λ = 0.15418 nm). N 2 adsorption-desorption experiments were performed on a Micromeritics ASAP 2420 automatic analyzer to achieve the specific surface area and pore volume. Prior to testing, the samples were pretreated at 200 • C for 12 h to remove impurities. The microstructure of samples was analyzed via scanning electron microscopy (SEM, JEOL, JEM-2100F, Tokyo, Japan) and transmission electron microscopy (TEM, FEI Tecnai G2 F20, Waltham, MA, USA) at 200 kV. An AutoChem II 2920 (Thermo Scientific, Waltham, MA, USA) was engaged to study the reduction behavior of the NiO(PtO x )/yLSBA-T catalysts. A 30 mg sample was used, which was pretreated under Ar flow (30 mL/min) at 300 • C for 1 h. After that, the sample was heated in a 30 mL/min 10% H 2 /Ar flow with a ramping rate of 10 • C /min ranging from 50 • C to 800 • C. A thermal conductivity detector (TCD) was used to record the hydrogen consumption, which was calibrated using a 99.99% CuO reference. Ni K-edge X-ray absorption near edge structure (XANES) investigations were carried out using XAFCA beamline in the transmission mode (Shiga, Japan), and Ni K-edge spectra of pre-reduced catalysts (reduced at 700 • C for 1 h under 10% H 2 /He mixed gases and cooled down to 30 • C under He) were calibrated with respect to the spectrum of a Ni foil and NiO references. Weight loss curves were obtained on a TGA Discovery SDT-650 instrument to evaluate the carbon deposition amount for the spent samples.

Catalytic Activity Testing
The dry reforming of methane (DRM) reaction was performed in a fixed-bed quartz reactor (ID: 7 mm) at atmospheric pressure. Specifically, catalysts (0.15 g, 40-60 mesh) were added to the central reactor tube under the support of quartz wool. The catalyst was pretreated in 10 vol% H 2 / He (50 mL/min) at 700 • C for 1 h. Then, the reaction gas (CO 2 /CH 4 /Ar/N 2 = 3:3:3:1) with a total flow rate of 50 mL/min (GHSV = 20,000 mL·g cat −1 ·h −1 ) was introduced to the reactor. The exhausted products were analyzed via a Gas Chromatograph (GC6890, NYSE: A, Palo Alto, CA, USA) equipped with a TCD detector (an HP-Plot capillary column combined with a Carbon-Plot) online.
Temperature-programmed surface reaction-mass spectrometry (TPSR-MS) was employed to evaluate the catalytic activity. An 0.15 g catalyst was pre-reduced as mentioned above. After that, it was cooled down to 300 • C under helium gas with a flow of 45 mL/min. The TPSR-MS analysis was engaged under the mixture gas (CO 2 :CH 4 :Ar = 6/4/15) at 50 mL/min from 300 • C to 850 • C with a heating rate of 10 • C/min. The changes in concentration for CH 4 , CO 2 , H 2 and CO gases were recorded on a PerkinElmer mass spectrometer.  [25,26]. Moreover, the diffraction peaks located at 37.2, 43.2 and 62.8 should be ascribed to the (111), (200) and (220) planes of cubic NiO [27], and their intensities vary with the content of LaFeO 3 (from 30 wt.% to 70 wt.%) and hydrothermal temperature (from 120 to 160 • C). The high concentration of LaFeO 3 combined with the high hydrothermal temperature improved the dispersion of NiO nanoparticles, as displayed in Figure 1a,b. The crystallite sizes of NiO active nanoparticles calculated by Scherrer's equation were ca. 13 nm (Table S1). However, no diffraction peak of platinum oxide could be observed due to the detection limit of X-ray diffraction, as indicated in Figure 1b. According to our previous reports, the grain size of NiO deposited on the CeO 2 (≤5 wt.%) doped SBA-15-CTA could be reduced to ca. 13 nm, and the obtained catalysts exhibit high DRM catalytic activity [24]. Herein, the optimized LaFeO 3 doping content on the SBA-15-CTA carriers can also enhance the dispersion of the active phase of NiO and lead to high DRM catalytic performance.

N2-BET and Morphology Studies
It is generally accepted that the catalyst's physicochemical properties, such as specific surface area, microstructure, grains size, redox capability and valence states, are closely related to the catalytic activity [28,29].

N 2 -BET and Morphology Studies
It is generally accepted that the catalyst's physicochemical properties, such as specific surface area, microstructure, grains size, redox capability and valence states, are closely related to the catalytic activity [28,29]. Figure 2a-c present the N 2 adsorption-desorption isotherms of the synthesized NiO(PtO x )/yLSBA-T catalysts with y value ranges from 30-70 wt.% displaying a type of IV isotherm with H1-type hysteresis loop under the wide hydrothermal condition, revealing their mesoporous characteristic. In addition, the pore size distribution centered at ca. 7 nm for all the catalysts is in good agreement with the hysteresis loops shape (Figure 2a). However, an increase in hydrothermal temperature will result in larger pore size, as depicted in Figure 2b. It is reported that increasing hydrothermal temperature could lead to thinner walls and could broaden mesostructure pore size to some extent [22]. When it comes to the value of the specific surface area (SSA) for the prepared catalysts, the high LaFeO 3 content coupled with the high in situ growth hydrothermal temperature will cause a decrease in specific surface area. Typically, the SSA of the NiO/3LSBA-140 catalyst was 314.4 m 2 /g, while it was decreased to 123.7 m 2 /g for the high LaFeO 3 content doped sample (NiO/7LSBA-140) (Figure 2a). On the other hand, the SSA of the NiO/5LSBA-120 catalyst was 219.5 m 2 /g, but the SSA of NiO/5LSBA-160 was reduced to 180.0 m 2 /g ( Figure 2b). However, the descending mechanism of SSA was indeed different. The decrease in SSA was caused by the pore blockage for high LaFeO 3 content modified catalysts, while the decrease in SSA for hydrothermal temperature should be attributed to the enlarged pore diameter, though a 2D-hexagonal mesostructure (Supplementary Material Figure S1) can be formed under a wide range of hydrothermal temperature from 120 to 160 • C.

TEM Measurements
Regarding the introduction of platinum noble metal, it was noted that the pore structure and the value of SSA for the NiOPtOx/5LSBA-160 catalyst were almost unchanged compared to the parent catalyst of NiO/5LSBA-160, as shown in Figure 2c and Table 1. Moreover, all the prepared NiO(PtOx)/yLSBA-T catalysts showed a rod shape morphology (Figure 2d), and the basic morphology was mainly derived from hydrothermal conditions, which corresponds to our previous reports [22]. In order to investigate the relationship between the catalytic activity and particle size of the catalysts, TEM was employed on the outstanding catalysts, namely reduced NiO/5LSBA-160 ( Figure 3a) and

TEM Measurements
Regarding the introduction of platinum noble metal, it was noted that the pore structure and the value of SSA for the NiOPtO x /5LSBA-160 catalyst were almost unchanged compared to the parent catalyst of NiO/5LSBA-160, as shown in Figure 2c and Table 1. Moreover, all the prepared NiO(PtO x )/yLSBA-T catalysts showed a rod shape morphology (Figure 2d), and the basic morphology was mainly derived from hydrothermal conditions, which corresponds to our previous reports [22]. In order to investigate the relationship between the catalytic activity and particle size of the catalysts, TEM was employed on the outstanding catalysts, namely reduced NiO/5LSBA-160 ( Figure 3a) and NiOPtO x /5LSBA-160 (Figure 3b) catalysts. It was inferred that introducing Pt could target a higher dispersion of active Ni nanoparticles than that of single LaFeO 3 -doped Ni/5LSBA-160 catalysts. This is due to the stronger interaction of Ni-Pt [30].

TEM Measurements
Regarding the introduction of platinum noble metal, it was noted that the pore structure and the value of SSA for the NiOPtOx/5LSBA-160 catalyst were almost unchanged compared to the parent catalyst of NiO/5LSBA-160, as shown in Figure 2c and Table 1. Moreover, all the prepared NiO(PtOx)/yLSBA-T catalysts showed a rod shape morphology (Figure 2d), and the basic morphology was mainly derived from hydrothermal conditions, which corresponds to our previous reports [22]. In order to investigate the relationship between the catalytic activity and particle size of the catalysts, TEM was employed on the outstanding catalysts, namely reduced NiO/5LSBA-160 ( Figure 3a) and NiOPtOx/5LSBA-160 (Figure 3b) catalysts. It was inferred that introducing Pt could target a higher dispersion of active Ni nanoparticles than that of single LaFeO3-doped Ni/5LSBA-160 catalysts. This is due to the stronger interaction of Ni-Pt [30].

H 2 -TPR for Catalysts
To understand the impact of the high SSA LaFeO 3 carrier on the reductivity of large amounts of active O species of catalysts under various conditions (hydrothermal temperature, concentration and Pt additive), H 2 -TPR experiments were performed, and the reflected results are shown in Figure 4. It was found that the reduction peak can be effectively lagged by inducing the LaFeO 3 owing to the strong interaction between NiO and LaFeO 3 ; the high LaFeO 3 was more conducive to the formation of a stronger NiO-support interaction under the same hydrothermal temperature. Two reduction peaks appeared at approximately 415 and 480 • C for NiO/1LSBA-140, while significantly higher positions (460 and 669 • C) were observed for NiO/5LSBA-140. Moreover, the interaction of the NiO-support can be further enhanced via the adjustment of hydrothermal temperature. The peak position of NiO/5LSBA-160 is located at 484 and 644 • C, which should be attributed to the reduction peaks of amorphous NiO species having stronger interaction with the LaFeO 3 which can be retained as highly dispersed active Ni centers after reduction [23]. However, the reduction peak temperature was significantly reduced to 423 • C after the addition of Pt precious metal, which was assignable to a stronger interaction of Ni-O-Pt than that of the NiO-supports [31].

H2-TPR for Catalysts
To understand the impact of the high SSA LaFeO3 carrier on the reductivity of large amounts of active O species of catalysts under various conditions (hydrothermal temperature, concentration and Pt additive), H2-TPR experiments were performed, and the reflected results are shown in Figure 4. It was found that the reduction peak can be effectively lagged by inducing the LaFeO3 owing to the strong interaction between NiO and LaFeO3; the high LaFeO3 was more conducive to the formation of a stronger NiO-support interaction under the same hydrothermal temperature. Two reduction peaks appeared at approximately 415 and 480 °C for NiO/1LSBA-140, while significantly higher positions (460 and 669 °C) were observed for NiO/5LSBA-140. Moreover, the interaction of the NiOsupport can be further enhanced via the adjustment of hydrothermal temperature. The peak position of NiO/5LSBA-160 is located at 484 and 644 °C, which should be attributed to the reduction peaks of amorphous NiO species having stronger interaction with the LaFeO3 which can be retained as highly dispersed active Ni centers after reduction [23]. However, the reduction peak temperature was significantly reduced to 423 °C after the addition of Pt precious metal, which was assignable to a stronger interaction of Ni-O-Pt than that of the NiO-supports [31].

XANES Spectra for Catalysts
According to the above discussion on the dispersion as well as reducibility of NiO loaded on the high SSA LaFeO3-SBA-15-CTA catalysts, it was found that the introduction of high SSA LaFeO3-SBA-15-CTA with the optimized content (50 wt.%) under the adjusted

XANES Spectra for Catalysts
According to the above discussion on the dispersion as well as reducibility of NiO loaded on the high SSA LaFeO 3 -SBA-15-CTA catalysts, it was found that the introduction of high SSA LaFeO 3 -SBA-15-CTA with the optimized content (50 wt.%) under the adjusted hydrothermal environment (160 • C) could enhance the interaction of NiO-supports, and improve the dispersion of Ni active species, leading to better activity and sintering resistance during the DRM reaction. XANES is an effective tool for analyzing the valence state of metal elements [32]. As presented in Figure 5, the metallic state of Ni can be well retained by introducing the optimized content of LaFeO 3 and alloying of Pt-Ni compared to the XANES spectra of Ni foil and NiO, being consistent with what is studied in the literature [33,34]. It was confirmed that the addition of both LaFeO 3 and Pt plays a key role in stabilizing the metallic state of active Ni species, most probably through the strong interaction between Ni and high SSA mesoporous LaFeO 3 -silica (LSBA) matrix. However, the Ni-Pt nanoparticles present a stronger interaction than that of the Ni-LaFeO 3 species due to their intrinsic properties, which are proven by numerous studies [35,36]. Therefore, it was inferred that the alloying of Ni-Pt could enhance their tolerance to carbon coking more than that of a Pt-free Ni/5LSBA-160 catalyst.

Catalytic Activity in DRM Reaction
Figure 6a-c depict the catalytic activity of the series of Ni/yLSBA-140 catalysts. It was found that the most optimized doping content of LaFeO3 was listed as 50 wt.%, and corresponding catalysts (Ni/5LSBA-140) exhibited higher catalytic performance and thermal stability (48 h) compared to the undoped 5Ni/SBA-15-CTA catalyst [24], where the CO2 conversion (Figure 6a), CH4 conversion (Figure 6b), H2/CO molar ratio (Supplementary Material Figure S2a) and H2 selectivity (Figure 6c) were increased to 70.4%, 66.0%, 87.5% and 86.5%, respectively. Moreover, their catalytic activity was further promoted by controlling the hydrothermal temperature, as Figure 6d-f displays. Notably, the corresponding activity values were increased to 72.1%, 65.5%, 91.4% and 92.0% over the Ni/5LSBA-160 catalyst. This indicates that the catalytic performance and thermal stability, namely CH4 conversion (Figure 6d), CO2 conversion (Figure 6e), H2/CO molar ratio (Supplementary Material Figure S2b) and H2 selectivity (Figure 6f), was significantly enhanced by La-FeO3 addition as well as the adjustment of the hydrothermal conditions.

Catalytic Activity in DRM Reaction
Figure 6a-c depict the catalytic activity of the series of Ni/yLSBA-140 catalysts. It was found that the most optimized doping content of LaFeO 3 was listed as 50 wt.%, and corresponding catalysts (Ni/5LSBA-140) exhibited higher catalytic performance and thermal stability (48 h) compared to the undoped 5Ni/SBA-15-CTA catalyst [24], where the CO 2 conversion (Figure 6a), CH 4 conversion (Figure 6b), H 2 /CO molar ratio (Supplementary Material Figure S2a) and H 2 selectivity (Figure 6c) were increased to 70.4%, 66.0%, 87.5% and 86.5%, respectively. Moreover, their catalytic activity was further promoted by controlling the hydrothermal temperature, as Figure 6d-f displays. Notably, the corresponding activity values were increased to 72.1%, 65.5%, 91.4% and 92.0% over the Ni/5LSBA-160 catalyst. This indicates that the catalytic performance and thermal stability, namely CH 4 conversion (Figure 6d), CO 2 conversion (Figure 6e), H 2 /CO molar ratio (Supplementary Material Figure S2b) and H 2 selectivity (Figure 6f), was significantly enhanced by LaFeO 3 addition as well as the adjustment of the hydrothermal conditions.

Temperature Programmed Reaction
It was confirmed that the dispersion or the particle sizes of active Ni nanospecies could determine the catalytic activity of Ni-based catalysts for DRM. The well-dispersion Ni particles lead to high catalytic activity [37]. The introduction of the noble metal of Pt improves the dispersion of nickel due to a stronger interaction of Ni-Pt alloy compared to that of the Ni-LaFeO3 [30]. In this contribution, it can be observed that the conversion of CO2 ( Figure 6g) and CH4 (Figure 6h), H2/CO molar ratio (Supplementary Material Figure  S2c) and H2 selectivity (Figure 6i) over the Pt-decorated Ni/LaFeO3-SBA-CTA (PtNi/5LSBA-160) catalyst exhibited higher catalytic activity and maintained better stable catalytic activity than that of the Pt-free Ni/LaFeO3-SBA-CTA (Ni/5LSBA-160) sample. Moreover, Temperature Programmed Surface Reactions (TPSR-MS) were performed to illustrate the alloying effects of Pt on catalytic performance, as depicted in Figure 7. On the one hand, it was found that there exists a lower temperature for the DRM reaction being initiated over the Pt-doped 5Ni/5LSBA-160 catalyst with a higher reaction rate than the undoped 5Ni/5LSBA-160 sample from the MS signals of the species detected, suggesting that the alloying of the Ni-Pt/5LSBA-160 catalyst process has a stronger capability for activating CO2 and CH4 than that of the undoped Ni/5LSBA-160 catalyst. On the other hand, the initial temperature for CO2 conversion was obviously lower than that of the CH4 conversion over both catalysts, which corresponds well to the catalytic activity. This should mainly be attributed to the reversed water gas shift (RWGS) side reaction (Equation (4)), co-existing with DRM [38]. However, it can be inferred that the alloying Pt-Ni nanoparticles improve their interaction to receive better activity, stability and resistance to carbon deposition. Ni/5LSBA-120 Ni/5LSBA-140 Ni/5LSBA-160

Temperature Programmed Reaction
It was confirmed that the dispersion or the particle sizes of active Ni nanospecies could determine the catalytic activity of Ni-based catalysts for DRM. The well-dispersion Ni particles lead to high catalytic activity [37]. The introduction of the noble metal of Pt improves the dispersion of nickel due to a stronger interaction of Ni-Pt alloy compared to that of the Ni-LaFeO 3 [30]. In this contribution, it can be observed that the conversion of CO 2 ( Figure 6g) and CH 4 (Figure 6h), H 2 /CO molar ratio (Supplementary Material Figure S2c) and H 2 selectivity (Figure 6i) over the Pt-decorated Ni/LaFeO 3 -SBA-CTA (PtNi/5LSBA-160) catalyst exhibited higher catalytic activity and maintained better stable catalytic activity than that of the Pt-free Ni/LaFeO 3 -SBA-CTA (Ni/5LSBA-160) sample. Moreover, Temperature Programmed Surface Reactions (TPSR-MS) were performed to illustrate the alloying effects of Pt on catalytic performance, as depicted in Figure 7. On the one hand, it was found that there exists a lower temperature for the DRM reaction being initiated over the Pt-doped 5Ni/5LSBA-160 catalyst with a higher reaction rate than the undoped 5Ni/5LSBA-160 sample from the MS signals of the species detected, suggesting that the alloying of the Ni-Pt/5LSBA-160 catalyst process has a stronger capability for activating CO 2 and CH 4 than that of the undoped Ni/5LSBA-160 catalyst. On the other hand, the initial temperature for CO 2 conversion was obviously lower than that of the CH 4 conversion over both catalysts, which corresponds well to the catalytic activity. This should mainly be attributed to the reversed water gas shift (RWGS) side reaction (Equation (4)), co-existing with DRM [38]. However, it can be inferred that the alloying Pt-Ni nanoparticles improve their interaction to receive better activity, stability and resistance to carbon deposition.

TG for Spent Catalysts
TGA analysis was proved as an effective technique to evaluate the tolerance capacity to carbon-coking for DRM catalysts. As displayed in Figure 8a, it was found that the weight loss profiles of the spent catalysts showed an inverted volcanic shape (inserted image of Figure 8a) with the increase of LaFeO3 contents up to 70 wt.%. Over the Ni/5LSBA-140 catalyst (spent for 12 h), only 8.1% weight loss was detected, which might be closely associated with the enhanced interaction of Ni-LaFeO3. From a practical point of view, having higher activity and thermal stability for catalysts is urgently needed. Figure 8b show the weight loss curves of the spent Ni (Pt)/5LSBA-T (T = 120, 140 and 160 °C) catalysts for 48 h. It can be seen that the weight loss increased with the increase of hydrothermal temperature up to 160 °C and the introduction of noble Pt, which might be related to enhanced catalytic performance. The weight loss for the spent Ni/5LSBA-140 catalyst for 48 h was 10.2%, slightly higher than the spent catalyst for 12 h (8.1%), while the weight loss over the NiPt/5LSBA-160 catalyst was increased to 35.8%. However, the types of carbonaceous species deposited on the spent Pt-doped Ni/5LSBA-160 and Pt-free Ni/5LSBA-160 catalysts are evidently different, as shown in the inserted picture of Figure 8b. The DTA peak (643 °C) for the Pt-doped Ni/5LSBA-160 catalyst was lower than that of the Ptfree Ni/5LSBA-160 sample (655 °C), indicating the carbon deposits on the NiPt/5LSBA-160 catalyst were more reactive and easily removed by oxidation under the DRM process to meet the practical application [39].  48 h (b), it was noted that the inserted image of (a) displayed the weight loss trends for the used catalyst, the inserted image of (b) presented the decomposition temperature of carbon species.

TG for Spent Catalysts
TGA analysis was proved as an effective technique to evaluate the tolerance capacity to carbon-coking for DRM catalysts. As displayed in Figure 8a, it was found that the weight loss profiles of the spent catalysts showed an inverted volcanic shape (inserted image of Figure 8a) with the increase of LaFeO 3 contents up to 70 wt.%. Over the Ni/5LSBA-140 catalyst (spent for 12 h), only 8.1% weight loss was detected, which might be closely associated with the enhanced interaction of Ni-LaFeO 3 . From a practical point of view, having higher activity and thermal stability for catalysts is urgently needed. Figure 8b show the weight loss curves of the spent Ni (Pt)/5LSBA-T (T = 120, 140 and 160 • C) catalysts for 48 h. It can be seen that the weight loss increased with the increase of hydrothermal temperature up to 160 • C and the introduction of noble Pt, which might be related to enhanced catalytic performance. The weight loss for the spent Ni/5LSBA-140 catalyst for 48 h was 10.2%, slightly higher than the spent catalyst for 12 h (8.1%), while the weight loss over the NiPt/5LSBA-160 catalyst was increased to 35.8%. However, the types of carbonaceous species deposited on the spent Pt-doped Ni/5LSBA-160 and Ptfree Ni/5LSBA-160 catalysts are evidently different, as shown in the inserted picture of Figure 8b. The DTA peak (643 • C) for the Pt-doped Ni/5LSBA-160 catalyst was lower than that of the Pt-free Ni/5LSBA-160 sample (655 • C), indicating the carbon deposits on the NiPt/5LSBA-160 catalyst was more reactive and easily removed by oxidation under the DRM process to meet the practical application [39].

TG for Spent Catalysts
TGA analysis was proved as an effective technique to evaluate the tolerance capacity to carbon-coking for DRM catalysts. As displayed in Figure 8a, it was found that the weight loss profiles of the spent catalysts showed an inverted volcanic shape (inserted image of Figure 8a) with the increase of LaFeO3 contents up to 70 wt.%. Over the Ni/5LSBA-140 catalyst (spent for 12 h), only 8.1% weight loss was detected, which might be closely associated with the enhanced interaction of Ni-LaFeO3. From a practical point of view, having higher activity and thermal stability for catalysts is urgently needed. Figure 8b show the weight loss curves of the spent Ni (Pt)/5LSBA-T (T = 120, 140 and 160 °C) catalysts for 48 h. It can be seen that the weight loss increased with the increase of hydrothermal temperature up to 160 °C and the introduction of noble Pt, which might be related to enhanced catalytic performance. The weight loss for the spent Ni/5LSBA-140 catalyst for 48 h was 10.2%, slightly higher than the spent catalyst for 12 h (8.1%), while the weight loss over the NiPt/5LSBA-160 catalyst was increased to 35.8%. However, the types of carbonaceous species deposited on the spent Pt-doped Ni/5LSBA-160 and Pt-free Ni/5LSBA-160 catalysts are evidently different, as shown in the inserted picture of Figure 8b. The DTA peak (643 °C) for the Pt-doped Ni/5LSBA-160 catalyst was lower than that of the Ptfree Ni/5LSBA-160 sample (655 °C), indicating the carbon deposits on the NiPt/5LSBA-160 catalyst were more reactive and easily removed by oxidation under the DRM process to meet the practical application [39].  48 h (b), it was noted that the inserted image of (a) displayed the weight loss trends for the used catalyst, the inserted image of (b) presented the decomposition temperature of carbon species.  48 h (b), it was noted that the inserted image of (a) displayed the weight loss trends for the used catalyst, the inserted image of (b) presented the decomposition temperature of carbon species.

Conclusions
In this contribution, a series of mesoporous perovskites with large SSAs were successfully prepared by the in-situ growth of LaFeO 3 on mesoporous SBA-15-CTA supports under a hydrothermal process. The optimized content (50 wt.%) of LaFeO 3 was used as a Ni-based catalyst support to synthesize DRM catalysts of Ni/5LSBA-160. It was found that the SSA of mesoporous 5LaFeO 3 -SBA-15-CTA can be up to 180 m 2 /g, which displays it as an excellent DRM catalysts carrier candidate to obtain enhanced catalytic activity and anti-coking properties due to the controllable interaction of Ni-LaFeO 3 by adjusting the content of LaFeO 3 and hydrothermal temperature (e.g., 160 • C). Moreover, adding noble Pt over Ni/5LSBA-160 catalyst would further enhance the interaction between Ni and the support to promote the dispersion of active Ni species and achieve a higher syngas formation rate as the TPSR depicted. In addition, the capacity of anti-coking and resistance to sintering can also be improved compared to the Pt-free Ni/5LSBA-160 catalyst sample. This study will pave the way for designing high SSA mesoporous perovskite and utilizing it in heterogeneous catalysis.