Study on Methanol Oxidation at Pt and PtRu Electrodes by Combining in situ Infrared Spectroscopy and Differential Electrochemical Mass Spectrometry

Methanol oxidation reaction （MOR） at Pt and Pt electrode surface deposited with various amounts of Ru （denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML） in 0.1 mol/L HClO4＋0.5 mol/L MeOH has been studied under potentiostatic conditions by in situ FTIR spectroscopy in attenuated-total-reflection con guration and di erential electro-chemical mass spectrometry under controlled flow conditions. Results reveal that （i） CO is the only methanol-related adsorbate observed by IR spectroscopy at all the Pt and PtRu electrodes examined at potentials from 0.3 V to 0.6 V （vs. RHE）; （ii） at Pt0.56Ru0.44, two IR bands, one from CO adsorbed at Ru islands and the other from COL at Pt substrate are detected, while at other electrodes, only a single band for COL adsorbed at Pt is observed; （iii） MOR activity decreases in the order of Pt0.73Ru0.27〉Pt0.56Ru0.44〉Pt0.83Ru0.17〉Pt; （iv） at 0.5 V, MOR at Pt0.73Ru0.27 reaches a current e ciency of 50% for CO2 production, the turn-over frequency from CH3OH to CO2 is ca. 0.1 molecule/（site sec）. Suggestions for further improving of PtRu catalysts for MOR are provided.

In situ Fourier Transform Infrared Spectroscopy Diagnostic for Characterization and Performance Test of Catalysts

The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy （FTIR） for the investigation of the crystal structure, thermal stability, redox behavior （temperature-programmed reduction/temperatureprogrammed re-oxidation） as well as the catalytic properties of Co3O4 thin films. The syntheses of Co3O4 were achieved by chemical vapor deposition in the temperature range of 400-500℃. The structure analysis of the as-prepared material revealed the presence of two prominent IR bands peaking at 544 cm-1 （υ1） and 650 cm-1 （υ2） respectively, which originate from the stretching vibrations of the Co-O bond, characteristic of the Co3O4 spinel. The lattice stability limit of Co3O4 was estimated to be above 650℃. The redox properties of the spinel structure were determined by integrating the area under the emission bands υ1 and υ2 as a function of the temperature. Moreover, Co3O4 has been successfully tested as a catalyst towards complete oxidation of dimethyl ether below 340 ℃. The exhaust gas analysis during the catalytic process by in situ absorption FTIR revealed that only CO2 and H2O were detected as the final products in the catalytic reaction. The redox behavior suggests that the oxidation of dimethyl ether over Co3O4 follows a Mars-van Krevelen type mechanism. The comprehensive application of in situ FTIR provides a novel diagnostic tool in characterization and performance test of catalysts.

In situ studies on ceria promoted cobalt oxide for CO oxidation

In situ studies of catalysts play valuable roles in observing phase transformation, understanding the corresponding surface chemistry and the mechanism of the reaction. In this paper, ceria promoted cobalt oxide was prepared by the calcination method and investigated for the CO oxidation. The microstructure and morphology of CeO2-Co3O4 were investigated by the Scanning Electron Microscope, High-resolution transmission electron microscopy, Raman and X-ray photoelectron spectroscopy characterization. The effect of CeO2 doping on Co3O4 for CO oxidation was characterized by in situ X-ray Diffraction (in situ XRD) and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS). In situ XRD was carried out under H2 atmosphere to evaluate the redox property of catalysts. The results indicated that the ceria doping can enhance the reducibility of Co2+ and promote the Co3+-Co2+-Co3+ cycle, owing to the oxygen replenish property of CeO2. Furthermore, adsorbed carbonate species on the surface of CeO2-Co3O4 were investigated by in situ-DRIFTS experiment. It was turned out that carbonate species on ceria promoted cobalt oxide catalysts showed different IR peaks compared with pure cobalt oxide. The carbonate species on ceria promoted catalyst are more active, and similar to free state carbonate species with weak bonding to catalyst surface, which can effectively inhibit catalyst inactivation. This study revealed the mechanism of ceria promoting CO oxidation over cobalt oxide, which will provide theoretical support for the design of efficient CO oxidation catalysts.

Facile synthesis of Bi_(12)O_(17)Br_2 and Bi_4O_5Br_2 nanosheets:In situ DRIFTS investigation of photocatalytic NO oxidation conversion pathway

Bi12O17Br2and Bi4O5Br2visible‐light driven photocatalysts,were respectively fabricated by hydrothermal and room‐temperature deposition methods with the use of BiBr3and NaOH as precursors.Both Bi12O17Br2and Bi4O5Br2were composed of irregular nanosheets.The Bi4O5Br2nanosheets exhibited high and stable visible‐light photocatalytic efficiency for ppb‐level NO removal.The performance of Bi4O5Br2was markedly higher than that of the Bi12O17Br2nanosheets.The hydroxyl radical(?OH)was determined to be the main reactive oxygen species for the photo‐degradation processes of both Bi12O17Br2and Bi4O5Br2.However,in situ diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that Bi12O17Br2and Bi4O5Br2featured different conversion pathways for visible light driven photocatalytic NO oxidation.The excellent photocatalytic activity of Bi4O5Br2resulted from a high surface area and large pore volumes,which facilitated the transport of reactants and intermediate products,and provided more active sites for photochemical reaction.Furthermore,the Bi4O5Br2nanosheets produced more?OH and presented stronger valence band holeoxidation.In addition,the oxygen atoms of NO could insert into oxygen‐vacancies of Bi4O5Br2,whichprovided more active sites for the reaction.This work gives insight into the photocatalytic pollutant‐degradation mechanism of bismuth oxyhalide.

Promotional roles of ZrO_2 and WO_3 in V_2O_5-WO_3/TiO_2-ZrO_2 catalysts for NO_x reduction by NH_3:Catalytic performance,morphology,and reaction mechanism

V2O5/TiO2-ZrO2 catalysts containing various amounts of WO3 were synthesized.The catalyst morphologies,catalytic performances,and reaction mechanisms in the selective catalytic reduction of NOx by NH3 were investigated using in situ diffuse-reflectance infrared Fourier-transform spectroscopy,temperature-programmed reduction（TPR）,X-ray diffraction,and the Brunauer-Emmett-Teller（BET） method.The BET surface area of the triple oxides increased with increasing ZrO2 doping but gradually decreased with increasing WO3 loading.Addition of sufficient WO3 helped to stabilize the pore structure and the combination of WO3 and ZrO2 improved dispersion of all the metal oxides.The mechanisms of reactions using V2O5-9%WO3/TiO2-ZrO2 and V2O5-9%WO3/TiO2were compared by using either a single or mixed gas feed and various pretreatments.The results suggest that both reactions followed the Eley-Ridel mechanism;however,the dominant acid sites,which depended on the addition of WO3 or ZrO2,determined the pathways for NOx reduction,and involved[NH4^＋-NO-Bronsted acid site]^＊ and[NH2-NO-Lewis acid site]^＊ intermediates,respectively.NH3-TPR and H2-TPR showed that the metal oxides in the catalysts were not reduced by NH3 and O2did not reoxidize the catalyst surfaces but participated in the formation of H2O and NO2.

Resistance to SO_2 poisoning of V_2O_5/TiO_2-PILC catalyst for the selective catalytic reduction of NO by NH_3

A titania pillared interlayered clay（Ti-PILC） supported vanadia catalyst（V2O5/TiO2-PILC） was prepared by wet impregnation for the selective catalytic reduction（SCR） of NO with ammonia. Compared to the traditional V2O5/TiO2 and V2O5-MoO3/TiO2 catalysts, the V2O5/TiO2-PILC catalyst exhibited a higher activity and better SO2 and H2O resistance in the NH3-SCR reaction. Characterization using TPD, in situ DRIFT and XPS showed that surface sulfate and/or sulfite species and ionic SO4^（2-）species were formed on the catalyst in the presence of SO2. The ionic SO4^（2-） species on the catalyst surface was one reason for deactivation of the catalyst in SCR. The formation of the ionic SO4^（2-） species was correlated with the amount of surface adsorbed oxygen species. Less adsorbed oxygen species gave less ionic SO4^（2-） species on the catalyst.

Enhanced plasmonic photocatalysis by SiO_2@Bi microspheres with hot-electron transportation channels via Bi–O–Si linkages

The semimetal Bi has received increasing interest as an alternative to noble metals for use in plasmonic photocatalysis. To enhance the photocatalytic efficiency of metallic Bi, Bi microspheres modified by SiO2 nanoparticles were fabricated by a facile method. Bi-O-Si bonds were formed between Bi and SiO2, and acted as a transportation channel for hot electrons. The SiO2@Bi microspheres exhibited an enhanced plasmon-mediated photocatalytic activity for the removal of NO in air under 280 nm light irradiation, as a result of the enlarged specific surface areas and the promotion of electron transfer via the Bi-O-Si bonds. The reaction mechanism of photocatalytic oxidation of NO by SiO2@Bi was revealed with electron spin resonance and in situ diffuse reflectance infrared Fourier transform spectroscopy experiments, and involved the chain reaction NO -> NO2 -> NO3- with center dot OH and center dot O-2(-) radicals as the main reactive species. The present work could provide new insights into the in-depth mechanistic understanding of Bi plasmonic photocatalysis and the design of high-performance Bi-based photocatalysts. (C) 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Improving visible-light-driven photocatalytic NO oxidation over BiOBr nanoplates through tunable oxygen vacancies

In this work,a series of BiOBr nanoplates with oxygen vacancies(OVs)were synthesized by a solvothermal method using a water/ethylene glycol solution.The number of OVs and facets of BiOBr were tuned by changing the water/ethylene glycol ratio.Although the role of OVs in photocatalysis has been investigated,the underlying mechanisms of charge transfer and reactant activation remain unknown.To unravel the effect of OVs on the reactant activation and photocatalytic NO oxidation process,in situ diffuse reflectance infrared Fourier transform spectroscopy,so‐called DRIFTS,and theoretical calculations were performed and their results combined.The photocatalytic efficiency of the as‐prepared BiOBr was significantly increased by increasing the amount of OVs.The oxygen vacancies had several effects on the photocatalysts,including the introduction of intermediate energy levels that enhanced light absorption,promoted electron transfer,acted as active sites for catalytic reaction and the activation of oxygen molecules,and facilitated the conversion of the intermediate products to the final product,thus increasing the overall visible light photocatalysis efficiency.The present work provides new insights into the understanding of the role of OVs in photocatalysts and the mechanism of photocatalytic NO oxidation.

Surface Modification of (001) Facets Dominated TiO2 with Ozone for Adsorption and Photocatalytic Degradation of Gaseous Toluene

This study investigated the positive effect of surface modification with ozone on the photocatalytic performance of anatase TiO2 with dominated（001） facets for toluene degradation.The performance of photocatalyst was tested on a home-made volatile organic compounds degradation system. The ozone modification, toluene adsorption and degradation mechanism were established by a combination of various characterization methods, in situ diffuse reflectance infrared fourier transform spectroscopy, and density functional theory calculation.The surface modification with ozone can significantly enhance the photocatalytic degradation performance for toluene. The abundant unsaturated coordinated 5 c-Ti sites on（001）facets act as the adsorption sites for ozone. The formed Ti–O bonds reacted with H2O to generate a large amount of isolated Ti5 c-OH which act as the adsorption sites for toluene,and thus significantly increase the adsorption capacity for toluene. The outstanding photocatalytic performance of ozone-modified TiO2 is due to its high adsorption ability for toluene and the abundant surface hydroxyl groups, which produce very reactive OH·radicals under irradiation. Furthermore, the O2 generated via ozone dissociation could combine with the photogenerated electrons to form superoxide radicals which are also conductive to the toluene degradation.

N_(2)photofixation promoted by in situ photoinduced dynamic iodine vacancies at step edge in Bi_(5)O_(7)I nanotubes

Heterogeneous photosynthesis is a promising route for sustainable ammonia production,which can utilize renewable energy and water as the hydrogen source under ambient condition.In this study,a series of Bi_(5)O_(7)I(BOI)nanosheets and nanotubes are synthesized,the surface tensile strain is formed by curling the nanosheets into nanotubes to tune the concentration and location of dynamic vacancies.Scanning transmission electron microscopy(STEM)with spherical aberration correction confirms the presence of intrinsic areal defects on the surface of the BOI nanotube resulted from surface tensile strain.The presence of areal defects lowers the formation energy of I vacancies(IV)at step edge site,thus the IV with higher concentration would be favorably generated under visible light.Rapid scan in situ Fourier transform infrared(FT-IR)analysis in the aqueous media reveals that the IV promotes photocatalytic N_(2) activation and reduction,proceeds through an associative alternating mechanism.Specially,after turning off the light,the surface vacancy sites can be reoccupied by I−ions,which enables the protection and regeneration of photocatalyst surface in an aerobic and dark environment.This work provides an innovative strategy to tune concentration and location of dynamic surface vacancies on photocatalysts by building surface tensile strain for advancing sustainable ammonia production.

Cu/Mo2C synthesized through Anderson-type polyoxometalates modulate interfacial water structure to achieve hydrogen evolution at high current density

The development of efficient non-precious metal catalysts is important for the large-scale application of alkaline hydrogen evolution reaction(HER).Here,we synthesized a composite catalyst of Cu and Mo_(2)C(Cu/Mo_(2)C)using Anderson-type polyoxometalates(POMs)synthesized by the facile soaking method as precursors.The electronic interaction between Cu and Mo_(2)C drives the positive charge of Cu,alleviating the strong adsorption of hydrogen at the Mo site by modulating the d-band center of Mo_(2)C.By studying the interfacial water structure using in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS),we determined that the positively charged Cu crystals have the function of activating water molecules and optimizing the interfacial water structure.The interfacial water of Cu/Mo_(2)C contains a large amount of free water,which could facilitate the transport of reaction intermediates.Due to activated water molecules and optimized interfacial water structure and hydrogen adsorption energy,the overpotential of Cu/Mo_(2)C is 24 mV at a current density of 10 mA·cm^(-2) and 178 mV at a current density of 1000 mA·cm^(-2).This work improves catalyst performance in terms of interfacial water structure optimization and deepens the understanding of water-mediated catalysis.

In situ DRIFTS study of photocatalytic CO_(2) reduction under UV irradiation

Photocatalytic reduction of CO_(2) on TiO_(2) and Cu/TiO_(2) photocatalysts was studied by in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)under UV irradiation.The photocatalysts were prepared by sol-gel method via controlled hydrolysis of titanium(IV)butoxide.Copper precursor was loaded onto TiO_(2) during sol-gel procedure.A large amount of adsorbed H_(2)O and surface OH groups was detected at 25℃on the TiO_(2) photocatalyst after being treated at 500℃under air stream.Carbonate and bicarbonate were formed rapidly due to the reaction of CO_(2) with oxygen-vacancy and OH groups,respectively,on TiO_(2) surface upon CO_(2)adsorption.The IR spectra indicated that,under UV irradiation,gas-phase CO_(2) further combined with oxygen-vacancy and OH groups to produce more carbonate or bicarbonate.The weak signals of reaction intermediates were found on the IR spectra,which were due to the slow photocatalytic CO_(2) reduction on photocatalysts.Photogenerated electrons merge with H^(+)ions to form H atoms,which progressively reduce CO_(2) to form formic acid,dioxymethylene,formaldehyde and methoxy as observed in the IR spectra.The well-dispersed Cu,acting as the active site significantly increases the amount of formaldehyde and dioxymethylene,thus promotes the photoactivity of CO_(2) reduction on Cu/TiO_(2).A possible mechanism of the photocatalytic CO_(2) reduction is proposed based on these intermediates and products on the photocatalysts.

Effects of Activation Atmospheres on Structure and Activity of Mo-based Catalyst for Synthesis of Higher Alcohols

Activated carbon supported Mo-based catalysts were prepared and reduced under different activation atmospheres, including pure H2, syngas （H2/CO=2/1）, and pure CO. The cat- alysts structures were characterized by X-ray diffraction , X-ray absorption fine structure, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The catalytic per- formance for the higher alcohol synthesis from syngas was tested. The pure H2 treatment showed a high reduction capacity. The presence of a large amount of metallic CoO and low valence state Mo^φ＋ （0〈φ〈2） on the surface suggested a super activity for the CO dissoci- ation and hydrogenation, which promoted hydrocarbons formation and reduced the alcohol selectivity. In contrast, the pure CO-reduced catalyst had a low reduction degree. The Mo and Co species at the catalyst mainly existed in the form of Mo^4＋ and Co^2＋. The syngas- reduced catalyst showed the highest activity and selectivity for the higher alcohols synthesis. We suggest that the syngas treatment had an appropriate reduction capacity that is between those of pure H2 and pure CO and led to the coexistence of multivalent Co species as well as the enrichment of Mo~＋ on the catalyst＇s surface. The synergistic effects between these active species provided a better cooperativity and equilibrium between the CO dissociation, hydrogenation and CO insertion and thus contributed beneficially to the formation of higher alcohols.

Large anisotropic negative thermal expansion in Cu-TDPAT metalorganic framework:A combined in situ X-ray diffraction and DRIFTS study

Cu-TDPAT(H_(6)TDPAT=2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine),a stable nanoporous metal-organic framework with rht topology,has sparked broad interest as an adsorbent for several chemical separation processes.In this work,in situ synchrotron diffraction experiments followed by sequential LeBail refinements reveal that Cu-TDPAT shows unusually large anisotropic negative thermal expansion(NTE).The PASCal crystallography tool,used to analyze the magnitude of the NTE,reveals an average volumetric thermal expansion coefficientαv=-20.3 MK^(-1).This value is significantly higher than the one reported for Cu-BTC(also known as HKUST-1),which contains the same Cu-paddlewheel building unit,αv=-12 MK^(-1).In situ synchrotron single crystal X-ray diffraction and in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)were employed to shed light on the NTE mechanism.Using these two methods,we were able to elucidate the three main structural motions that are responsible for the NTE effect.The more pronounced NTE behavior of Cu-TDPAT is attributed to the lower symmetry combined with the more complex ligand structure when compared to Cu-BTC.The knowledge obtained in this work is important for understanding the behavior of the adsorbent under transient variable temperature conditions in fixed adsorption beds.

Coordinately unsaturated nickel single atom electrocatalyst for efficient CO_(2)conversion

Single-atom catalysts(SACs)have shown unexpected catalytic activity due to their unique electronic structure and coordination environment.Nonetheless,the synthesis of an atomically precise low-coordination single-atom catalyst remains a grand challenge.Herein,we report a coordinately unsaturated Ni-N_(3)single-atom electrocatalyst using a metal-organic framework(MOF)derived N-C support with abundant exposed N for excellent electrochemical CO_(2)reduction.The obtained Ni-N_(3)/NC active site exhibited highly efficient CO_(2)-to-CO conversion with a Faradaic efficiency of 94.6%at the current density of 100 mA/cm^(2).In situ X-ray absorption spectroscopy(XAS)measurement suggested that the Ni atomic center with unsaturated coordination had the lower initial chemical state and higher charge transfer ability.In situ Fourier transform infrared(FT-IR)and theoretical calculation results revealed that the unsaturated catalytically active center could facilitate activation of CO_(2)and thus heighten CO_(2)electroreduction activity.These findings provided insights into the rational design of definitive coordination structure of SACs for boosting activity and selectivity.

Reaction Mechanism of H2-Assisted C3H6-SCR over Ag-CexZr Catalyst as Investigated by In situ FTIR

A series of silver-doped cerium zirconium oxide(Ag-CevZr)samples was synthesized successfully for selective catalytic reduction of nitric oxide(NO)with hydrogen and propene(H2/C3H6-SCR)under excess oxygen condition.The catalytic activity test proved that Ag-Ce0.4Zr exhibited the best C3H6-SCR activity.Hydrogen(H2)significantly enlianced NO conversion and widened the temperature window.Multi-technology characterizations were conducted to ascertain the properties of fabricated catalysts including X-ray diflraction(XRD),Fourier transform infrared spectrometry(FTIR),scanning electron microscopy(SEM)and H2 temperature programmed reduction(H2-TPR).In situ FTIR results demonstrated that various types of nitrates and chelating nitrite were generated on Ag-CexZr after introduction of NO.Besides,adding H2 could increase the concentration of bidentate nitrate and chelated bidentate nitrate dramatically,especially for Ce0.4Zr catalyst.Transient reaction between pre-adsorbing NO and C3H/C3H6+H2 illuminated that the most active intermediate was chelating nitrite,which was promoted significantly by H2 participation.Furthermore,adding H2 improved the formation of organo-nitro(R-N02),which was the key intennediate in C3H6-SCR.The reaction mechanism over Ag-CexZr catalysts was proposed at 200℃ as follows:nitric oxide(NO)+pr opene(C 3H6)+hy dr ogen(H2)+oxy gen(O2)→chelating nitrite (N O2-)+acry late-type species(CxHyOz)→organo-nitro(R-NO2)→isocyanate(-NCO)+cyanide(—CN)→nitrogen(N2).

Supported Cu/Ni Bimetallic Cluster Electrocatalysts Boost CO_(2) Reduction

Supported metal clusters with the integrated advantages of single-atom catalysts and conventional nanoparticles held great promise in the electrocatalytic carbon dioxide reduction(ECO_(2)R)operated at low overpotential and high current density.However,its precise synthesis and the understanding of synergisti-cally catalytic effects remain challenging.Herein,we report a facile method to synthesize the bimetallic Cu and Ni clusters anchored on porous carbon(Cu/Ni-NC)and achieve an enhanced ECO_(2)R.The aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy were employed to verify the metal dispersion and the coordination of Cu/Ni clusters on NC.As a result of this route,the target Cu/Ni-NC exhibits excellent electrocatalytic performance including a stable 30 h electrolysis at 200 mA cm^(-2) with carbon monoxide Faradaic efficiency of∼95.1%using a membrane electrode assembly electrolysis cell.Combined with the in situ analysis of the surface-enhanced Fourier transform infrared spectroelectrochemistry,we propose that the synergistic effects between Ni and Cu can effectively promote the H_(2)O dissociation,thereby accelerate the hydrogenation of CO_(2)to*COOH and the overall reaction process.

Laser-assisted synthesis of PtPd alloy for efficient ethanol oxidation

The inefficiency of ethanol oxidation reaction(EOR)presents a significant obstacle in harnessing renewable biofuels with high energy density into electricity.Despite efforts,most Pt-based catalysts still suffer from drawbacks such as poor activity and susceptibility to CO poisoning,particularly in acidic conditions.Herein,we employed a physical laser-assisted approach to synthetize a PtPd alloy with a 1:1 atomic ratio.This alloy demonstrates remarkable performance in acidic EOR,boasting a high mass activity of 1.86 A·mgPt^(−1)and competitive resistance to poisoning.Combining in situ synchrotron radiation infrared spectroscopy with theoretical calculations,we reveal that the synergic interaction between Pt and Pd enhances both the adsorption of OH*intermediate and the dehydrogenation ability of ethanol.This work will prove the feasibility of synthesizing bimetallic alloys by a physical laser-assisted strategy and promote the development of advanced alloy electrocatalysts.

Highly efficient photo-thermal synergistic catalysis of CO_(2)methanation over La_(1-x)Ce_(x)NiO_(3)perovskite-catalyst

Solar-driven photo-thermal catalytic CO_(2)methanation reaction is a promising technology to alleviate the problems posed by greenhouse gases emissions.However,designing advanced photo-thermal catalysts remains a research challenge for CO_(2)methanation reaction.In this work,a series of ABO3(A=lanthanide,B=transition metal)perovskite catalysts with Ce-substituted LaNiO3(La_(1-x)Ce_(x)NiO_(3),x=0,0.2,0.5,0.8,1)were synthesized for CO_(2)methanation.The La_(0.2)Ce_(0.8)NiO_(3) exhibited the highest CH_(4) formation rate of 258.9 mmol·g^(-1)·hcat-1,CO_(2)conversion of 55.4%and 97.2%CH_(4) selectivity at 300℃with the light intensity of 2.9 W·cm^(-2).Then the catalysts were thoroughly analyzed by physicochemical structure and optical properties characterizations.The partial substitution of the A-site provided more active sites for the adsorption and activation of CO_(2)/H_(2).The sources of the active sites were considered to be the oxygen vacancies(O_(v))created by lattice distortions due to different species of ions(La^(3+),Ce^(4+),Ce^(3+))and exsolved Ni0 by H_(2)reduction.The catalysts have excellent light absorption absorbance and low electron-hole(e^(-)/h^(+))recombination rate,which greatly contribute to the excellent performance in photo-thermal synergistic catalysis(PTC)CO_(2)methanation.The results of in situ irradiated electron paramagnetic resonance spectrometer(ISI-EPR)and ISI-X-ray photoelectron spectroscopy(XPS)indicated that the aggregation of unpaired electrons near the defects and Ni metal(from La and Ce ions to Ov and Ni0)accelerated adsorption and activation of CO_(2)/H_(2).At last,the catalyst properties and structure were correlated with the proposed reaction mechanism from the in situ diffuse reflection infrared Fourier transform spectrum(DRIFTS)measurements.The in situ precipitation of the B-site enhanced the dispersion of Ni,while its enriched photoelectrons upon illumination further promote hydrogen dissociation.More H^(*)spillover accelerated the rate-determining step(RDS)of HCOO*hydrogenation.This work provides the theoretical basis for the development of catalysts and industrial application.

Phosphorus-doping-tuned PtNi concave nanocubes with high-index facets for enhanced methanol oxidation reaction

Surface engineering has been found to be an efficient strategy to boost the catalytic performance of noble-metal-based nanocatalysts.In this work,a small amount of P was doped to the surface of PtNi concave cube(P-PtNi CNC).Interestingly,the P-PtNi CNC nanocatalyst shows an enhanced methanol oxidation reaction(MOR)performance with achieving 8.19 times of specific activity than that of comercial Pt/C.The electrochemical in situ Fourier transform infrared spectroscopy(FTIR)results reveal that the surface P doping promotes the adsorption energy of OH,enhancing the resistance against CO poisoning.Therefore,the intermediate adsorbed CO(COads)reacted with adsorbed OH(OHads)through the Langmuir–Hinshelwood(LH)mechanism to generate CO_(2)and release surface active sites for further adsorption.This work provides a promising strategy via the incorporation of non-metallic elements into the PtNi alloys bounded with high-index facets(HIFs)as efficient fuel cell catalysts.