Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.展开更多
The photocatalytic oxidation of methane(CH_(4)) to valuable chemicals like low alcohols(CH_(3)OH and C_(2)H_(5)OH) represents a significant technological advancement with implications for energy conversion and environ...The photocatalytic oxidation of methane(CH_(4)) to valuable chemicals like low alcohols(CH_(3)OH and C_(2)H_(5)OH) represents a significant technological advancement with implications for energy conversion and environmental purification.A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes,which can lead to over-oxidation and reduced selectivity and efficiency.To address these issues,we have developed a sodium-doped zinc oxide(Na-ZnO) modified with cobalt oxide(CoO) catalyst.This catalyst has demonstrated excellent performance in converting methane to low alcohols,achieving a yield of 130 μmol g^(-1)h^(-1) and a selectivity of up to 96 %.The doping of Na in ZnO significantly enhances methane adsorption,while the surface-modified CoO effectively captures photogenerated holes,activates water molecules,and uses hydroxyl radicals to activate methane,thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products.This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols,offering a new perspective for the application of photocatalytic technology in energy and environmental fields.展开更多
Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchan...Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.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support from the Zhejiang Provincial Natural Science Foundation of China (No.LQ24B030011)the Ningbo Natural Science Foundation (No.2023J181)+4 种基金the Open Research Fund of Key Laboratory of Functional Inorganic Materials Chemistry of the Ministry of Education (Heilongjiang University)the Start-up Funding offered by Ningbo University of Technology to J.D.LiNational Natural Science Foundation of China (No.U24A2071)Postdoctoral Research Start-up Fund (No.2111224002)Harbin Normal University Talent Plan (No.1305124213) to Y.D.Liu。
文摘The photocatalytic oxidation of methane(CH_(4)) to valuable chemicals like low alcohols(CH_(3)OH and C_(2)H_(5)OH) represents a significant technological advancement with implications for energy conversion and environmental purification.A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes,which can lead to over-oxidation and reduced selectivity and efficiency.To address these issues,we have developed a sodium-doped zinc oxide(Na-ZnO) modified with cobalt oxide(CoO) catalyst.This catalyst has demonstrated excellent performance in converting methane to low alcohols,achieving a yield of 130 μmol g^(-1)h^(-1) and a selectivity of up to 96 %.The doping of Na in ZnO significantly enhances methane adsorption,while the surface-modified CoO effectively captures photogenerated holes,activates water molecules,and uses hydroxyl radicals to activate methane,thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products.This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols,offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
基金financially supported the National Key R&D Program of China (No.2022YFA1502902)the National Natural Science Foundation of China (NSFC,Nos.22475152 and U21A20286)the 111 Project of China (No.D17003)。
文摘Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.
