CuZnAl(CZA)is a classic industrial catalyst widely used for the synthesis of methanol from syngas,but its catalytic performance is not optimal for the hydrogenation of CO_(2) to methanol.Meanwhile,understanding the ca...CuZnAl(CZA)is a classic industrial catalyst widely used for the synthesis of methanol from syngas,but its catalytic performance is not optimal for the hydrogenation of CO_(2) to methanol.Meanwhile,understanding the catalytic mechanism of Cu species in the CZA catalyst remains a great challenge.In this study,we systematically investigated the valence state change of active Cu species in CZA catalyst and their influence on catalytic performance by modifying the catalysts with varying amounts of electron donor K,thus identifying the catalytic function of Cu species with different valence states.H2-TPR,XPS and HR-TEM characterizations reveal that the highly dispersed K species supported on CZA catalysts will inhibit the reduction of CuO,resulting in a small amount of Cu_(2)O active species being produced under reaction conditions thus causing a decrease in catalytic activity.Furthermore,XRD and Cu LMM spectra show that the proportion of Cu^(0) in K-modified CZA catalysts increases with K loading,but a higher proportion of Cu^(0) species on the surface obviously promotes the reverse water gas shift(RWGS)reaction.According to the results of in situ infrared spectroscopy,CZA catalyst follows the reaction pathway mediated by HCOO^(*)in the hydrogenation of CO_(2) to methanol.展开更多
Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tai...Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tailored electronic configurations and unique metal-support interactions,exhibit superior performance in CO_(2) activation and methanol synthesis.This review systematically compares reaction mechanisms and pathways across thermal,photocatalytic and electrocatalytic systems,emphasizing structure-activity relationships governed by active sites,coordination microenvironments and support functionalities.Through case studies of representative SACs,we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity.A critical analysis of reaction parameters(e.g.,temperature,pressure)reveals condition-dependent catalytic behaviors in thermal system,with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps.While thermal catalysis achieves industrially viable methanol yields,the scalability is constrained by energy-intensive operation and catalyst sintering.Conversely,photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations.To address the challenges,we propose strategic research priorities on precise design of active sites,synergy of multiple technological pathways,development of intelligent catalytic systems and diverse CO_(2) feedstock compatibility.These insights establish a framework for developing next-generation SACs,offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.展开更多
The breaking of the symmetric electronic distribution of single-atom catalysts is effective in improving the intrinsic activity.However,traditional modification strategies can only disrupt the electronic distribution ...The breaking of the symmetric electronic distribution of single-atom catalysts is effective in improving the intrinsic activity.However,traditional modification strategies can only disrupt the electronic distribution in one dimension,resulting in limited regulation of electronic structure.Herein,we report a multidimensional coordination strategy to significantly break the symmetrical electron distribution of the metal single site to achieve highly efficient electrochemical CO_(2) reduction reaction(CO_(2) RR).Ni singleatom sites decorated with planar P and axial Cl atoms are successfully constructed on carbon support(Ni-NPCl-C).Ni-NPCl-C affords CO Faraday efficiency over 90%in a wide potential window range from-0.5 to-1.2 V and an ultrahigh turnover frequency of 1.17×10^(5)h^(-1),much superior to its counterparts with single-dimensional coordination.Ni-NPCl-C can be further applied as a bifunctional catalyst to construct a rechargeable Zn-CO_(2) battery.Spectroscopic characterizations and theoretical calculations demonstrate that the dual adjustments with axial Cl and planar P can synergistically disrupt the electron distribution in two dimensions to increase electrons around Ni sites with the upshift of the d-band center,thereby facilitating the formation of*COOH intermediates and improving the CO_(2) RR performance.展开更多
Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespr...Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.展开更多
Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm thr...Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm through experimental results that Bi-based catalysts containing halogen ions(I^(-),Cl^(-),Br^(-))and SO_(4)^(2-)maintain the system stability,keeping Faraday efficiency of formic acid above90%in the current range of 50-800 mA cm^(-2).In contrast,anions containing S^(2-)and NO_(3)^(-)in the electrolyte can be reduced to produce by-products.These anions and their by-products could poison the active center,leading to increased side reactions and thus significantly reducing the Faraday efficiency of formic acid.The combination of non-in situ and in situ characterization results revealed that the Bi-based catalysts all underwent the transition from the initial state to the Bi/Bi_(2)O_(2)CO_(3)(BOC)intermediate state in high-concentration KHCO_(3) solution,and the different anions could selectively modulate the degree of exposure of specific crystalline surfaces of BOC.At the late stage of the reaction,BOC was completely converted to metal Bi and became the real active center.Combined with in situ IR and DFT calculations,it is further verified that^(*)OCHO is the key intermediate on the metallic Bi surface,which is most favorable for formic acid formation.This study reveals the key mechanism by which anions affect the formation of active sites via modulating the catalyst reconstruction process,which provides an important theoretical basis for the design and optimization of test conditions of Bi-based catalysts.展开更多
Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon di...Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.展开更多
Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especi...Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especially for CO_(2)methanation(the Sabatier reaction),which has attracted significant attention due to its economic benefits and the potential for safe energy transportation via existing natural gas pipelines.The development of high-performance CO_(2)methanation catalysts remains an ongoing and long-term objective,and there is a lack of adequate in-situ characterization techniques to investigate the mechanisms.This study focuses on the Ni/La_(2)O_(3)(LN)catalyst and introduces two CO_(2)activation strategies through F and Na modifications:the Ni-Ov-Ni site activation with electron transfer from Ni0 under low-power conditions and basic site activation under high-power conditions.The LN-NaF catalysts enhance CO_(2)methanation activity across the entire power range compared to LN,achieving a CO_(2)conversion of 86.3%and CH4 selectivity of 99.4%.Additionally,LN-F(h)reaches a CH4 yield 4.15 times higher than that of LN at low power.Furthermore,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy with a self-made reactor are performed under plasma-catalytic conditions to reveal the CO_(2)adsorption and conversion mechanisms,indicating that different dopants(F,Na,and NaF)exhibit promoting effects on different intermediates,resulting in variations in CO_(2)methanation activity.This study provides valuable insights for improving catalyst performance and a thorough comprehension of mechanisms in CO_(2)methanation.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low r...Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.展开更多
Single-atom catalysts(SACs)offer a promising approach for maximizing noble metals utilization in catalytic processes.However,their performance in CO_(2)hydrogenation is often constrained by the nature of metal-support...Single-atom catalysts(SACs)offer a promising approach for maximizing noble metals utilization in catalytic processes.However,their performance in CO_(2)hydrogenation is often constrained by the nature of metal-support interactions.In this study,we synthesized TiO_(2)supported Pt SACs(Pt1/TiO_(2)),with Pt single atoms dispersed on rutile(Pt1/R)and anatase(Pt1/A)phases of TiO_(2)for the reverse water-gas shift(RWGS)reaction.While both catalysts maintained 100%CO selectivity over time,Pt1/A achieved a CO_(2)conversion of 7.5%,significantly outperforming Pt1/R(3.6%).In situ diffuse reflectance infrared Fourier-transform spectroscopy and X-ray photoelectron spectroscopy revealed distinct reaction pathways:the COOH pathway was dominant on Pt1/A,whereas the–OH+HCO pathway was more competitive on Pt1/R.Analysis of electron metal-support interactions and energy barrier calculations indicated that Pt1/A better stabilized metallic Pt species and facilitates more favorable reaction pathways with lower energy barriers.These findings provide valuable insights for the design of more efficient SAC systems in CO_(2)hydrogenation processes.展开更多
Dry reforming of methane(DRM)converts CH4 and CO_(2) to syngas.Photothermal DRM,which integrates temperature and light,is a sustainable method for storing solar energy in molecules.However,challenges such as limited l...Dry reforming of methane(DRM)converts CH4 and CO_(2) to syngas.Photothermal DRM,which integrates temperature and light,is a sustainable method for storing solar energy in molecules.However,challenges such as limited light absorption,low photocarrier separation efficiency,Ni sintering,and carbon deposition hinder DRM stability.Herein,we regulated Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance the optical characteristics while addressing Ni sintering and carbon deposition issues.The(3Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst had insufficient Ni content,while the(9Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst showed excessive carbon deposition,leading to lower stability compared to the(6Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst,which achieved CH4 and CO_(2) rates to 231.0 μmol gcat^(-1)s^(-1) and 294.3 μmol gcat^(-1)s^(-1) ,respectively,at 973 K,with only 0.2 wt.%carbon deposition and no Ni sintering.This work adjusted Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance DRM performance,which has implications for improving other reactions.展开更多
Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.展开更多
The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with eth...The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with ethanol vapor exhibited better catalytic activity than the pristine CrOx/SiO2,generating 41.4% propane conversion and 84.8% propylene selectivity.The various catalyst samples prepared were characterized by X-ray diffraction,transmission electron microscopy,temperature-programmed reduction,X-ray photoelectron spectroscopy and reflectance UV-Vis spectroscopy.The data show that coordinative Cr^3＋ species represent the active sites during the dehydrogenation of propane and that these species serve as precursors for the generation of Cr^3＋.Cr^3＋ is reduced during the reaction,leading to a decrease in catalytic activity.Following ethanol vapor pretreatment,the reduced CrOx in the catalyst is readily re-oxidized to Cr^6＋ by CO2.The pretreated catalyst thus exhibits high activity during the propane dehydrogenation reaction by maintaining the active Cr^3＋ states.展开更多
With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Ni...With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.展开更多
Ce and its oxide(CeO_(2))have garnered extensive research attention in catalytic elimination of various air pollutants owing to their superior redox performance and oxygen storage capacity,which might originate from t...Ce and its oxide(CeO_(2))have garnered extensive research attention in catalytic elimination of various air pollutants owing to their superior redox performance and oxygen storage capacity,which might originate from the overlap of Ce 4f-5d atomic orbitals,as depicted in Cotton atomic orbital energy level diagram.To further tap the potential of CeO_(2),strategic integration with diverse transition metals and noble metals has been implemented.The distinctive nature of Cu in forming strong interactions with CeO_(2),coupled with its economic viability,has propelled substantial investigations into CuO-CeO_(2)composite catalysts for air pollutant removal.In this review,starting from a discussion on the classical dispersion model of Cu on CeO_(2),the current development in the synthesis and characterization of CuOCeO_(2) catalysts is systematically summarized.Subsequently,the application of CuO-CeO_(2) catalysts in several common air pollutant elimination-related reactions(e.g.,CO oxidation,NO reduction by CO,NH_(3)-SCR and NH_(3)-SCO)is discussed in depth.The review can provide significant guidance for the rational engineering of high-efficiency CuO-CeO_(2) catalysts.展开更多
To promote CO_(2)redox kinetics on the cathode of hybrid sodium-carbon dioxide(Na-CO_(2))batteries,hollow cubic CuS nanoboxes were encapsulated in polypyrrole and polydopamine by in situ polymerization of pyrrole and ...To promote CO_(2)redox kinetics on the cathode of hybrid sodium-carbon dioxide(Na-CO_(2))batteries,hollow cubic CuS nanoboxes were encapsulated in polypyrrole and polydopamine by in situ polymerization of pyrrole and dopamine monomers,respectively,and coupled with high-temperature heat treatment to obtain nitrogen-carbon encapsulated Cu_(x)S@NC_(PPy)and Cu_(x)S@NCPDA catalysts.The results show that the encapsulation of nitrogen-doped carbon not only increases the specific surface area and improves the electron affinity but also promotes the synergistic interaction between the CuS-based active species and the defect carbon,thus providing abundant active sites for CO_(2)conversion.The electrochemical performances of the carbon-coated modified samples were all improved,especially the hybrid Na-CO_(2)battery based on Cu_(x)S@NC_(PPy),which showed a low voltage gap of 0.74 V at 0.1 mA/cm^(2)and a high power density of 3.42 mW/cm^(2).展开更多
Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O cr...Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.展开更多
基金Supported by the National Key Research and Development Program of China(2022YFB4101800)the National Natural Science Foundation of China(22172032,U22A20431)。
文摘CuZnAl(CZA)is a classic industrial catalyst widely used for the synthesis of methanol from syngas,but its catalytic performance is not optimal for the hydrogenation of CO_(2) to methanol.Meanwhile,understanding the catalytic mechanism of Cu species in the CZA catalyst remains a great challenge.In this study,we systematically investigated the valence state change of active Cu species in CZA catalyst and their influence on catalytic performance by modifying the catalysts with varying amounts of electron donor K,thus identifying the catalytic function of Cu species with different valence states.H2-TPR,XPS and HR-TEM characterizations reveal that the highly dispersed K species supported on CZA catalysts will inhibit the reduction of CuO,resulting in a small amount of Cu_(2)O active species being produced under reaction conditions thus causing a decrease in catalytic activity.Furthermore,XRD and Cu LMM spectra show that the proportion of Cu^(0) in K-modified CZA catalysts increases with K loading,but a higher proportion of Cu^(0) species on the surface obviously promotes the reverse water gas shift(RWGS)reaction.According to the results of in situ infrared spectroscopy,CZA catalyst follows the reaction pathway mediated by HCOO^(*)in the hydrogenation of CO_(2) to methanol.
基金supported by the National Natural Science Foundation of China(No.52300170).
文摘Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tailored electronic configurations and unique metal-support interactions,exhibit superior performance in CO_(2) activation and methanol synthesis.This review systematically compares reaction mechanisms and pathways across thermal,photocatalytic and electrocatalytic systems,emphasizing structure-activity relationships governed by active sites,coordination microenvironments and support functionalities.Through case studies of representative SACs,we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity.A critical analysis of reaction parameters(e.g.,temperature,pressure)reveals condition-dependent catalytic behaviors in thermal system,with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps.While thermal catalysis achieves industrially viable methanol yields,the scalability is constrained by energy-intensive operation and catalyst sintering.Conversely,photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations.To address the challenges,we propose strategic research priorities on precise design of active sites,synergy of multiple technological pathways,development of intelligent catalytic systems and diverse CO_(2) feedstock compatibility.These insights establish a framework for developing next-generation SACs,offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.
基金supported by the National Natural Science Foundation of China(Nos.22422806,22378136,and 22138003)the Guangdong Pearl River Talents Program(Nos.2021QN02C847and 2021ZT09Z109)+4 种基金the Natural Science Foundation of Guangdong Province(Nos.2024A1515011196 and 2023B1515040005)the Fundamental Research Funds for the Central Universities(Nos.2024ZYGXZR011,2025ZYGXZR025)the Science and Technology Program of Guangzhou(No.2025A04J5244)the State Key Laboratory of Pulp and Paper Engineering(No.2024ZD09)the TCL Young Talent Program。
文摘The breaking of the symmetric electronic distribution of single-atom catalysts is effective in improving the intrinsic activity.However,traditional modification strategies can only disrupt the electronic distribution in one dimension,resulting in limited regulation of electronic structure.Herein,we report a multidimensional coordination strategy to significantly break the symmetrical electron distribution of the metal single site to achieve highly efficient electrochemical CO_(2) reduction reaction(CO_(2) RR).Ni singleatom sites decorated with planar P and axial Cl atoms are successfully constructed on carbon support(Ni-NPCl-C).Ni-NPCl-C affords CO Faraday efficiency over 90%in a wide potential window range from-0.5 to-1.2 V and an ultrahigh turnover frequency of 1.17×10^(5)h^(-1),much superior to its counterparts with single-dimensional coordination.Ni-NPCl-C can be further applied as a bifunctional catalyst to construct a rechargeable Zn-CO_(2) battery.Spectroscopic characterizations and theoretical calculations demonstrate that the dual adjustments with axial Cl and planar P can synergistically disrupt the electron distribution in two dimensions to increase electrons around Ni sites with the upshift of the d-band center,thereby facilitating the formation of*COOH intermediates and improving the CO_(2) RR performance.
基金supports from the National Natural Science Foundation of China(Grant Nos.12305372 and 22376217)the National Key Research&Development Program of China(Grant Nos.2022YFA1603802 and 2022YFB3504100)+1 种基金the projects of the key laboratory of advanced energy materials chemistry,ministry of education(Nankai University)key laboratory of Jiangxi Province for persistent pollutants prevention control and resource reuse(2023SSY02061)are gratefully acknowledged.
文摘Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.
基金funded by the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C03017)China Postdoctoral Science Foundation(No.GZC20230373)+5 种基金Zhejiang Provincial Natural Science Foundation of China(No.LQ24B070010)CMA Key Open Laboratory of Transforming Climate Resources to Economy(No.2024004K)Natural Science Foundation of Huzhou City(No.2024YZ19)the National Natural Science Foundation of China(Nos.22202032,22406020 and 22406019)the Key Research and Development Projects of Xinjiang Uygur Autonomous Region,China(No.2022B02031)Joint Fund of the Zhejiang Provincial Natural Science Foundation of China(No.LBMHY25E060009)。
文摘Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm through experimental results that Bi-based catalysts containing halogen ions(I^(-),Cl^(-),Br^(-))and SO_(4)^(2-)maintain the system stability,keeping Faraday efficiency of formic acid above90%in the current range of 50-800 mA cm^(-2).In contrast,anions containing S^(2-)and NO_(3)^(-)in the electrolyte can be reduced to produce by-products.These anions and their by-products could poison the active center,leading to increased side reactions and thus significantly reducing the Faraday efficiency of formic acid.The combination of non-in situ and in situ characterization results revealed that the Bi-based catalysts all underwent the transition from the initial state to the Bi/Bi_(2)O_(2)CO_(3)(BOC)intermediate state in high-concentration KHCO_(3) solution,and the different anions could selectively modulate the degree of exposure of specific crystalline surfaces of BOC.At the late stage of the reaction,BOC was completely converted to metal Bi and became the real active center.Combined with in situ IR and DFT calculations,it is further verified that^(*)OCHO is the key intermediate on the metallic Bi surface,which is most favorable for formic acid formation.This study reveals the key mechanism by which anions affect the formation of active sites via modulating the catalyst reconstruction process,which provides an important theoretical basis for the design and optimization of test conditions of Bi-based catalysts.
基金financially supported by the National Natural Science Foundation of China(52271200)Guangdong Basic and Applied Basic Research Foundation(2024A1515010393)USTB MatCom of Beijing Advanced Innovation Center for Materials Genome Engineering。
文摘Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.
基金supported by the National Natural Science Foundation of China(No.51878292).
文摘Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especially for CO_(2)methanation(the Sabatier reaction),which has attracted significant attention due to its economic benefits and the potential for safe energy transportation via existing natural gas pipelines.The development of high-performance CO_(2)methanation catalysts remains an ongoing and long-term objective,and there is a lack of adequate in-situ characterization techniques to investigate the mechanisms.This study focuses on the Ni/La_(2)O_(3)(LN)catalyst and introduces two CO_(2)activation strategies through F and Na modifications:the Ni-Ov-Ni site activation with electron transfer from Ni0 under low-power conditions and basic site activation under high-power conditions.The LN-NaF catalysts enhance CO_(2)methanation activity across the entire power range compared to LN,achieving a CO_(2)conversion of 86.3%and CH4 selectivity of 99.4%.Additionally,LN-F(h)reaches a CH4 yield 4.15 times higher than that of LN at low power.Furthermore,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy with a self-made reactor are performed under plasma-catalytic conditions to reveal the CO_(2)adsorption and conversion mechanisms,indicating that different dopants(F,Na,and NaF)exhibit promoting effects on different intermediates,resulting in variations in CO_(2)methanation activity.This study provides valuable insights for improving catalyst performance and a thorough comprehension of mechanisms in CO_(2)methanation.
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.
文摘Single-atom catalysts(SACs)offer a promising approach for maximizing noble metals utilization in catalytic processes.However,their performance in CO_(2)hydrogenation is often constrained by the nature of metal-support interactions.In this study,we synthesized TiO_(2)supported Pt SACs(Pt1/TiO_(2)),with Pt single atoms dispersed on rutile(Pt1/R)and anatase(Pt1/A)phases of TiO_(2)for the reverse water-gas shift(RWGS)reaction.While both catalysts maintained 100%CO selectivity over time,Pt1/A achieved a CO_(2)conversion of 7.5%,significantly outperforming Pt1/R(3.6%).In situ diffuse reflectance infrared Fourier-transform spectroscopy and X-ray photoelectron spectroscopy revealed distinct reaction pathways:the COOH pathway was dominant on Pt1/A,whereas the–OH+HCO pathway was more competitive on Pt1/R.Analysis of electron metal-support interactions and energy barrier calculations indicated that Pt1/A better stabilized metallic Pt species and facilitates more favorable reaction pathways with lower energy barriers.These findings provide valuable insights for the design of more efficient SAC systems in CO_(2)hydrogenation processes.
基金support from the National Natural Science Foundation of China(22078134)State Key Laboratory of Clean and Efficient Coal Utilization of Taiyuan University of Technology(SKL2022006)Natural Science Foundation of Chongqing(CSTB2023NSCQ-MSX0162)are greatly appreciated for the work.
文摘Dry reforming of methane(DRM)converts CH4 and CO_(2) to syngas.Photothermal DRM,which integrates temperature and light,is a sustainable method for storing solar energy in molecules.However,challenges such as limited light absorption,low photocarrier separation efficiency,Ni sintering,and carbon deposition hinder DRM stability.Herein,we regulated Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance the optical characteristics while addressing Ni sintering and carbon deposition issues.The(3Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst had insufficient Ni content,while the(9Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst showed excessive carbon deposition,leading to lower stability compared to the(6Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst,which achieved CH4 and CO_(2) rates to 231.0 μmol gcat^(-1)s^(-1) and 294.3 μmol gcat^(-1)s^(-1) ,respectively,at 973 K,with only 0.2 wt.%carbon deposition and no Ni sintering.This work adjusted Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance DRM performance,which has implications for improving other reactions.
基金Supported by the National Key Research and Development Program of China(2023YFB4104500,2023YFB4104502)the National Natural Science Foundation of China(22138013)the Taishan Scholar Project(ts201712020).
文摘Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.
基金the financial support from China Postdoctoral Science Foundation (2014M560224)
文摘The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with ethanol vapor exhibited better catalytic activity than the pristine CrOx/SiO2,generating 41.4% propane conversion and 84.8% propylene selectivity.The various catalyst samples prepared were characterized by X-ray diffraction,transmission electron microscopy,temperature-programmed reduction,X-ray photoelectron spectroscopy and reflectance UV-Vis spectroscopy.The data show that coordinative Cr^3＋ species represent the active sites during the dehydrogenation of propane and that these species serve as precursors for the generation of Cr^3＋.Cr^3＋ is reduced during the reaction,leading to a decrease in catalytic activity.Following ethanol vapor pretreatment,the reduced CrOx in the catalyst is readily re-oxidized to Cr^6＋ by CO2.The pretreated catalyst thus exhibits high activity during the propane dehydrogenation reaction by maintaining the active Cr^3＋ states.
基金supported by the Natural Science Foundation of Shanxi Province(202203021221155)the Foundation of National Key Laboratory of High Efficiency and Low Carbon Utilization of Coal(J23-24-902)。
文摘With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.
基金Project supported by the National Natural Science Foundation of China(22306090,22272077,22402027)the Natural Science Foundation of Jiangsu Province(BK20230773,BK20231513)+1 种基金the Young Elite Scientists Sponsorship Program by CAST(YESS20230298)the Sinopec Group(H25007)。
文摘Ce and its oxide(CeO_(2))have garnered extensive research attention in catalytic elimination of various air pollutants owing to their superior redox performance and oxygen storage capacity,which might originate from the overlap of Ce 4f-5d atomic orbitals,as depicted in Cotton atomic orbital energy level diagram.To further tap the potential of CeO_(2),strategic integration with diverse transition metals and noble metals has been implemented.The distinctive nature of Cu in forming strong interactions with CeO_(2),coupled with its economic viability,has propelled substantial investigations into CuO-CeO_(2)composite catalysts for air pollutant removal.In this review,starting from a discussion on the classical dispersion model of Cu on CeO_(2),the current development in the synthesis and characterization of CuOCeO_(2) catalysts is systematically summarized.Subsequently,the application of CuO-CeO_(2) catalysts in several common air pollutant elimination-related reactions(e.g.,CO oxidation,NO reduction by CO,NH_(3)-SCR and NH_(3)-SCO)is discussed in depth.The review can provide significant guidance for the rational engineering of high-efficiency CuO-CeO_(2) catalysts.
基金financially supported by the National Natural Science Foundation of China(No.52172264)the National Key Research and Development Program of China(No.2022YFC3900802)。
文摘To promote CO_(2)redox kinetics on the cathode of hybrid sodium-carbon dioxide(Na-CO_(2))batteries,hollow cubic CuS nanoboxes were encapsulated in polypyrrole and polydopamine by in situ polymerization of pyrrole and dopamine monomers,respectively,and coupled with high-temperature heat treatment to obtain nitrogen-carbon encapsulated Cu_(x)S@NC_(PPy)and Cu_(x)S@NCPDA catalysts.The results show that the encapsulation of nitrogen-doped carbon not only increases the specific surface area and improves the electron affinity but also promotes the synergistic interaction between the CuS-based active species and the defect carbon,thus providing abundant active sites for CO_(2)conversion.The electrochemical performances of the carbon-coated modified samples were all improved,especially the hybrid Na-CO_(2)battery based on Cu_(x)S@NC_(PPy),which showed a low voltage gap of 0.74 V at 0.1 mA/cm^(2)and a high power density of 3.42 mW/cm^(2).
基金the financial support from the National Natural Science Foundation of China (Nos.U23A20677,22022610 and 52400137)"Pioneer" and "Leading Goose" R&D Program of Zhejiang (Nos.2022C03146 and 2023C03017)+2 种基金China Postdoctoral Science Foundation (No.2024T170805)Zhejiang Provincial Natural Science Foundation of China (No.LDT23E06015B06)the support of the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University for assistance with the calculations。
文摘Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.
