As a novel chemical marker,methanol has been widely applied to evaluate the ageing state of insulating paper in recent years.Methanol gas sensor(MGS)could be applied to detect the methanol content in transformer oil f...As a novel chemical marker,methanol has been widely applied to evaluate the ageing state of insulating paper in recent years.Methanol gas sensor(MGS)could be applied to detect the methanol content in transformer oil for its high portability and stability.However,it has the defects of a high limit of detection(LOD)and poor anti-interference performance.Therefore,a novel method of detecting methanol in transformer oil based on MGS with the solid-phase extraction(SPE)technology was investigated in this paper.A detection platform for methanol in transformer oil based on SPE was established,and the SPE experimental process and the crucial parameters were optimised.The results show that the SPE decreased the LOD of MGS from 0.4 to 0.2 ppm and effectively eliminated the interfering substances in oil.Although a part of methanol would be lost during the SPE process,the regression correction coefficient was proposed to correct the evaluation errors.The results indicate that the average relative errors decreased from 17.09%to 4.38%,and the proposed method has good applicability.展开更多
The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synt...The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synthesis technique is reported to fabricate atom-nanoisland-sea structured SACs for the first time.The resultant catalysts are constructed by Pt single atoms on In_(2)O_(3)supported by Co3O4nanoislands uniformly dispersed in the sea of reduced graphene oxide.The laser process,with a maximum temperature of 2349 K within~100μs,produced abundant oxygen vacancies(up to 70.8%)and strong interactions between the Pt single atoms and In_(2)O_(3).The laser-synthesized catalysts exhibited a remarkable catalytic performance towards CO_(2)hydrogenation to methanol at 300°C with a CO_(2)conversion of 30.3%,methanol selectivity of 90.6%and exceptional stability over 48 h without any deactivation,outperforming most of the relevant catalysts reported in the literature.Characterization of the spent catalysts after testing for 48 h reveals that the Pt single atoms were retained and the oxygen vacancies remained almost unchanged.In situ diffuse reflectance infrared Fourier transform spectrum was conducted to establish the reaction mechanism supported by the density functional theory simulations.It is believed that this laser synthesis strategy opens a new avenue towards rapidly manufacturing highly active and robust thermal SACs.展开更多
Methanol-assisted water electrolysis presents a promising yet challenging technique for electrochemical hydrogen production,as limited by the easy poisoning issue of Pt active sites.In this study,we successfully synth...Methanol-assisted water electrolysis presents a promising yet challenging technique for electrochemical hydrogen production,as limited by the easy poisoning issue of Pt active sites.In this study,we successfully synthesized an efficient bifunctional catalyst composed of three-dimensional(3D)flower-like MoTe_(2) embedded nitrogen-doped carbon(NC)nanospheres,assembled by nanosheets,to support Pt nanoparticles(Pt-MoTe_(2)/NC)for methanol-assisted water electrolysis.This innovative Pt-MoTe_(2)/NC catalyst demonstrated superior catalytic performance targeting both hydrogen evolution reaction(HER)and methanol oxidation reaction(MOR)due to the strong metal-support interaction and the promotional effect of oxophilic molybdenum telluride.In situ infrared spectroscopy and CO stripping measurements revealed their excellent anti-poisoning ability.In particular,the onset potential of CO oxidation decreased by 130 mV relative to the standard Pt/C electrode.Theoretical calculations indicated the proper H*adsorption energy for HER and weakened CO adsorption energy for MOR in the optimized electronic structure.Therefore,the Pt-MoTe_(2)/NC electrode achieved the highest forward peak current density(76.6 mA·cm^(−2))for MOR,approximately 2.8-fold that of the commercial Pt/C,and only 34 mV was needed to deliver 10 mA·cm^(−2) for HER in acidic electrolyte.When employed as the bifunctional electrode in methanol electrolysis,Pt-MoTe_(2)/NC enabled efficient hydrogen generation with good stability,requiring merely 0.65 V to achieve 10 mA·cm^(−2),approximately 1090 mV less than traditional water electrolysis.This work presents an anti-poisoning catalyst in energy-saving hydrogen production from methanol electrolysis.展开更多
The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation...The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.展开更多
Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active...Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.展开更多
This work investigates the potential of low-pressure,medium-speed dual-fuel engines for cleaner maritime transportation.The thermodynamic performance of these engines is explored using three alternative fuels:liquefie...This work investigates the potential of low-pressure,medium-speed dual-fuel engines for cleaner maritime transportation.The thermodynamic performance of these engines is explored using three alternative fuels:liquefied natural gas(LNG),methanol,and ammonia.A parametric analysis examines the effect of adjustments to key engine parameters(compression ratio,boost pressure,and air-fuel ratio)on performance.Results show an initial improvement in performance with an increase in compression ratio,which reaches a peak and then declines.Similarly,increases in boost pressure and air-fuel ratio lead to linear performance gains.However,insufficient cooling reduces the amount of fuel burned,which hinders performance.Exergy analysis reveals significant exergy destruction within the engine,which ranges from 69.96%(methanol)to 78.48%(LNG).Notably,the combustion process is the leading cause of exergy loss.Among the fuels tested,methanol exhibits the lowest combustion-related exergy destruction(56.41%),followed by ammonia(62.12%)and LNG(73.77%).These findings suggest that methanol is a promising near-term alternative to LNG for marine fuel applications.展开更多
Iron-Vanadium(FeV)catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde;however,due to its complex compositions,the identification of catalytic active sites still remains ...Iron-Vanadium(FeV)catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde;however,due to its complex compositions,the identification of catalytic active sites still remains challenging,inhibiting the rational design of excellent FeV-based catalysts.Here,in this work,a series of FeV catalysts with various compositions,including FeVO_(4),isolated VO_(x),low-polymerized V_(n)O_(x),and crystalline V_(2)O_(5) were prepared by controlling the preparation conditions,and were applied to methanol oxidation to formaldehyde reaction.A FeV_(1.1) catalyst,which consisted of FeVO_(4) and low-polymerized V_(n)O_(x) species showed an excellent catalytic performance with a methanol conversion of 92.3%and a formaldehyde selectivity of 90.6%,which was comparable to that of conventional iron-molybdate catalyst.The results of CH_(3)OH-IR,O_(2) pulse and control experiments revealed a crucial synergistic effect between FeVO_(4) and low-polymerized V_(n)O_(x).It enhanced the oxygen supply capacity and suitable binding and adsorption strengths for formaldehyde intermediates,contributing to the high catalytic activity and formaldehyde selectivity.This study not only advances the understanding of FeV structure but also offers valuable guidelines for selective methanol oxidation to formaldehyde.展开更多
The direct oxidation of methane to methanol(DOMM) has been recognized as a significant technology for efficiently utilizing low-concentration coalbed methane(LCMM) and supplying liquid fuel.Herein,the noble metals(Pt,...The direct oxidation of methane to methanol(DOMM) has been recognized as a significant technology for efficiently utilizing low-concentration coalbed methane(LCMM) and supplying liquid fuel.Herein,the noble metals(Pt,Pd and Ru) modified Cu/alkalized sepiolite(CuX/SEPA) catalysts were prepared and used for the DOMM in a gas-phase system at low temperatures.The CuRu/SEPA exhibited the highest methanol production of 53 μmol·g^(-1)·h^(-1) and methanol selectivity of 90% under the optimal reaction conditions.Various characterizations demonstrated that the addition of Ru promoted the formation of Cu^(2+)and the contraction of Cu—Si/Al bonds to reduce the distance between framework Al atoms of SEPA to further generate more Al pairs,which facilitated the formation of reactive dicopper species([Cu_(2)O]^(2+)or [Cu_(2)O_(2)]^(2+)).Investigation of the reaction mechanism revealed that [Cu_(2)O]^(2+) or [Cu_(2)O_(2)]^(2+) species could adsorb and activate methane to form CH_(3)O^(*) species and ultimately generated methanol with the assistance of water.展开更多
CuZn-based catalyst is an attractive catalyst for methanol synthesis from CO_(2)hydrogenation,but it early deactivates and its methanol yield still needs to improve.In this study,Y_(2)O_(3)was introduced to Cu/ZnO usi...CuZn-based catalyst is an attractive catalyst for methanol synthesis from CO_(2)hydrogenation,but it early deactivates and its methanol yield still needs to improve.In this study,Y_(2)O_(3)was introduced to Cu/ZnO using a one-pot hydrothermal method,and exhibits a synergistic effect of ZnO and Y_(2)O_(3)on enhancing methanol yield and the stability.We found that the interaction between Y_(2)O_(3)and ZnO results in abundant oxygen vacancies formation,thereby enhancing CO_(2)adsorption and activation.Kinetic analysis and in situ DRIFTS suggest that RWGS forming CO and methanol formation compete for a mutual intermediate HCOO^(*),and the introduction of Y_(2)O_(3)to Cu/ZnO raises the energy barrier for the CO formation but lowers that for methanol formation,thus enhancing the methanol yield on Cu/ZnO/Y_(2)O_(3).展开更多
Designing advanced electrocatalysts with high methanol tolerance in the oxygen reduction reaction process is crucial for the sustainable implementation of direct methanol fuel cells.Herein,we present a Pt/C catalyst m...Designing advanced electrocatalysts with high methanol tolerance in the oxygen reduction reaction process is crucial for the sustainable implementation of direct methanol fuel cells.Herein,we present a Pt/C catalyst modified with black phosphorus(BP)nanodots(BPNDs-Pt/C)by using a facile ultrasonic mixing method.Experimental and computational investigations reveal that the electron transfer from BP to Pt leads to weak adsorption of hydroxyl groups on the Pt surface.As a result,the BPNDs-Pt/C catalyst exhibits efficient activity and anti-methanol ability for cathodic oxygen reduction electrocatalysis in an acidic medium.Additionally,it demonstrates high activity for oxygen reduction reaction(ORR)in an alternative alkaline system with cation exchange membrane and eliminable methanol penetration.This work highlights the feasibility of using non-metallic elements to regulate the electronic structure and surface properties of Pt-based nanomaterials.Furthermore,the designed BPNDs-Pt/C electrocatalyst,with controllable ORR performance,can be applied across various scenarios based on demand.展开更多
Metal-based catalysts are prevalent in the CO_(2) hydrogenation to methanol owing to their remarkable catalytic activity.Herein,Ru/In_(2)O_(3) catalysts with different morphologies obtained by doping Ru into In_(2)O_(...Metal-based catalysts are prevalent in the CO_(2) hydrogenation to methanol owing to their remarkable catalytic activity.Herein,Ru/In_(2)O_(3) catalysts with different morphologies obtained by doping Ru into In_(2)O_(3) with irregular,rod-like,and flower-like morphologies are used for catalytic CO_(2) hydrogenation to methanol.Results indicate that the flower-like Ru/In_(2)O_(3)(Ru/In_(2)O_(3)-F)exhibits higher catalytic performance than Ru/In_(2)O_(3) with other morphologies,achieving a 12.9%CO_(2) conversion,74.02%methanol selectivity,and 671.36 mg_(MeOH) h^(−1) g_(cat)^(−1) methanol spatiotemporal yield.Furthermore,Ru/In_(2)O_(3)-F maintains its catalytic stability over 200 h at 5 MPa and 290℃.The promotional effect mainly stems from the fact that electronic structure of Ru can be effectively adjusted by modulating the morphology of In_(2)O_(3).The strong interaction between atomically dispersed Ru and In_(2)O_(3)-F enhances the structural stability of Ru,inhibiting the agglomeration of the catalyst during the reaction process.Furthermore,density-functional theory calculations reveal that highly dispersed Ru atoms not only perform efficient and rapid electronic gain and loss processes,facilitating the catalytic activation of H_(2) into H intermediates.It also enables the generated reactive H to rapidly overflow to the surrounding In sites to participate in CO_(2) reduction.These findings provide a theoretical basis for the development of high-performance catalysts for CO_(2) hydrogenation.展开更多
ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a signifi...ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a significant synthetic challenge.Herein,we demonstrate the possibility to control the Al distribution in ITR zeolites using zeolite A as an aluminum source(A-ITR).The A-ITR exhibited similar crystallinity,nanosheet morphology,textual parameters,and acidic concentration with those of conventional ITR made zeolites using aluminum isopropoxide as an aluminum source(C-ITR).Characterizations of the zeolite product with^(27)Al MQ.MAS NMR spectra,^(27)Al MAS NMR spectra,and 1-hexene cracking reveal that the A-ITR zeolites have more Al species distributed in T6 and T8 sites located in relatively smaller micropores of the framework than C-ITR.As a result,the A-ITR gave enhanced catalyst lifetime and propylene selectivity due to the suppression of the aromatic cycle in the MTP reaction,compared with the C-ITR.This work provides an alternative approach to prepare efficient ITR zeolites for MTP reaction.展开更多
One-step direct production of methanol from methane and water(PMMW)under mild conditions is challenging in heterogeneous catalysis owing to the absence of highly effective catalysts.Herein,we designed a series of“Sin...One-step direct production of methanol from methane and water(PMMW)under mild conditions is challenging in heterogeneous catalysis owing to the absence of highly effective catalysts.Herein,we designed a series of“Single-Atom”-“Frustrated Lewis Pair”(SA-FLP)dual active sites for the direct PMMW via density functional theory(DFT)calculations combined with a machine learning(ML)approach.The results indicate that the nine designed SA-FLP catalysts are capable of efficiently activate CH4 and H_(2)O and facilitate the coupling of OH^(*)and CH_(3)^(*)into methanol.The DFT-based microkinetic simulation(MKM)results indicate that CH_(3)OH production on Co1-FLP and Pt1-FLP catalysts can reach the turnover frequencies(TOFs)of 1.01×10^(−3)s^(-1)and 8.80×10^(−4)s^(-1),respectively,which exceed the experimentally reported values by three orders of magnitude.ML results unveil that the gradient boosted regression model with 13 simple features could give satisfactory predictions for the TOFs of CH_(3)OH production with RMSE and R^(2)of 0.009 s^(-1)and 1.00,respectively.The ML-predicted MKM results indicate that four catalysts including V_(1-),Fe_(1-),Ti_(1-),and Mn_(1)-FLP exhibit higher TOFs of CH_(3)OH production than the value that the most relevant experiments reported,indicating that the four catalysts are also promising catalysts for the PMMW.This study not only develops a simple and efficient approach for design and screening SA-FLP catalysts but also provides mechanistic insights into the direct PMMW.展开更多
The increasingly serious climate issue compels urgent greenhouse gas mitigation strategies.As a budget,plentiful,renewable feedstock and major contributor to global warming,the large-scale catalytic transformation of ...The increasingly serious climate issue compels urgent greenhouse gas mitigation strategies.As a budget,plentiful,renewable feedstock and major contributor to global warming,the large-scale catalytic transformation of CO_(2)has attracted widespread attention from society due to its potential as a solution to the environment and energy crises.At present,catalytic hydrogenation of carbon dioxide to organic chemicals is the primary approach in its industrial applications.In recent decades,various materials containing Cu-,precious metal-,In-,Zn-,and Ga-based catalysts have been designed for CO_(2)hydrogenation to methanol.Likewise,great advances have been made in CO_(2)-to-chemicals,such as olefins,aromatics,and gasoline by combining CO_(2)-to-CH3OH with methanol transformation or tandem reaction of reverse water-gas shift and Fischer-Tropsch(FT)synthesis.This review exhibits the recent advances in the hydrogenation of CO_(2)-to-CH3OH including the catalyst system,CO_(2)activation,nature of active sites,intermediate species(formate or carboxyl),structure-activity relationship,and reaction mechanism.Finally,challenges and outlooks in CO_(2)hydrogenation to methanol are summarized.展开更多
The sluggish reaction kinetics of the oxygen evolution reaction(OER)and methanol oxidation reaction(MOR)remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells.Considering the vi...The sluggish reaction kinetics of the oxygen evolution reaction(OER)and methanol oxidation reaction(MOR)remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells.Considering the vital role of noble metals in electrocatalytic activity,this work focuses on the rational synthesis of Ni-noble metal composite nanocatalysts for overcoming the drawbacks of high cost and susceptible oxidized surfaces of noble metals.The inherent catalytic activity is improved by the altered electronic structure and effective active sites of the catalyst induced by the size effect of noble metal clusters.In particular,a series of Ni-noble metal nanocomposites are successfully synthesized by partially introducing noble metal into Ni with porous interfacial defects derived from Ni-Al layered double hydroxide(LDH).The Ni_(10)Pd_(1)nanocomposite exhibits high OER catalytic activity with an overpotential of 0.279 V at 10 m A/cm^(2),surpassing Ni_(10)Ag_(1)and Ni_(10)Au_(1)counterparts.Furthermore,the average diameter of Pd clusters gradually increases from 5.57 nm to 44.44 nm with the increased proportion of doped Pd,leading to the passivation of catalytic activity due to the exacerbated surface oxidation of Pd in the form of Pd^(2+).After optimization,Ni_(10)Pd_(1)delivers significantly enhanced OER and MOR electroactivities and long-term stability compared to that of Ni_(2)Pd_(1),Ni_(1)Pd_(1)and Ni_(1)Pd_(2),which is conducive to the effective utilization of Pd and alleviation of surface oxidation.展开更多
Photo-reforming methanol into valuable chemicals represents an energetically sustainable alternative to conventional thermal catalysis,yet controlling-specific C-C coupling way still remains elusive.In this work,we re...Photo-reforming methanol into valuable chemicals represents an energetically sustainable alternative to conventional thermal catalysis,yet controlling-specific C-C coupling way still remains elusive.In this work,we report a sulfide-based photocatalytic paradigm,where atomic-level control of nickel species directly dictates reaction selectivity.The electrostatic constructing ZnIn_(2)S_(4)/Zn_(0.5)Cd_(0.5)S(ZIS/ZCS)heterostructures enable single atom Ni to facilitate ethylene glycol(EG)production with a rate of 11.2 mmol·gcat^(−1)·h^(−1),surpassing reported non-precious metal systems,whereas the Ni aggregates drive exclusive formaldehyde formation.The operando spectroscopy and density functional theory reveal dual roles of Ni as electron reservoir and chemical bond breakage inducers,lowering C-H activation barriers while stabilizing·CH2OH intermediates for cross-coupling.This interfacial configuration engineering creates an electron highway that couples carrier dissociation with radical recombination kinetics,achieving atom-economic steering of methanol oxidative valorization.The metal dispersion assisting catalysis correlation here provides a design blueprint for selective bond scission and reconstruction in sustainable organic synthesis.展开更多
Alloying and interface effects are effective strategies for enhancing the performance of electrocatalysts in energy-related devices.Herein,dendritic Au-doped platinum-palladium alloy/dumbbell-like bismuth telluride he...Alloying and interface effects are effective strategies for enhancing the performance of electrocatalysts in energy-related devices.Herein,dendritic Au-doped platinum-palladium alloy/dumbbell-like bismuth telluride heterostructures(denoted PtPdAu/BiTe)were synthesized using a visible-light-assisted strategy.The coupling alloy and interfacial effects of PtPdAu/BiTe significantly improved the performance and stability of both the ethanol oxidation reaction(EOR)and methanol oxidation reaction(MOR).Introducing a small amount of Au effectively enhanced the CO tolerance of PtPdAu/BiTe compared to dendritic platinum-palladium alloy/dumbbell-like bismuth telluride heterostructures.PtPdAu/BiTe exhibited mass activities of 31.5 and 13.3 A·mg_(Pt)^(-1)in EOR and MOR,respectively,which were 34.4 and 13.2 times higher than those of commercial Pt black,revealing efficient Pt atom utilization.In-situ Fourier transform infrared spectroscopy demonstrated complete 12e^(-)and 6e^(-)oxidation of ethanol and methanol on PtPdAu/BiTe.The PtPdAu/BiTe/C achieved mass peak power densities of 131 and 156 mW·mg_(Pt)^(-1),which were 2.4 and 2.2 times higher than those of Pt/C in practical direct ethanol fuel cell(DEFC)and direct methanol fuel cell(DMFC),respectively,highlighting their potential application in DEFC and DMFC.This study introduces an effective strategy for designing efficient and highly CO tolerant anodic electrocatalysts for practical DEFC and DMFC applications.展开更多
Against the backdrop of global energy and environmental crises,the technology of CO_(2)hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution.Bimet...Against the backdrop of global energy and environmental crises,the technology of CO_(2)hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution.Bimetallic oxide catalysts have emerged as the most promising research subject in the field due to their exceptional catalytic performance and stability.The performance of bimetallic oxide catalysts is influenced by multiple factors,including the selection of carrier materials,the addition of promoters,and the synthesis process.Different types of bimetallic oxide catalysts exhibit significant differences in microstructure,surface active sites,and electronic structure,which directly determine the yield and selectivity of methanol.Although bimetallic oxide catalysts offer significant advantages over traditional copper-based catalysts,they still encounter challenges related to activity and cost.In order to enhance catalyst performance,future investigations must delve into microstructure control,surface modification,and reaction kinetics.展开更多
CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synerg...CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.展开更多
To efficiently diminish the Pt consumption while concurrently enhancing the anodic reaction kinetics,a straightforward synthesis for PtPdAg nanotrees(NTs)with exceedingly low Pt content is presented,utilizing the galv...To efficiently diminish the Pt consumption while concurrently enhancing the anodic reaction kinetics,a straightforward synthesis for PtPdAg nanotrees(NTs)with exceedingly low Pt content is presented,utilizing the galvanic replacement reaction between the initially prepared PdAg NTs and Pt ions.Due to the multilevel porous tree-like structure and the incorporation of low amounts of Pt,the electrocatalytic activity and stability of PtPdAg NTs are markedly enhanced,achieving 1.65 and 1.69 A·mg^(-1)Pt+Pd for the anodic reactions of formic acid oxidation(FAOR)and methanol oxidation(MOR)within DLFCs,surpassing the performance of PdAg NTs,as well as that of commercial Pt and Pd black.Density functional theory(DFT)calculations reveal that the addition of low amounts of Pt leads to an increase in the d-band center of PtPdAg NTs and lower the COads adsorption energy to-1.23 eV,enhancing the anti-CO toxicity properties optimally.This approach offers an effective means for designing low Pt catalysts as exceptional anodic electrocatalysts for direct liquid fuel cells.展开更多
基金supported by the State Grid Heilongjiang Electric Power Company Ltd.,Electric Power Research Institute Project(52243724000M)the China Postdoctoral Science Foundation(2020M670921)the National Natural Science Foundation of China(52307164).
文摘As a novel chemical marker,methanol has been widely applied to evaluate the ageing state of insulating paper in recent years.Methanol gas sensor(MGS)could be applied to detect the methanol content in transformer oil for its high portability and stability.However,it has the defects of a high limit of detection(LOD)and poor anti-interference performance.Therefore,a novel method of detecting methanol in transformer oil based on MGS with the solid-phase extraction(SPE)technology was investigated in this paper.A detection platform for methanol in transformer oil based on SPE was established,and the SPE experimental process and the crucial parameters were optimised.The results show that the SPE decreased the LOD of MGS from 0.4 to 0.2 ppm and effectively eliminated the interfering substances in oil.Although a part of methanol would be lost during the SPE process,the regression correction coefficient was proposed to correct the evaluation errors.The results indicate that the average relative errors decreased from 17.09%to 4.38%,and the proposed method has good applicability.
基金supported by the Ningbo Yongjiang Science and Technology Programme(2023A-161-C)。
文摘The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synthesis technique is reported to fabricate atom-nanoisland-sea structured SACs for the first time.The resultant catalysts are constructed by Pt single atoms on In_(2)O_(3)supported by Co3O4nanoislands uniformly dispersed in the sea of reduced graphene oxide.The laser process,with a maximum temperature of 2349 K within~100μs,produced abundant oxygen vacancies(up to 70.8%)and strong interactions between the Pt single atoms and In_(2)O_(3).The laser-synthesized catalysts exhibited a remarkable catalytic performance towards CO_(2)hydrogenation to methanol at 300°C with a CO_(2)conversion of 30.3%,methanol selectivity of 90.6%and exceptional stability over 48 h without any deactivation,outperforming most of the relevant catalysts reported in the literature.Characterization of the spent catalysts after testing for 48 h reveals that the Pt single atoms were retained and the oxygen vacancies remained almost unchanged.In situ diffuse reflectance infrared Fourier transform spectrum was conducted to establish the reaction mechanism supported by the density functional theory simulations.It is believed that this laser synthesis strategy opens a new avenue towards rapidly manufacturing highly active and robust thermal SACs.
基金supported by the National Natural Science Foundation of China(Nos.22302168 and 22272148).
文摘Methanol-assisted water electrolysis presents a promising yet challenging technique for electrochemical hydrogen production,as limited by the easy poisoning issue of Pt active sites.In this study,we successfully synthesized an efficient bifunctional catalyst composed of three-dimensional(3D)flower-like MoTe_(2) embedded nitrogen-doped carbon(NC)nanospheres,assembled by nanosheets,to support Pt nanoparticles(Pt-MoTe_(2)/NC)for methanol-assisted water electrolysis.This innovative Pt-MoTe_(2)/NC catalyst demonstrated superior catalytic performance targeting both hydrogen evolution reaction(HER)and methanol oxidation reaction(MOR)due to the strong metal-support interaction and the promotional effect of oxophilic molybdenum telluride.In situ infrared spectroscopy and CO stripping measurements revealed their excellent anti-poisoning ability.In particular,the onset potential of CO oxidation decreased by 130 mV relative to the standard Pt/C electrode.Theoretical calculations indicated the proper H*adsorption energy for HER and weakened CO adsorption energy for MOR in the optimized electronic structure.Therefore,the Pt-MoTe_(2)/NC electrode achieved the highest forward peak current density(76.6 mA·cm^(−2))for MOR,approximately 2.8-fold that of the commercial Pt/C,and only 34 mV was needed to deliver 10 mA·cm^(−2) for HER in acidic electrolyte.When employed as the bifunctional electrode in methanol electrolysis,Pt-MoTe_(2)/NC enabled efficient hydrogen generation with good stability,requiring merely 0.65 V to achieve 10 mA·cm^(−2),approximately 1090 mV less than traditional water electrolysis.This work presents an anti-poisoning catalyst in energy-saving hydrogen production from methanol electrolysis.
基金the Canadian NRCan OERD Energy Innovation Programthe Natural Sciences and Engineering Research Council of Canada,and the Carbon Solution Program for their financial support.
文摘The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.
基金supported by Research Grant from China Petroleum and Chemical Corp。
文摘Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.
文摘This work investigates the potential of low-pressure,medium-speed dual-fuel engines for cleaner maritime transportation.The thermodynamic performance of these engines is explored using three alternative fuels:liquefied natural gas(LNG),methanol,and ammonia.A parametric analysis examines the effect of adjustments to key engine parameters(compression ratio,boost pressure,and air-fuel ratio)on performance.Results show an initial improvement in performance with an increase in compression ratio,which reaches a peak and then declines.Similarly,increases in boost pressure and air-fuel ratio lead to linear performance gains.However,insufficient cooling reduces the amount of fuel burned,which hinders performance.Exergy analysis reveals significant exergy destruction within the engine,which ranges from 69.96%(methanol)to 78.48%(LNG).Notably,the combustion process is the leading cause of exergy loss.Among the fuels tested,methanol exhibits the lowest combustion-related exergy destruction(56.41%),followed by ammonia(62.12%)and LNG(73.77%).These findings suggest that methanol is a promising near-term alternative to LNG for marine fuel applications.
文摘Iron-Vanadium(FeV)catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde;however,due to its complex compositions,the identification of catalytic active sites still remains challenging,inhibiting the rational design of excellent FeV-based catalysts.Here,in this work,a series of FeV catalysts with various compositions,including FeVO_(4),isolated VO_(x),low-polymerized V_(n)O_(x),and crystalline V_(2)O_(5) were prepared by controlling the preparation conditions,and were applied to methanol oxidation to formaldehyde reaction.A FeV_(1.1) catalyst,which consisted of FeVO_(4) and low-polymerized V_(n)O_(x) species showed an excellent catalytic performance with a methanol conversion of 92.3%and a formaldehyde selectivity of 90.6%,which was comparable to that of conventional iron-molybdate catalyst.The results of CH_(3)OH-IR,O_(2) pulse and control experiments revealed a crucial synergistic effect between FeVO_(4) and low-polymerized V_(n)O_(x).It enhanced the oxygen supply capacity and suitable binding and adsorption strengths for formaldehyde intermediates,contributing to the high catalytic activity and formaldehyde selectivity.This study not only advances the understanding of FeV structure but also offers valuable guidelines for selective methanol oxidation to formaldehyde.
基金financial assistance from the Anhui Provincial Major Science and Technology Project(202003a05020022)the Institute of Energy,Hefei Comprehensive National Science Center(21KZS219)。
文摘The direct oxidation of methane to methanol(DOMM) has been recognized as a significant technology for efficiently utilizing low-concentration coalbed methane(LCMM) and supplying liquid fuel.Herein,the noble metals(Pt,Pd and Ru) modified Cu/alkalized sepiolite(CuX/SEPA) catalysts were prepared and used for the DOMM in a gas-phase system at low temperatures.The CuRu/SEPA exhibited the highest methanol production of 53 μmol·g^(-1)·h^(-1) and methanol selectivity of 90% under the optimal reaction conditions.Various characterizations demonstrated that the addition of Ru promoted the formation of Cu^(2+)and the contraction of Cu—Si/Al bonds to reduce the distance between framework Al atoms of SEPA to further generate more Al pairs,which facilitated the formation of reactive dicopper species([Cu_(2)O]^(2+)or [Cu_(2)O_(2)]^(2+)).Investigation of the reaction mechanism revealed that [Cu_(2)O]^(2+) or [Cu_(2)O_(2)]^(2+) species could adsorb and activate methane to form CH_(3)O^(*) species and ultimately generated methanol with the assistance of water.
文摘CuZn-based catalyst is an attractive catalyst for methanol synthesis from CO_(2)hydrogenation,but it early deactivates and its methanol yield still needs to improve.In this study,Y_(2)O_(3)was introduced to Cu/ZnO using a one-pot hydrothermal method,and exhibits a synergistic effect of ZnO and Y_(2)O_(3)on enhancing methanol yield and the stability.We found that the interaction between Y_(2)O_(3)and ZnO results in abundant oxygen vacancies formation,thereby enhancing CO_(2)adsorption and activation.Kinetic analysis and in situ DRIFTS suggest that RWGS forming CO and methanol formation compete for a mutual intermediate HCOO^(*),and the introduction of Y_(2)O_(3)to Cu/ZnO raises the energy barrier for the CO formation but lowers that for methanol formation,thus enhancing the methanol yield on Cu/ZnO/Y_(2)O_(3).
基金supported by the National Natural Science Foundation of China(No.22208322)the Natural Science Foundation of Henan(No.242300421230)+1 种基金the Key Research Projects of Higher Education Institutions of Henan Province(No.24A530009)the Special Fund for Young Teachers from Zhengzhou University(No.JC23257011).
文摘Designing advanced electrocatalysts with high methanol tolerance in the oxygen reduction reaction process is crucial for the sustainable implementation of direct methanol fuel cells.Herein,we present a Pt/C catalyst modified with black phosphorus(BP)nanodots(BPNDs-Pt/C)by using a facile ultrasonic mixing method.Experimental and computational investigations reveal that the electron transfer from BP to Pt leads to weak adsorption of hydroxyl groups on the Pt surface.As a result,the BPNDs-Pt/C catalyst exhibits efficient activity and anti-methanol ability for cathodic oxygen reduction electrocatalysis in an acidic medium.Additionally,it demonstrates high activity for oxygen reduction reaction(ORR)in an alternative alkaline system with cation exchange membrane and eliminable methanol penetration.This work highlights the feasibility of using non-metallic elements to regulate the electronic structure and surface properties of Pt-based nanomaterials.Furthermore,the designed BPNDs-Pt/C electrocatalyst,with controllable ORR performance,can be applied across various scenarios based on demand.
基金financially supported by the Key Laboratory of Carbon-based Energy Molecular Chemical Utilization Technology in Guizhou Province(No.2023008)Guizhou Provincial Science and Technology Projects(No.ZKZD2023004)+1 种基金One Hundred Person Project of Guizhou Province(No.GCC 2023013)Scientific and Technological Innovation Talents Team Project of Guizhou Province(No.CXTD2023029).
文摘Metal-based catalysts are prevalent in the CO_(2) hydrogenation to methanol owing to their remarkable catalytic activity.Herein,Ru/In_(2)O_(3) catalysts with different morphologies obtained by doping Ru into In_(2)O_(3) with irregular,rod-like,and flower-like morphologies are used for catalytic CO_(2) hydrogenation to methanol.Results indicate that the flower-like Ru/In_(2)O_(3)(Ru/In_(2)O_(3)-F)exhibits higher catalytic performance than Ru/In_(2)O_(3) with other morphologies,achieving a 12.9%CO_(2) conversion,74.02%methanol selectivity,and 671.36 mg_(MeOH) h^(−1) g_(cat)^(−1) methanol spatiotemporal yield.Furthermore,Ru/In_(2)O_(3)-F maintains its catalytic stability over 200 h at 5 MPa and 290℃.The promotional effect mainly stems from the fact that electronic structure of Ru can be effectively adjusted by modulating the morphology of In_(2)O_(3).The strong interaction between atomically dispersed Ru and In_(2)O_(3)-F enhances the structural stability of Ru,inhibiting the agglomeration of the catalyst during the reaction process.Furthermore,density-functional theory calculations reveal that highly dispersed Ru atoms not only perform efficient and rapid electronic gain and loss processes,facilitating the catalytic activation of H_(2) into H intermediates.It also enables the generated reactive H to rapidly overflow to the surrounding In sites to participate in CO_(2) reduction.These findings provide a theoretical basis for the development of high-performance catalysts for CO_(2) hydrogenation.
基金supported by the National Key Research and Development Program of China(2022YFA1503602)the National Natural Science Foundation of China(22288101,U21B20101 and 22172141)+1 种基金the BASF International Network of Centers of Excellence projectthe Zhejiang Provincial Natural Science Foundation of China(LR24B030001)。
文摘ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a significant synthetic challenge.Herein,we demonstrate the possibility to control the Al distribution in ITR zeolites using zeolite A as an aluminum source(A-ITR).The A-ITR exhibited similar crystallinity,nanosheet morphology,textual parameters,and acidic concentration with those of conventional ITR made zeolites using aluminum isopropoxide as an aluminum source(C-ITR).Characterizations of the zeolite product with^(27)Al MQ.MAS NMR spectra,^(27)Al MAS NMR spectra,and 1-hexene cracking reveal that the A-ITR zeolites have more Al species distributed in T6 and T8 sites located in relatively smaller micropores of the framework than C-ITR.As a result,the A-ITR gave enhanced catalyst lifetime and propylene selectivity due to the suppression of the aromatic cycle in the MTP reaction,compared with the C-ITR.This work provides an alternative approach to prepare efficient ITR zeolites for MTP reaction.
文摘One-step direct production of methanol from methane and water(PMMW)under mild conditions is challenging in heterogeneous catalysis owing to the absence of highly effective catalysts.Herein,we designed a series of“Single-Atom”-“Frustrated Lewis Pair”(SA-FLP)dual active sites for the direct PMMW via density functional theory(DFT)calculations combined with a machine learning(ML)approach.The results indicate that the nine designed SA-FLP catalysts are capable of efficiently activate CH4 and H_(2)O and facilitate the coupling of OH^(*)and CH_(3)^(*)into methanol.The DFT-based microkinetic simulation(MKM)results indicate that CH_(3)OH production on Co1-FLP and Pt1-FLP catalysts can reach the turnover frequencies(TOFs)of 1.01×10^(−3)s^(-1)and 8.80×10^(−4)s^(-1),respectively,which exceed the experimentally reported values by three orders of magnitude.ML results unveil that the gradient boosted regression model with 13 simple features could give satisfactory predictions for the TOFs of CH_(3)OH production with RMSE and R^(2)of 0.009 s^(-1)and 1.00,respectively.The ML-predicted MKM results indicate that four catalysts including V_(1-),Fe_(1-),Ti_(1-),and Mn_(1)-FLP exhibit higher TOFs of CH_(3)OH production than the value that the most relevant experiments reported,indicating that the four catalysts are also promising catalysts for the PMMW.This study not only develops a simple and efficient approach for design and screening SA-FLP catalysts but also provides mechanistic insights into the direct PMMW.
基金supported by the National Key R&D Program of China(2022YFA1504500,2022YFB4003100)the National Natural Science Foundation of China(U21B2092,22072162,22202213,22402210)+1 种基金the International Partnership Program of Chinese Academy of Sciences(172GJHZ2022028MI)Hua Dian Liaoning Energy Development CO.,LTD.(CHDKJ24-04-02-223).
文摘The increasingly serious climate issue compels urgent greenhouse gas mitigation strategies.As a budget,plentiful,renewable feedstock and major contributor to global warming,the large-scale catalytic transformation of CO_(2)has attracted widespread attention from society due to its potential as a solution to the environment and energy crises.At present,catalytic hydrogenation of carbon dioxide to organic chemicals is the primary approach in its industrial applications.In recent decades,various materials containing Cu-,precious metal-,In-,Zn-,and Ga-based catalysts have been designed for CO_(2)hydrogenation to methanol.Likewise,great advances have been made in CO_(2)-to-chemicals,such as olefins,aromatics,and gasoline by combining CO_(2)-to-CH3OH with methanol transformation or tandem reaction of reverse water-gas shift and Fischer-Tropsch(FT)synthesis.This review exhibits the recent advances in the hydrogenation of CO_(2)-to-CH3OH including the catalyst system,CO_(2)activation,nature of active sites,intermediate species(formate or carboxyl),structure-activity relationship,and reaction mechanism.Finally,challenges and outlooks in CO_(2)hydrogenation to methanol are summarized.
基金support by the National Natural Science Foundation of China(Nos.U20A20123,51874357,22379166)Natural Science Foundation for Distinguished Young Scholars of Hunan Province(No.2022JJ10089)。
文摘The sluggish reaction kinetics of the oxygen evolution reaction(OER)and methanol oxidation reaction(MOR)remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells.Considering the vital role of noble metals in electrocatalytic activity,this work focuses on the rational synthesis of Ni-noble metal composite nanocatalysts for overcoming the drawbacks of high cost and susceptible oxidized surfaces of noble metals.The inherent catalytic activity is improved by the altered electronic structure and effective active sites of the catalyst induced by the size effect of noble metal clusters.In particular,a series of Ni-noble metal nanocomposites are successfully synthesized by partially introducing noble metal into Ni with porous interfacial defects derived from Ni-Al layered double hydroxide(LDH).The Ni_(10)Pd_(1)nanocomposite exhibits high OER catalytic activity with an overpotential of 0.279 V at 10 m A/cm^(2),surpassing Ni_(10)Ag_(1)and Ni_(10)Au_(1)counterparts.Furthermore,the average diameter of Pd clusters gradually increases from 5.57 nm to 44.44 nm with the increased proportion of doped Pd,leading to the passivation of catalytic activity due to the exacerbated surface oxidation of Pd in the form of Pd^(2+).After optimization,Ni_(10)Pd_(1)delivers significantly enhanced OER and MOR electroactivities and long-term stability compared to that of Ni_(2)Pd_(1),Ni_(1)Pd_(1)and Ni_(1)Pd_(2),which is conducive to the effective utilization of Pd and alleviation of surface oxidation.
基金supported by the National Natural Science Foundation of China(No.22275139)the Key Project of Natural Science Foundation of Tianjin City(No.22JCZDJC00510)The authors thank the Shanghai Synchrotron Radiation Facility of Experiment Assist System(https://cstr.cn/31124.02.SSRF.LAB)for the assistance on BL11B.
文摘Photo-reforming methanol into valuable chemicals represents an energetically sustainable alternative to conventional thermal catalysis,yet controlling-specific C-C coupling way still remains elusive.In this work,we report a sulfide-based photocatalytic paradigm,where atomic-level control of nickel species directly dictates reaction selectivity.The electrostatic constructing ZnIn_(2)S_(4)/Zn_(0.5)Cd_(0.5)S(ZIS/ZCS)heterostructures enable single atom Ni to facilitate ethylene glycol(EG)production with a rate of 11.2 mmol·gcat^(−1)·h^(−1),surpassing reported non-precious metal systems,whereas the Ni aggregates drive exclusive formaldehyde formation.The operando spectroscopy and density functional theory reveal dual roles of Ni as electron reservoir and chemical bond breakage inducers,lowering C-H activation barriers while stabilizing·CH2OH intermediates for cross-coupling.This interfacial configuration engineering creates an electron highway that couples carrier dissociation with radical recombination kinetics,achieving atom-economic steering of methanol oxidative valorization.The metal dispersion assisting catalysis correlation here provides a design blueprint for selective bond scission and reconstruction in sustainable organic synthesis.
基金supported by the National Natural Science Foundation of China(No.22465009)the Education Department of Guizhou Province(No.2021312)the Foundation of Guizhou Province(No.2019-5666).
文摘Alloying and interface effects are effective strategies for enhancing the performance of electrocatalysts in energy-related devices.Herein,dendritic Au-doped platinum-palladium alloy/dumbbell-like bismuth telluride heterostructures(denoted PtPdAu/BiTe)were synthesized using a visible-light-assisted strategy.The coupling alloy and interfacial effects of PtPdAu/BiTe significantly improved the performance and stability of both the ethanol oxidation reaction(EOR)and methanol oxidation reaction(MOR).Introducing a small amount of Au effectively enhanced the CO tolerance of PtPdAu/BiTe compared to dendritic platinum-palladium alloy/dumbbell-like bismuth telluride heterostructures.PtPdAu/BiTe exhibited mass activities of 31.5 and 13.3 A·mg_(Pt)^(-1)in EOR and MOR,respectively,which were 34.4 and 13.2 times higher than those of commercial Pt black,revealing efficient Pt atom utilization.In-situ Fourier transform infrared spectroscopy demonstrated complete 12e^(-)and 6e^(-)oxidation of ethanol and methanol on PtPdAu/BiTe.The PtPdAu/BiTe/C achieved mass peak power densities of 131 and 156 mW·mg_(Pt)^(-1),which were 2.4 and 2.2 times higher than those of Pt/C in practical direct ethanol fuel cell(DEFC)and direct methanol fuel cell(DMFC),respectively,highlighting their potential application in DEFC and DMFC.This study introduces an effective strategy for designing efficient and highly CO tolerant anodic electrocatalysts for practical DEFC and DMFC applications.
文摘Against the backdrop of global energy and environmental crises,the technology of CO_(2)hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution.Bimetallic oxide catalysts have emerged as the most promising research subject in the field due to their exceptional catalytic performance and stability.The performance of bimetallic oxide catalysts is influenced by multiple factors,including the selection of carrier materials,the addition of promoters,and the synthesis process.Different types of bimetallic oxide catalysts exhibit significant differences in microstructure,surface active sites,and electronic structure,which directly determine the yield and selectivity of methanol.Although bimetallic oxide catalysts offer significant advantages over traditional copper-based catalysts,they still encounter challenges related to activity and cost.In order to enhance catalyst performance,future investigations must delve into microstructure control,surface modification,and reaction kinetics.
文摘CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.
基金supported by the National Natural Science Foundation of China(Nos.22202104,22279062,22232004 and 22072067)the Natural Science Foundation of Jiangsu Province(No.BK20220933)Shuangchuang Doctor Plan of Jiangsu Province(No.JSSCBS20220273).
文摘To efficiently diminish the Pt consumption while concurrently enhancing the anodic reaction kinetics,a straightforward synthesis for PtPdAg nanotrees(NTs)with exceedingly low Pt content is presented,utilizing the galvanic replacement reaction between the initially prepared PdAg NTs and Pt ions.Due to the multilevel porous tree-like structure and the incorporation of low amounts of Pt,the electrocatalytic activity and stability of PtPdAg NTs are markedly enhanced,achieving 1.65 and 1.69 A·mg^(-1)Pt+Pd for the anodic reactions of formic acid oxidation(FAOR)and methanol oxidation(MOR)within DLFCs,surpassing the performance of PdAg NTs,as well as that of commercial Pt and Pd black.Density functional theory(DFT)calculations reveal that the addition of low amounts of Pt leads to an increase in the d-band center of PtPdAg NTs and lower the COads adsorption energy to-1.23 eV,enhancing the anti-CO toxicity properties optimally.This approach offers an effective means for designing low Pt catalysts as exceptional anodic electrocatalysts for direct liquid fuel cells.
