Photocatalytic synthesis of hydrogen peroxide(H_(2)O_(2))has emerged as a promising approach because of its simplicity and environmental benefits.However,significant challenges remain obstacles to their advancement,su...Photocatalytic synthesis of hydrogen peroxide(H_(2)O_(2))has emerged as a promising approach because of its simplicity and environmental benefits.However,significant challenges remain obstacles to their advancement,such as the rapid recombination of photogenerated charge carriers and sluggish surface redox reactions on nonmetallic organic catalysts.Metal-based organic catalysts with tunable electronic structures are considered ideal for exploring the mechanisms and structure-performance relationships in H_(2)O_(2) synthesis.This review summarizes the fundamental principles of photocatalytic H_(2)O_(2) synthesis via oxygen reduction and water oxidation reactions.Recent advancements in electronic structure tuning strategies for metal-based organic catalysts are critically examined,focusing on their impact on light absorption range,photogenerated carrier separation,O_(2) activation,and the selective generation of H_(2)O_(2).In addition,this review comprehensively evaluates the applications of sacrificial agents in photocatalytic reaction systems and offers insights into the future development of metal-based organic catalysts for H_(2)O_(2) photosynthesis.展开更多
Hydrogen peroxide(H_(2)O_(2))is highly required in various applications.The development of catalysts exhibiting elevated catalytic activity,selectivity,and stability is essential for H_(2)O_(2)production technology.Me...Hydrogen peroxide(H_(2)O_(2))is highly required in various applications.The development of catalysts exhibiting elevated catalytic activity,selectivity,and stability is essential for H_(2)O_(2)production technology.Metalbased catalysts are widely used for 2e^(-)ORR(oxygen reduction reaction)because of their adjustable structure,chemical stability,and availability.However,due to competition with the 4e^(-)ORR,modifications are often conducted to balance activity and selectivity.Common techniques include altering the surface electronic structure of catalysts and the interaction between active sites and intermediates.This review discusses diverse catalyst types(including precious and transition metals,single-atom catalysts,and MOFs/COFs)along with modification strategies(such as morphological control,electronic structure tuning,conductivity enhancement,and wettability improvement).The objective is to elucidate catalyst design and associated reaction mechanisms,as well as the relationship between catalyst structure and activity,in order to provide an insight for producing H_(2)O_(2)in an efficient,highly selective,and stable manner.展开更多
Hydrogen peroxide(H_(2)O_(2))is an important chemical that can be sustainably produced through a twoelectron pathway in the electrocatalytic oxygen reduction reaction(ORR).However,the high cost and low reaction effici...Hydrogen peroxide(H_(2)O_(2))is an important chemical that can be sustainably produced through a twoelectron pathway in the electrocatalytic oxygen reduction reaction(ORR).However,the high cost and low reaction efficiency of catalysts currently limit the widespread application of this technology.Developing high-selectivity and scalable catalysts and accurately identifying the reaction active sites remain challenges.In this work,we have developed a promising nanodiamond(ND)catalyst to achieve high-selectivity H_(2)O_(2)production by oxygen reduction.Through surface carbon hybridization regulation to identify specific oxygen-containing functional groups combined with titration,model catalysis and DFT methods,it is found that the presence of carbonyl groups inducing the surrounding carbon atoms exhibit an optimal*OOH adsorption strength,thus promoting the two-electron pathway in ORR.Specifically,dynamic evolution processes of carbonyl groups and key adsorbed intermediate products including O_(2)(ads),superoxide anion*O_(2)^(-),and *OOH are monitored in situ spectroscopy.In the flowcell device,ND catalyst realizes the high H_(2)O_(2)Faradaic efficiency around 92% with a rate activity up to 105 mol gC=O^(-1)h^(-1),surpassing among reported non-metallic catalysts.The total H_(2)O_(2)yield reaches to 23.79 m M after a ten-hour test,which is 2.56 times higher than that of carbonyl-passivated ND,demonstrating its potential in scale-up application.Both titration and model catalytic processes proposed in this study further offer methods of designing efficient electrocatalysts for H_(2)O_(2)production.展开更多
文摘Photocatalytic synthesis of hydrogen peroxide(H_(2)O_(2))has emerged as a promising approach because of its simplicity and environmental benefits.However,significant challenges remain obstacles to their advancement,such as the rapid recombination of photogenerated charge carriers and sluggish surface redox reactions on nonmetallic organic catalysts.Metal-based organic catalysts with tunable electronic structures are considered ideal for exploring the mechanisms and structure-performance relationships in H_(2)O_(2) synthesis.This review summarizes the fundamental principles of photocatalytic H_(2)O_(2) synthesis via oxygen reduction and water oxidation reactions.Recent advancements in electronic structure tuning strategies for metal-based organic catalysts are critically examined,focusing on their impact on light absorption range,photogenerated carrier separation,O_(2) activation,and the selective generation of H_(2)O_(2).In addition,this review comprehensively evaluates the applications of sacrificial agents in photocatalytic reaction systems and offers insights into the future development of metal-based organic catalysts for H_(2)O_(2) photosynthesis.
基金financially supported by the National Natural Science Foundation of China(Nos.22466011 and 22165004)the Innovative Research Team for Science and Technology of Shanxi Province(No.2022TD-04)。
文摘Hydrogen peroxide(H_(2)O_(2))is highly required in various applications.The development of catalysts exhibiting elevated catalytic activity,selectivity,and stability is essential for H_(2)O_(2)production technology.Metalbased catalysts are widely used for 2e^(-)ORR(oxygen reduction reaction)because of their adjustable structure,chemical stability,and availability.However,due to competition with the 4e^(-)ORR,modifications are often conducted to balance activity and selectivity.Common techniques include altering the surface electronic structure of catalysts and the interaction between active sites and intermediates.This review discusses diverse catalyst types(including precious and transition metals,single-atom catalysts,and MOFs/COFs)along with modification strategies(such as morphological control,electronic structure tuning,conductivity enhancement,and wettability improvement).The objective is to elucidate catalyst design and associated reaction mechanisms,as well as the relationship between catalyst structure and activity,in order to provide an insight for producing H_(2)O_(2)in an efficient,highly selective,and stable manner.
基金supported by the Natural Science Foundation of Xiamen City,China(3502Z20227256)National Natural Science Foundation of China(22202205,22209170)+3 种基金XMIREM Autonomously Deployment Project,China(2023CX14,2023GG01)Major Science and Technology Program of Xiamen City,China(3502Z20231054)National Natural Science Foundation of Fujian Province,China(2022J01502,2024J01185)STS Program of the Chinese Academy of Sciences,China(2023T3071)。
文摘Hydrogen peroxide(H_(2)O_(2))is an important chemical that can be sustainably produced through a twoelectron pathway in the electrocatalytic oxygen reduction reaction(ORR).However,the high cost and low reaction efficiency of catalysts currently limit the widespread application of this technology.Developing high-selectivity and scalable catalysts and accurately identifying the reaction active sites remain challenges.In this work,we have developed a promising nanodiamond(ND)catalyst to achieve high-selectivity H_(2)O_(2)production by oxygen reduction.Through surface carbon hybridization regulation to identify specific oxygen-containing functional groups combined with titration,model catalysis and DFT methods,it is found that the presence of carbonyl groups inducing the surrounding carbon atoms exhibit an optimal*OOH adsorption strength,thus promoting the two-electron pathway in ORR.Specifically,dynamic evolution processes of carbonyl groups and key adsorbed intermediate products including O_(2)(ads),superoxide anion*O_(2)^(-),and *OOH are monitored in situ spectroscopy.In the flowcell device,ND catalyst realizes the high H_(2)O_(2)Faradaic efficiency around 92% with a rate activity up to 105 mol gC=O^(-1)h^(-1),surpassing among reported non-metallic catalysts.The total H_(2)O_(2)yield reaches to 23.79 m M after a ten-hour test,which is 2.56 times higher than that of carbonyl-passivated ND,demonstrating its potential in scale-up application.Both titration and model catalytic processes proposed in this study further offer methods of designing efficient electrocatalysts for H_(2)O_(2)production.
