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
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
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
Magnesium hydride(MgH_(2)),a promising high-capacity hydrogen storage material,is hindered by slow dehydrogenation kinetics.AIdriven catalyst discovery to address this is often hampered by the laborious extraction of ...Magnesium hydride(MgH_(2)),a promising high-capacity hydrogen storage material,is hindered by slow dehydrogenation kinetics.AIdriven catalyst discovery to address this is often hampered by the laborious extraction of data from unstructured literature.To overcome this,we introduce a transformative“LLM to Agent”framework that synergistically integrates Large Language Models(LLMs)for automated data curation with Machine Learning(ML)for predictive design.We automatically constructed a comprehensive database of 809 MgH_(2)catalysts(6555 data rows)with high fidelity and an~40-fold acceleration over manual methods.The resulting ML models achieved high accuracy(average R^(2)>0.91)in predicting dehydrogenation temperature and activation energy,subsequently guiding a Genetic Algorithm(GA)in an exploratory inverse design that autonomously uncovered key design principles for high-performance catalysts.Encouragingly,a strong alignment was found between these AI-discovered principles and the design strategies of recently reported,state-of-the-art experimental systems,providing substantial evidence for the validity of our approach.The framework culminates in Cat-Advisor,a novel,domain-adapted multi-agent system.Cat-Advisor translates ML predictions and retrieval-augmented knowledge into actionable design guidance,demonstrating capabilities that surpass those of general-purpose LLMs in this specialized domain.This work delivers a practical AI toolkit for accelerated materials discovery and advances the emerging Agent-based paradigm for designing next-generation energy technologies.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
Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrat...Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrate that bio-based benzaldehyde,a noteworthy high-value chemical,is able to be directionally prepared from lignocellulosic biomass.This new control-lable transformation was materialized by uniting catalytic-pyrolysis of lignocellulose to toluene intermediate and catalytic oxidation of toluene intermediate to bio-based benzalde-hyde.This work also developed a highly active magnetic catalyst(CoFe_(2)O_(4)@Biochar(HTR)),achieving 77.1%benzaldehyde selectivity and 46.7%benzaldehyde yield using this catalyst.It was found that introducing the biochar carrier into the cobalt iron composite metal oxide cat-alyst enhanced hydroxyl radical formation and bio-based benzaldehyde synthesis.Based on catalyst characterizations and hydroxyl radical analysis,potential reaction mechanism for bio-based benzaldehyde synthesis was proposed.This strategy may provide a beneficial pathway for developing high-value bio-based chemical(benzaldehyde)using renewable lignocellulosic biomass.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
Supported metal catalysts are the backbone of heterogeneous catalysis,playing a crucial role in the modern chemical industry.Metal-support interactions(MSIs)are known important in determining the catalytic performance...Supported metal catalysts are the backbone of heterogeneous catalysis,playing a crucial role in the modern chemical industry.Metal-support interactions(MSIs)are known important in determining the catalytic performance of supported metal catalysts.This is particularly true for single-atom catalysts(SACs)and pseudo-single-atom catalysts(pseudo-SACs),where all metal atoms are dispersed on,and interact directly with the support.Consequently,the MSI of SACs and pseudo-SACs are theoretically more sensitive to modulation compared to that of traditional nanoparticle catalysts.In this work,we experimentally demonstrated this hypothesis by an observed size-dependent MSI modulation.We fabricated CoFe_(2)O_(4) supported Pt pseudo-SACs and nanoparticle catalysts,followed by a straightforward water treatment process.It was found that the covalent strong metal-support interaction(CMSI)in pseudo-SACs can be weakened,leading to a significant activity improvement in methane combustion reaction.This finding aligns with our recent observation of CoFe_(2)O_(4) supported Pt SACs.By contrast,the MSI in Pt nanoparticle catalyst was barely affected by the water treatment,giving rise to almost unchanged catalytic performance.This work highlights the critical role of metal size in determining the MSI modulation,offering a novel strategy for tuning the catalytic performance of SACs and pseudo-SACs by fine-tuning their MSIs.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
The role of catalysts in enhancing the hydrogen storage kinetics of the Mg/MgH_(2)system is pivotal.However,the exploration of efficient catalysts and the underlying principles of their design remain both a prominent ...The role of catalysts in enhancing the hydrogen storage kinetics of the Mg/MgH_(2)system is pivotal.However,the exploration of efficient catalysts and the underlying principles of their design remain both a prominent focus and a significant challenge in current research.In this study,we present a bimetallic oxide of Bi_(2)Ti_(2)O_(7)hollow sphere as a highly effective catalyst for MgH_(2).As a result,the Bi_(2)Ti_(2)O_(7)-catalyzed Mg/MgH_(2)system lowers the hydrogen desorption initiation temperature to 194.3℃,reduces the peak desorption temperature to 245.6℃,decreases the dehydrogenation activation energy to 82.14 kJ·mol^(−1),and can absorb 5.4 wt.%of hydrogen within 60 s at 200℃,demonstrating outstanding hydrogen ab/desorption kinetics,compared to pure MgH_(2).Additionally,it can maintain a high hydrogen capacity of 5.2 wt.%,even after 50 dehydrogenation cycles,showing good cycle stability.The characterization results show that the high-valent Bi and Ti in Bi_(2)Ti_(2)O_(7)are reduced to their low-valent or even zero-valent metallic states during the dehydrogenation and hydrogenation process,thus establishing an in-situ multivalent and multi-element catalytic environment.Density functional theory calculations further reveal that the synergistic effects between Bi and Ti in the Bi-Ti mixed oxide facilitate the cleavage of Mg-H bonds and lower the kinetic barrier for the dissociation of hydrogen molecules,thereby substantially enhancing the kinetics of the Mg/MgH_(2)system.This study presents a strategic method for developing efficient catalysts for hydrogen storage materials by harnessing the synergistic effects of metal elements.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
Catalytic activity and hydrothermal stability are both crucial for the application of the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)catalyst in diesel vehicles.In this study,a tin(Sn)-modified Ce-N...Catalytic activity and hydrothermal stability are both crucial for the application of the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)catalyst in diesel vehicles.In this study,a tin(Sn)-modified Ce-Nb mixed-oxide catalyst was synthesized as an NH_(3)-SCR catalyst for NO_(x)emission control.After the intro-duction of Sn,both the NH_(3)-SCR activity and the hydrothermal stability of the catalyst were remarkably promoted.Even after hydrothermal aging at 1000℃,the developed Ce_(1)Sn_(2)Nb_(1)O_(x)catalyst achieved more than 90%NO_(x)conversion at 325-500℃.Various methods,including N2-physisorption,X-ray diffraction,in-situ high-temperature X-ray diffraction,high-resolution transmission electron microscopy,X-ray pho-toelectron spectroscopy,X-ray absorption fine-structure spectroscopy,temperature-programmed reduc-tion of hydrogen,temperature-programmed desorption of ammonia,and density functional theory calculations were used to investigate the promotional effects induced by the Sn species.The characteri-zation results showed that the addition of Sn not only promoted the formation of the Ce-Nb active phase but also improved its thermal stability,contributing to the excellent NH_(3)-SCR performance and hydrothermal stability.This study provides an excellent sintering-resistance catalyst for the application of diesel engine NO_(x)emission control.展开更多
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supported by the Natural Science Foundation of Hebei Province(E2023502006)Fundamental Research Fund for the Central Universities(2025MS131).
文摘Magnesium hydride(MgH_(2)),a promising high-capacity hydrogen storage material,is hindered by slow dehydrogenation kinetics.AIdriven catalyst discovery to address this is often hampered by the laborious extraction of data from unstructured literature.To overcome this,we introduce a transformative“LLM to Agent”framework that synergistically integrates Large Language Models(LLMs)for automated data curation with Machine Learning(ML)for predictive design.We automatically constructed a comprehensive database of 809 MgH_(2)catalysts(6555 data rows)with high fidelity and an~40-fold acceleration over manual methods.The resulting ML models achieved high accuracy(average R^(2)>0.91)in predicting dehydrogenation temperature and activation energy,subsequently guiding a Genetic Algorithm(GA)in an exploratory inverse design that autonomously uncovered key design principles for high-performance catalysts.Encouragingly,a strong alignment was found between these AI-discovered principles and the design strategies of recently reported,state-of-the-art experimental systems,providing substantial evidence for the validity of our approach.The framework culminates in Cat-Advisor,a novel,domain-adapted multi-agent system.Cat-Advisor translates ML predictions and retrieval-augmented knowledge into actionable design guidance,demonstrating capabilities that surpass those of general-purpose LLMs in this specialized domain.This work delivers a practical AI toolkit for accelerated materials discovery and advances the emerging Agent-based paradigm for designing next-generation energy technologies.
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.
基金supported by the National Natural Sci-ence Foundation of China(Nos.U21A20288 and 21978280).
文摘Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrate that bio-based benzaldehyde,a noteworthy high-value chemical,is able to be directionally prepared from lignocellulosic biomass.This new control-lable transformation was materialized by uniting catalytic-pyrolysis of lignocellulose to toluene intermediate and catalytic oxidation of toluene intermediate to bio-based benzalde-hyde.This work also developed a highly active magnetic catalyst(CoFe_(2)O_(4)@Biochar(HTR)),achieving 77.1%benzaldehyde selectivity and 46.7%benzaldehyde yield using this catalyst.It was found that introducing the biochar carrier into the cobalt iron composite metal oxide cat-alyst enhanced hydroxyl radical formation and bio-based benzaldehyde synthesis.Based on catalyst characterizations and hydroxyl radical analysis,potential reaction mechanism for bio-based benzaldehyde synthesis was proposed.This strategy may provide a beneficial pathway for developing high-value bio-based chemical(benzaldehyde)using renewable lignocellulosic biomass.
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.
文摘Supported metal catalysts are the backbone of heterogeneous catalysis,playing a crucial role in the modern chemical industry.Metal-support interactions(MSIs)are known important in determining the catalytic performance of supported metal catalysts.This is particularly true for single-atom catalysts(SACs)and pseudo-single-atom catalysts(pseudo-SACs),where all metal atoms are dispersed on,and interact directly with the support.Consequently,the MSI of SACs and pseudo-SACs are theoretically more sensitive to modulation compared to that of traditional nanoparticle catalysts.In this work,we experimentally demonstrated this hypothesis by an observed size-dependent MSI modulation.We fabricated CoFe_(2)O_(4) supported Pt pseudo-SACs and nanoparticle catalysts,followed by a straightforward water treatment process.It was found that the covalent strong metal-support interaction(CMSI)in pseudo-SACs can be weakened,leading to a significant activity improvement in methane combustion reaction.This finding aligns with our recent observation of CoFe_(2)O_(4) supported Pt SACs.By contrast,the MSI in Pt nanoparticle catalyst was barely affected by the water treatment,giving rise to almost unchanged catalytic performance.This work highlights the critical role of metal size in determining the MSI modulation,offering a novel strategy for tuning the catalytic performance of SACs and pseudo-SACs by fine-tuning their MSIs.
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 the National Key Research and Development Program of China(No.2024YFB4007204,2022YFB4004301)the National Natural Science Founda-tion of China(Grant Nos.52477220,52301287,22005353)+2 种基金the Two-chain Integration Key Project of Shaanxi Province(2021LLRH-09)the Key Research and Development Program of Shaanxi Province(No.2024CY2-GJHX-44,2024CY2-GJHX-53,2024GX-ZDCYL-04-06)the Key Industrial Chain Technology Research Program of Xi’an city(23LL-RHZDZX0017).
文摘The role of catalysts in enhancing the hydrogen storage kinetics of the Mg/MgH_(2)system is pivotal.However,the exploration of efficient catalysts and the underlying principles of their design remain both a prominent focus and a significant challenge in current research.In this study,we present a bimetallic oxide of Bi_(2)Ti_(2)O_(7)hollow sphere as a highly effective catalyst for MgH_(2).As a result,the Bi_(2)Ti_(2)O_(7)-catalyzed Mg/MgH_(2)system lowers the hydrogen desorption initiation temperature to 194.3℃,reduces the peak desorption temperature to 245.6℃,decreases the dehydrogenation activation energy to 82.14 kJ·mol^(−1),and can absorb 5.4 wt.%of hydrogen within 60 s at 200℃,demonstrating outstanding hydrogen ab/desorption kinetics,compared to pure MgH_(2).Additionally,it can maintain a high hydrogen capacity of 5.2 wt.%,even after 50 dehydrogenation cycles,showing good cycle stability.The characterization results show that the high-valent Bi and Ti in Bi_(2)Ti_(2)O_(7)are reduced to their low-valent or even zero-valent metallic states during the dehydrogenation and hydrogenation process,thus establishing an in-situ multivalent and multi-element catalytic environment.Density functional theory calculations further reveal that the synergistic effects between Bi and Ti in the Bi-Ti mixed oxide facilitate the cleavage of Mg-H bonds and lower the kinetic barrier for the dissociation of hydrogen molecules,thereby substantially enhancing the kinetics of the Mg/MgH_(2)system.This study presents a strategic method for developing efficient catalysts for hydrogen storage materials by harnessing the synergistic effects of metal elements.
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.
基金supported by the National Natural Science Foundation of China(52225004 and 22276202)the National Key Research and Development Program of China(2022YFC3701804)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2019045).
文摘Catalytic activity and hydrothermal stability are both crucial for the application of the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)catalyst in diesel vehicles.In this study,a tin(Sn)-modified Ce-Nb mixed-oxide catalyst was synthesized as an NH_(3)-SCR catalyst for NO_(x)emission control.After the intro-duction of Sn,both the NH_(3)-SCR activity and the hydrothermal stability of the catalyst were remarkably promoted.Even after hydrothermal aging at 1000℃,the developed Ce_(1)Sn_(2)Nb_(1)O_(x)catalyst achieved more than 90%NO_(x)conversion at 325-500℃.Various methods,including N2-physisorption,X-ray diffraction,in-situ high-temperature X-ray diffraction,high-resolution transmission electron microscopy,X-ray pho-toelectron spectroscopy,X-ray absorption fine-structure spectroscopy,temperature-programmed reduc-tion of hydrogen,temperature-programmed desorption of ammonia,and density functional theory calculations were used to investigate the promotional effects induced by the Sn species.The characteri-zation results showed that the addition of Sn not only promoted the formation of the Ce-Nb active phase but also improved its thermal stability,contributing to the excellent NH_(3)-SCR performance and hydrothermal stability.This study provides an excellent sintering-resistance catalyst for the application of diesel engine NO_(x)emission control.
