MnO_x-CeO_2 catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO_2 and amorphous MnO_x existed in MnO_x-CeO_2 ca...MnO_x-CeO_2 catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO_2 and amorphous MnO_x existed in MnO_x-CeO_2 catalysts. High temperature calcination caused the sintering of amorphous MnO_x and transforming to bulk crystalline Mn_2O_3, H_2-TPR and XPS results suggested the valence of Mn in MnO_x-CeO_2 was higher than pure MnO_x, and decreased with the increasing calcination temperature, The turnover frequency（TOF） was calculated based on the initial reducibility according to H_2-TPR quantitation and kinetic study. The TOF results indicated that the initial reducibility of amorphous MnO_x with high valence manganese ions was equivalent to the active sites for NO oxidation. It can be inferred that the amorphous MnO_x plays a key role in low-temperature NO oxidation.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
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
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
Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have re...Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.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 use of fossil fuels significantly contributes to excess CO_(2) emissions.Catalytic hydrogenation of CO_(2) to dimethyl ether(DME)is an effective method for CO_(2) recycling,offering both environmental and economic...The use of fossil fuels significantly contributes to excess CO_(2) emissions.Catalytic hydrogenation of CO_(2) to dimethyl ether(DME)is an effective method for CO_(2) recycling,offering both environmental and economic benefits.Zeolites,known for their efficiency as solid catalysts,are widely utilized in the chemical industries.Bifunctional catalysts based on zeolites have gained attention for their applications in CO_(2) hydrogenation to DME.This review discusses key factors affecting the catalytic performance of zeolites,including topologies,Si/Al ratio,crystal size,and the proximity of metallic species to the zeolite catalysts.Although bifunctional catalytic systems enhance the conversion of CO_(2) to DME,they also lead to high CO selectivity at elevated temperatures,which can limit both DME yield and selectivity.We present recent advancements in the development of bifunctional catalysts for the direct hydrogenation of CO_(2) to DME,providing insights for designing optimized catalysts for tandem reaction systems.展开更多
Charge-neutral method(CNM)is extensively used in investigating the performance of catalysts and the mechanism of N_(2)electrochemical reduction(NRR).However,disparities remain between the predicted potentials required...Charge-neutral method(CNM)is extensively used in investigating the performance of catalysts and the mechanism of N_(2)electrochemical reduction(NRR).However,disparities remain between the predicted potentials required for NRR by the CNM methods and those observed experimentally,as the CNM method neglects the charge effect from the electrode potential.To address this issue,we employed the constant electrode potential(CEP)method to screen atomic transition metal-N-graphene(M_(1)/N-graphene)as NRR electrocatalysts and systematically investigated the underlying catalytic mechanism.Among eight types of M_(1)/N-graphene(M_(1)=Mo,W,Fe,Re,Ni,Co,V,Cr),W_(1)/N-graphene emerges as the most promising NRR electrocatalyst with a limiting potential as low as−0.13 V.Additionally,the W_(1)/N-graphene system consistently maintains a positive charge during the reaction due to its Fermi level being higher than that of the electrode.These results better match with the actual circumstances compared to those calculated by conventional CNM method.Thus,our work not only develops a promising electrocatalyst for NRR but also deepens the understanding of the intrinsic electrocatalytic mechanism.展开更多
Industrial decarbonization is critical for achieving net-zero goals.The carbon dioxide electrochemical reduction reaction(CO_(2)RR)is a promising approach for converting CO_(2)into high-value chemicals,offering the po...Industrial decarbonization is critical for achieving net-zero goals.The carbon dioxide electrochemical reduction reaction(CO_(2)RR)is a promising approach for converting CO_(2)into high-value chemicals,offering the potential for decarbonizing industrial processes toward a sustainable,carbon-neutral future.However,developing CO_(2)RR catalysts with high selectivity and activity remains a challenge due to the complexity of finding such catalysts and the inefficiency of traditional computational or experimental approaches.Here,we present a methodology integrating density functional theory(DFT)calculations,deep learning models,and an active learning strategy to rapidly screen high-performance catalysts.The proposed methodology is then demonstrated on graphene-based single-atom catalysts for selective CO_(2)electroreduction to methanol.First,we conduct systematic binding energy calculations for 3045 single-atom catalysts to identify thermodynamically stable catalysts as the design space.We then use a graph neural network,fine-tuned with a specialized adsorption energy database,to predict the relative activity and selectivity of the candidate catalysts.An autonomous active learning framework is used to facilitate the exploration of designs.After six learning cycles and 2180 adsorption calculations across 15 intermediates,we develop a surrogate model that identifies four novel catalysts on the Pareto front of activity and selectivity.Our work demonstrates the effectiveness of leveraging a domain foundation model with an active learning framework and holds potential to significantly accelerate the discovery of high-performance CO_(2)RR catalysts.展开更多
Copper(Cu)is widely used in the electrochemical carbon dioxide reduction reaction(ECO_(2)RR)for efficient methane(CH_(4))product.However,the morphology and valence of Cu-based catalysts are usually unstable under reac...Copper(Cu)is widely used in the electrochemical carbon dioxide reduction reaction(ECO_(2)RR)for efficient methane(CH_(4))product.However,the morphology and valence of Cu-based catalysts are usually unstable under reaction conditions.In this work,we prepared Ce-doped MOF-199 precursor(Ce/HKUST-1)and further obtained nanoparticle electrocatalyst Ce/CuO_(x)-NPs by cyclic voltammetry(CV)pretreatment.The Faradic efficiency of methane(FE_(CH_(4)))maintains above 62%within a broad potential window of 350 mV and the maximum FE_(CH_(4))reaches 67.4%with a partial current density of 293 mA/cm^(2)at-1.6 V vs.a reversible hydrogen electrode.Catalyst characterization and theoretical calculations revealed that the unique electronic structure and large ionic radius of Cerium(Ce)not only promoted the generation of key intermediate*CO but also lowered energy barrier of the*CO to*CHO step.This study provides a novel and efficient catalyst for methane production in ECO_(2)RR and offers profound insights into constructing high performance Cu-based catalysts.展开更多
CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synerg...CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.展开更多
The Li-CO_(2)battery has been highly rated as an intriguing technique for balancing the carbon cycle for years,but it is still significantly challenged by the obstacles such as limited reversibility,sluggish kinetics,...The Li-CO_(2)battery has been highly rated as an intriguing technique for balancing the carbon cycle for years,but it is still significantly challenged by the obstacles such as limited reversibility,sluggish kinetics,and poor energy efficiency.Hence,the design and development of advance catalysts that can enhance the kinetics and reversibility of the CO_(2)electrochemical cycling reactions are considered the imperative tasks.Transition metal-based catalysts are widely considered appealing owing to their unfilled dorbitals,rich and adjustable valences,as well as processibility.In this review,the working mechanism and the key issues of the CO_(2)electrochemical cycling reaction are discussed first.Then the strategies for composition and structure design of different type of transition metal-based catalysts are highlighted,including their benefits,limitations,and the ways to implement these strategies.Finally,based on the pioneering research,the perspectives on the challenges and key points for the future development of cathode catalyst are proposed.展开更多
The need to secure environmentally sustainable sources of clean fuel has led to intensive research into the catalytic conversion of CO_(2)into valuable C_(2)+compounds.However,the intrinsically sluggish reduction kine...The need to secure environmentally sustainable sources of clean fuel has led to intensive research into the catalytic conversion of CO_(2)into valuable C_(2)+compounds.However,the intrinsically sluggish reduction kinetics and competing reaction pathways present challenges in achieving high product selectivity and efficiency.Herein,we focus on the transformation of CO_(2)into C_(2)+products,particularly emphasizing advances in non-copper-based catalytic systems,which have emerged as promising alternatives that present unique electronic structures and adsorption properties.Unlike conventional copper catalysts,these systems offer distinct advantages in selectivity and stability,particularly through the modulation of surface defect engineering.We systematically analyze the main reaction pathways leading to C_(2)+products,including ethylene formation and higher hydrocarbon(C_(2)-4)alcohols and oxygenates,while critically assessing the mechanistic insights that differentiate non-copper catalysts from their Cu-based counterparts.By summarizing recent developments,the key challenges,and optimization strategies,we provide a comprehensive overview of how non-copper catalysts can enable efficient and scalable CO_(2)reduction reactions,with an aim of assisting researchers in their design of novel catalysts that may reach industrial applications.展开更多
Designing the coordination environment of heteroatoms around metal sites and optimizing the electronic structure of diatomic metal sites remain significant challenges in achieving efficient CO_(2)overall splitting.Her...Designing the coordination environment of heteroatoms around metal sites and optimizing the electronic structure of diatomic metal sites remain significant challenges in achieving efficient CO_(2)overall splitting.Herein,we report four configurations(Cu/Ni-N_(4)C_(2),Cu/Ni-N_(2)C_(4),Cu/Ni-N_(2)C_(3)and Cu/Ni-N_(2)C_(2))constructed by precise regulation of the coordination environment around bimetallic atoms.Cu/Ni-N_(2)C_(2)showed high performance in electrochemical CO_(2)reduction(ECR)and water oxidation evolution reaction(OER).In the electrochemical CO_(2)overall splitting reaction,it achieved a Faraday efficiency of CO(FECO)of98.0%at a low cell voltage of-2.9 V,significantly higher than widely reported values.Moreover,the FE_(CO)is above 90%over-2.7 to-4.1 V of cell voltages.Cu/Ni-N_(2)C_(2)achieved long-term ECR stability of 110 h at-100 mA cm^(-2).Mechanism studies revealed that the change of coordination environment around the diatomic pairs moves the d-band center of the Ni atom closer to the Fermi level,thereby modulating the adsorption capacity of the catalysts to the reaction intermediates^(*)COOH and^(*)O.This work presents valuable insights into the rational design of diatomic catalysts and elucidates the intricate structureperformance relationship in advancing electrochemical CO_(2)overall splitting technology and energyconversion applications.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
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
Electrocatalytic carbon dioxide reduction is one of the very effective ways to achieve carbon neutrality,by converting CO_(2) into fuels and high-value chemicals.Therefore,it is crucial to design efficient CO_(2) redu...Electrocatalytic carbon dioxide reduction is one of the very effective ways to achieve carbon neutrality,by converting CO_(2) into fuels and high-value chemicals.Therefore,it is crucial to design efficient CO_(2) reduction electrocatalysts and understand their reaction mechanism.Among various catalysts,dual-atom catalysts(DACs)offer several advantages,including a wide range of reaction types,high stability,customizable design,high re-action selectivity,tunable electronic structure,and strong catalytic activity.It is thus crucial to understand the reaction mechanism of DACs in CO_(2) reduction,especially the regulation of critical intermediates.In this review,we focus on the synthesis,structure-activity relationship,and application of DACs.Finally,some challenges and further prospects are also summarized,especially in terms of stability,product selectivity,and large-scale deployment.With the advancement of new materials and computational tools,DACs are poised to play increasingly important roles in CO_(2) reduction,providing effective solutions for sustainable energy and environ-mental protection.展开更多
The development of human industry inevitably leads to excessive carbon dioxide(CO_(2))emissions.It can cause critical ecological consequences,primarily global warming and ocean acidification.In this regard,close atten...The development of human industry inevitably leads to excessive carbon dioxide(CO_(2))emissions.It can cause critical ecological consequences,primarily global warming and ocean acidification.In this regard,close attention is paid to the carbon capture,utilization,and storage concept.The key component of this concept is the catalytic conversion of CO_(2)into valuable chemical compounds and fuels.Light olefins are one of the most industrially important chemicals,and their sustainable production via CO_(2)hydrogenation could be a prospective way to reach carbon neutrality.Fe-based materials are widely recognized as effective thermocatalysts and photothermal catalysts for that process thanks to their low cost,high activity,and good stability.This review critically examines the most recent progress in the development and optimization of Fe-based catalysts for CO_(2)hydrogenation into light olefins.Particular attention is paid to understanding the roles of catalyst composition,structural properties,and promoters in enhancing catalytic activity,selectivity,and stability.展开更多
The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synt...The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synthesis technique is reported to fabricate atom-nanoisland-sea structured SACs for the first time.The resultant catalysts are constructed by Pt single atoms on In_(2)O_(3)supported by Co3O4nanoislands uniformly dispersed in the sea of reduced graphene oxide.The laser process,with a maximum temperature of 2349 K within~100μs,produced abundant oxygen vacancies(up to 70.8%)and strong interactions between the Pt single atoms and In_(2)O_(3).The laser-synthesized catalysts exhibited a remarkable catalytic performance towards CO_(2)hydrogenation to methanol at 300°C with a CO_(2)conversion of 30.3%,methanol selectivity of 90.6%and exceptional stability over 48 h without any deactivation,outperforming most of the relevant catalysts reported in the literature.Characterization of the spent catalysts after testing for 48 h reveals that the Pt single atoms were retained and the oxygen vacancies remained almost unchanged.In situ diffuse reflectance infrared Fourier transform spectrum was conducted to establish the reaction mechanism supported by the density functional theory simulations.It is believed that this laser synthesis strategy opens a new avenue towards rapidly manufacturing highly active and robust thermal SACs.展开更多
Global investment in ethylene(C_(2)H_(4))production via nonpetroleum pathways is rising,highlighting its growing importance in the energy and environmental sectors.The electroreduction of carbon dioxide(CO_(2))to C_(2...Global investment in ethylene(C_(2)H_(4))production via nonpetroleum pathways is rising,highlighting its growing importance in the energy and environmental sectors.The electroreduction of carbon dioxide(CO_(2))to C_(2)H_(4) inflow cells is emerging as a promising technology with broad practical applications.Direct delivery of gaseous CO_(2) to the cathode catalyst layer overcomes mass transfer limitations,enhancing reaction rates and enabling high current density.This review summarizes recent research progress in the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR)for selective C_(2)H_(4) production inflow cells.It outlines the principles of eCO_(2)RR to C_(2)H_(4) and discusses the influence of copper-based catalyst morphology,crystal facet,oxidation state,surface modification strategy,and synergistic effects on catalytic performance.In addition,it highlights the compositional structure of theflow cell,and the selection and optimization of operating conditions,including gas diffusion electrodes,electrolytes,ion exchange membranes,and alternative anode reaction types beyond the oxygen evolution reaction.Finally,advances in machine learning are presented for accelerating catalyst screening and predicting dynamic changes in catalysts during reduction.This comprehensive review serves as a valuable reference for the development of efficient catalysts and the construction of electrolytic devices for the electrocatalytic reduction of CO_(2) to C_(2)H_(4).展开更多
基金Project supported by the National key research and development program(2016YFC0204901)the National Natural Science Foundation of China(21576207)the introduction of talent and technology cooperation plan of Tianjin(14RCGFGX00849)
文摘MnO_x-CeO_2 catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO_2 and amorphous MnO_x existed in MnO_x-CeO_2 catalysts. High temperature calcination caused the sintering of amorphous MnO_x and transforming to bulk crystalline Mn_2O_3, H_2-TPR and XPS results suggested the valence of Mn in MnO_x-CeO_2 was higher than pure MnO_x, and decreased with the increasing calcination temperature, The turnover frequency（TOF） was calculated based on the initial reducibility according to H_2-TPR quantitation and kinetic study. The TOF results indicated that the initial reducibility of amorphous MnO_x with high valence manganese ions was equivalent to the active sites for NO oxidation. It can be inferred that the amorphous MnO_x plays a key role in low-temperature NO oxidation.
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 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supported by the National Key R&D Program of China(2024YFB4106400)National Natural Science Foundation of China(22209200,52302331)。
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.
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 National Key Research and Development Program of China(2021YFA1500401)the National Natural Science Foundation of China(22288101)the‘111 Center’(B17020)for supporting this work.
文摘The use of fossil fuels significantly contributes to excess CO_(2) emissions.Catalytic hydrogenation of CO_(2) to dimethyl ether(DME)is an effective method for CO_(2) recycling,offering both environmental and economic benefits.Zeolites,known for their efficiency as solid catalysts,are widely utilized in the chemical industries.Bifunctional catalysts based on zeolites have gained attention for their applications in CO_(2) hydrogenation to DME.This review discusses key factors affecting the catalytic performance of zeolites,including topologies,Si/Al ratio,crystal size,and the proximity of metallic species to the zeolite catalysts.Although bifunctional catalytic systems enhance the conversion of CO_(2) to DME,they also lead to high CO selectivity at elevated temperatures,which can limit both DME yield and selectivity.We present recent advancements in the development of bifunctional catalysts for the direct hydrogenation of CO_(2) to DME,providing insights for designing optimized catalysts for tandem reaction systems.
基金Natural Science Foundation of Guangdong Province(No.2024A1515011094(C.Q Sun))National Natural Science Foundation of China(Nos.12304243(H.X.Fang),12150100(B.Wang))is gratefully acknowledged。
文摘Charge-neutral method(CNM)is extensively used in investigating the performance of catalysts and the mechanism of N_(2)electrochemical reduction(NRR).However,disparities remain between the predicted potentials required for NRR by the CNM methods and those observed experimentally,as the CNM method neglects the charge effect from the electrode potential.To address this issue,we employed the constant electrode potential(CEP)method to screen atomic transition metal-N-graphene(M_(1)/N-graphene)as NRR electrocatalysts and systematically investigated the underlying catalytic mechanism.Among eight types of M_(1)/N-graphene(M_(1)=Mo,W,Fe,Re,Ni,Co,V,Cr),W_(1)/N-graphene emerges as the most promising NRR electrocatalyst with a limiting potential as low as−0.13 V.Additionally,the W_(1)/N-graphene system consistently maintains a positive charge during the reaction due to its Fermi level being higher than that of the electrode.These results better match with the actual circumstances compared to those calculated by conventional CNM method.Thus,our work not only develops a promising electrocatalyst for NRR but also deepens the understanding of the intrinsic electrocatalytic mechanism.
基金supported by the National Key Research and Development Program of China(2022ZD0117501)the Scientific Research Innovation Capability Support Project for Young Faculty(ZYGXQNJSKYCXNLZCXM-E7)the Tsinghua University Initiative Scientific Research Program and the Carbon Neutrality and Energy System Transformation(CNEST)Program led by Tsinghua University.
文摘Industrial decarbonization is critical for achieving net-zero goals.The carbon dioxide electrochemical reduction reaction(CO_(2)RR)is a promising approach for converting CO_(2)into high-value chemicals,offering the potential for decarbonizing industrial processes toward a sustainable,carbon-neutral future.However,developing CO_(2)RR catalysts with high selectivity and activity remains a challenge due to the complexity of finding such catalysts and the inefficiency of traditional computational or experimental approaches.Here,we present a methodology integrating density functional theory(DFT)calculations,deep learning models,and an active learning strategy to rapidly screen high-performance catalysts.The proposed methodology is then demonstrated on graphene-based single-atom catalysts for selective CO_(2)electroreduction to methanol.First,we conduct systematic binding energy calculations for 3045 single-atom catalysts to identify thermodynamically stable catalysts as the design space.We then use a graph neural network,fine-tuned with a specialized adsorption energy database,to predict the relative activity and selectivity of the candidate catalysts.An autonomous active learning framework is used to facilitate the exploration of designs.After six learning cycles and 2180 adsorption calculations across 15 intermediates,we develop a surrogate model that identifies four novel catalysts on the Pareto front of activity and selectivity.Our work demonstrates the effectiveness of leveraging a domain foundation model with an active learning framework and holds potential to significantly accelerate the discovery of high-performance CO_(2)RR catalysts.
基金the funding support from the National Natural Science Foundation of China(No.22308066)the Science and Technology Major Program of Guangxi(No.Guike AA23062018)+2 种基金the Guangxi Science and Technology Base and Talent Special Project(Nos.2021AC19353,2022AC20018,AD23026311)the Natural Science Foundation of Guangxi Province(No.2024GXNSFAA010271)the Innovation Project of Guangxi Graduate Education(No.YCBZ2022012)。
文摘Copper(Cu)is widely used in the electrochemical carbon dioxide reduction reaction(ECO_(2)RR)for efficient methane(CH_(4))product.However,the morphology and valence of Cu-based catalysts are usually unstable under reaction conditions.In this work,we prepared Ce-doped MOF-199 precursor(Ce/HKUST-1)and further obtained nanoparticle electrocatalyst Ce/CuO_(x)-NPs by cyclic voltammetry(CV)pretreatment.The Faradic efficiency of methane(FE_(CH_(4)))maintains above 62%within a broad potential window of 350 mV and the maximum FE_(CH_(4))reaches 67.4%with a partial current density of 293 mA/cm^(2)at-1.6 V vs.a reversible hydrogen electrode.Catalyst characterization and theoretical calculations revealed that the unique electronic structure and large ionic radius of Cerium(Ce)not only promoted the generation of key intermediate*CO but also lowered energy barrier of the*CO to*CHO step.This study provides a novel and efficient catalyst for methane production in ECO_(2)RR and offers profound insights into constructing high performance Cu-based catalysts.
文摘CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.
基金financially supported by the National Natural Science Foundation of China(52201254,52234001,52074177)the National Key Research and Development Program(2022YFC3900905)+3 种基金the Natural Science Foundation of Shandong Province(ZR2020QE012,ZR2020MB090,ZR2023ME155,ZR2023ME085)the Scientific Research Foundation for New Talents in University of Jinan(XRC2406)the project of “20 Items of University”of Jinan(202228046)the Introducing Major Universities and Research Institutions to Jointly Build Innovative Carrier Project of Jining City(2023DYDS022)。
文摘The Li-CO_(2)battery has been highly rated as an intriguing technique for balancing the carbon cycle for years,but it is still significantly challenged by the obstacles such as limited reversibility,sluggish kinetics,and poor energy efficiency.Hence,the design and development of advance catalysts that can enhance the kinetics and reversibility of the CO_(2)electrochemical cycling reactions are considered the imperative tasks.Transition metal-based catalysts are widely considered appealing owing to their unfilled dorbitals,rich and adjustable valences,as well as processibility.In this review,the working mechanism and the key issues of the CO_(2)electrochemical cycling reaction are discussed first.Then the strategies for composition and structure design of different type of transition metal-based catalysts are highlighted,including their benefits,limitations,and the ways to implement these strategies.Finally,based on the pioneering research,the perspectives on the challenges and key points for the future development of cathode catalyst are proposed.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U24B20201)National Natural Science Foundation of China(22372007 and 21972010).
文摘The need to secure environmentally sustainable sources of clean fuel has led to intensive research into the catalytic conversion of CO_(2)into valuable C_(2)+compounds.However,the intrinsically sluggish reduction kinetics and competing reaction pathways present challenges in achieving high product selectivity and efficiency.Herein,we focus on the transformation of CO_(2)into C_(2)+products,particularly emphasizing advances in non-copper-based catalytic systems,which have emerged as promising alternatives that present unique electronic structures and adsorption properties.Unlike conventional copper catalysts,these systems offer distinct advantages in selectivity and stability,particularly through the modulation of surface defect engineering.We systematically analyze the main reaction pathways leading to C_(2)+products,including ethylene formation and higher hydrocarbon(C_(2)-4)alcohols and oxygenates,while critically assessing the mechanistic insights that differentiate non-copper catalysts from their Cu-based counterparts.By summarizing recent developments,the key challenges,and optimization strategies,we provide a comprehensive overview of how non-copper catalysts can enable efficient and scalable CO_(2)reduction reactions,with an aim of assisting researchers in their design of novel catalysts that may reach industrial applications.
基金supported by Shanxi Provincial Key Research and Development Project(No.20201102002)。
文摘Designing the coordination environment of heteroatoms around metal sites and optimizing the electronic structure of diatomic metal sites remain significant challenges in achieving efficient CO_(2)overall splitting.Herein,we report four configurations(Cu/Ni-N_(4)C_(2),Cu/Ni-N_(2)C_(4),Cu/Ni-N_(2)C_(3)and Cu/Ni-N_(2)C_(2))constructed by precise regulation of the coordination environment around bimetallic atoms.Cu/Ni-N_(2)C_(2)showed high performance in electrochemical CO_(2)reduction(ECR)and water oxidation evolution reaction(OER).In the electrochemical CO_(2)overall splitting reaction,it achieved a Faraday efficiency of CO(FECO)of98.0%at a low cell voltage of-2.9 V,significantly higher than widely reported values.Moreover,the FE_(CO)is above 90%over-2.7 to-4.1 V of cell voltages.Cu/Ni-N_(2)C_(2)achieved long-term ECR stability of 110 h at-100 mA cm^(-2).Mechanism studies revealed that the change of coordination environment around the diatomic pairs moves the d-band center of the Ni atom closer to the Fermi level,thereby modulating the adsorption capacity of the catalysts to the reaction intermediates^(*)COOH and^(*)O.This work presents valuable insights into the rational design of diatomic catalysts and elucidates the intricate structureperformance relationship in advancing electrochemical CO_(2)overall splitting technology and energyconversion applications.
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 star-up funding at Chengdu University(No.2081924059).
文摘Electrocatalytic carbon dioxide reduction is one of the very effective ways to achieve carbon neutrality,by converting CO_(2) into fuels and high-value chemicals.Therefore,it is crucial to design efficient CO_(2) reduction electrocatalysts and understand their reaction mechanism.Among various catalysts,dual-atom catalysts(DACs)offer several advantages,including a wide range of reaction types,high stability,customizable design,high re-action selectivity,tunable electronic structure,and strong catalytic activity.It is thus crucial to understand the reaction mechanism of DACs in CO_(2) reduction,especially the regulation of critical intermediates.In this review,we focus on the synthesis,structure-activity relationship,and application of DACs.Finally,some challenges and further prospects are also summarized,especially in terms of stability,product selectivity,and large-scale deployment.With the advancement of new materials and computational tools,DACs are poised to play increasingly important roles in CO_(2) reduction,providing effective solutions for sustainable energy and environ-mental protection.
基金supported by the Ministry of Higher Education,Science and Innovation,and the Slovenian Research Agency(ARIS)throughresearch grants J7-4638 and J2-4441.
文摘The development of human industry inevitably leads to excessive carbon dioxide(CO_(2))emissions.It can cause critical ecological consequences,primarily global warming and ocean acidification.In this regard,close attention is paid to the carbon capture,utilization,and storage concept.The key component of this concept is the catalytic conversion of CO_(2)into valuable chemical compounds and fuels.Light olefins are one of the most industrially important chemicals,and their sustainable production via CO_(2)hydrogenation could be a prospective way to reach carbon neutrality.Fe-based materials are widely recognized as effective thermocatalysts and photothermal catalysts for that process thanks to their low cost,high activity,and good stability.This review critically examines the most recent progress in the development and optimization of Fe-based catalysts for CO_(2)hydrogenation into light olefins.Particular attention is paid to understanding the roles of catalyst composition,structural properties,and promoters in enhancing catalytic activity,selectivity,and stability.
基金supported by the Ningbo Yongjiang Science and Technology Programme(2023A-161-C)。
文摘The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synthesis technique is reported to fabricate atom-nanoisland-sea structured SACs for the first time.The resultant catalysts are constructed by Pt single atoms on In_(2)O_(3)supported by Co3O4nanoislands uniformly dispersed in the sea of reduced graphene oxide.The laser process,with a maximum temperature of 2349 K within~100μs,produced abundant oxygen vacancies(up to 70.8%)and strong interactions between the Pt single atoms and In_(2)O_(3).The laser-synthesized catalysts exhibited a remarkable catalytic performance towards CO_(2)hydrogenation to methanol at 300°C with a CO_(2)conversion of 30.3%,methanol selectivity of 90.6%and exceptional stability over 48 h without any deactivation,outperforming most of the relevant catalysts reported in the literature.Characterization of the spent catalysts after testing for 48 h reveals that the Pt single atoms were retained and the oxygen vacancies remained almost unchanged.In situ diffuse reflectance infrared Fourier transform spectrum was conducted to establish the reaction mechanism supported by the density functional theory simulations.It is believed that this laser synthesis strategy opens a new avenue towards rapidly manufacturing highly active and robust thermal SACs.
基金supported by the National Natural Science Foundation of China(22272081 and 51802160)the Startup Foundation for Introducing Talent of NUIST(S8113082001).
文摘Global investment in ethylene(C_(2)H_(4))production via nonpetroleum pathways is rising,highlighting its growing importance in the energy and environmental sectors.The electroreduction of carbon dioxide(CO_(2))to C_(2)H_(4) inflow cells is emerging as a promising technology with broad practical applications.Direct delivery of gaseous CO_(2) to the cathode catalyst layer overcomes mass transfer limitations,enhancing reaction rates and enabling high current density.This review summarizes recent research progress in the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR)for selective C_(2)H_(4) production inflow cells.It outlines the principles of eCO_(2)RR to C_(2)H_(4) and discusses the influence of copper-based catalyst morphology,crystal facet,oxidation state,surface modification strategy,and synergistic effects on catalytic performance.In addition,it highlights the compositional structure of theflow cell,and the selection and optimization of operating conditions,including gas diffusion electrodes,electrolytes,ion exchange membranes,and alternative anode reaction types beyond the oxygen evolution reaction.Finally,advances in machine learning are presented for accelerating catalyst screening and predicting dynamic changes in catalysts during reduction.This comprehensive review serves as a valuable reference for the development of efficient catalysts and the construction of electrolytic devices for the electrocatalytic reduction of CO_(2) to C_(2)H_(4).
