The photoconversion of CO_(2) to carbon-containing fuels,splitting water into H_(2),selective organic synthesis,reduction of N_(2) to NH3,and hazardous organic contaminant degradation represent feasible schemes for so...The photoconversion of CO_(2) to carbon-containing fuels,splitting water into H_(2),selective organic synthesis,reduction of N_(2) to NH3,and hazardous organic contaminant degradation represent feasible schemes for solving environmental and energy issues.In 1972,TiO_(2) was applied for decomposing water into H_(2) and O_(2) via photocatalysis.Owing to its the low visible-light utilization,fast charge recombination,and high energy barrier for water oxidation,overall photocatalytic water-splitting efficiency is extremely low.Because H_(2) is more economically valuable than O_(2),sacrificial agent-assisted photocatalytic H_(2) evolution has been extensively investigated.Because the sacrificial agent can quickly consume photoexcited holes and effectively reduce the water oxidation energy barrier,photocatalytic H_(2) evolution efficiency can be increased by 3-4 orders of magnitude compared to photocatalytic water splitting.However,the overuse of sacrificial agents contributes to wasted photoexcited holes and expensive processes,while presenting potential environmental issues.Recently,overall charge utilization and improved redox efficiency have been achieved by coupling photocatalytic reduction with oxidation reactions.Moreover,overall charge utilization can boost charge separation and increase photocatalyst durability.However,the photocatalytic mechanism of the overall redox reactions remains unclear,owing to the complex reaction processes and design difficulties.Herein,the basic principles of photocatalysis are discussed from the perspective of light harvesting,photoexcited charge separation,thermodynamics,and redox reaction kinetics.Photocatalytic redox reactions,including overall water photodecomposition,photocatalytic H_(2) evolution coupled with organic oxidation,photocatalytic CO_(2) reduction coupled with organic oxidation,photocatalytic H_(2)O_(2) production coupled with organic oxidation,photocatalytic N_(2) reduction coupled with N_(2) oxidation,and photocatalytic organic reduction coupled with organic oxidation,can be systematically classified according to the coupling of photocatalytic oxidation reactions with photocatalytic reduction reactions.Subsequently,the design of photocatalytic redox reactions is considered in terms of the modulation of photocatalyst materials,reaction conditions,and diversity of reactants and products.In addition,the vital role of density functional theory(DFT)calculations for unveiling photoexcited charge transfer,rate-determining steps,and redox reaction barriers are discussed in the context of the work function,electron density difference,Bader charge,and variation in the intermediate adsorption free energy profiles.The activity and mechanism of various photocatalytic redox reactions were elaborately analyzed through in situ characterizations and DFT calculations using representative cases.Finally,the overall photocatalytic redox reactions were summarized with a focus on the construction of an S-scheme heterojunction photocatalyst,reasonable loading of cocatalysts,photocatalyst morphology regulation,novel photocatalyst development,reasonable selection of the oxidation half-reaction and reduction half-reaction for coupling,and combined in situ characterization and DFT calculations.This work provides a reference for promising design strategies and insight into the mechanism of overall photocatalytic redox reactions.展开更多
The roles of adsorbed oxygen and lattice oxygen on the surface of VPO catalyst for n butane selective oxidation were experimentally studied by using on line mass spectroscopy (MS) transient response measurement in a f...The roles of adsorbed oxygen and lattice oxygen on the surface of VPO catalyst for n butane selective oxidation were experimentally studied by using on line mass spectroscopy (MS) transient response measurement in a fixed bed micro reactor. The results showed that the lattice oxygen led to selective oxidation,while adsorbed oxygen led to deep oxidation. Gaseous oxygen could be adsorbed on the surface of the VPO catalyst and transformed to lattice oxygen but did not directly participate in selective oxidation. The diffusion of lattice oxygen from the bulk phase to the surface might be the rate controlling step of unsteady state oxidation when n butane selective oxidation and VPO catalyst re oxidation were performed separately.Increasing the diffusion rate of the lattice oxygen and usable lattice oxygen capacity in VPO catalyst could remarkably improve the reaction performance in a fixed bed reactor.展开更多
本实验以土壤提纯腐殖酸及国际标准腐殖酸(Pahokee Peat Humic Acid,PPHA)为研究对象,测定腐殖酸与3种不同氧化还原Eh的铁矿物(水铁矿(Ferrihydrite)Eh0'=0 m V,赤铁矿(Fe2O3)Eh0'=-287 m V,磁铁矿(Fe3O4)Eh0'=-314 m V及...本实验以土壤提纯腐殖酸及国际标准腐殖酸(Pahokee Peat Humic Acid,PPHA)为研究对象,测定腐殖酸与3种不同氧化还原Eh的铁矿物(水铁矿(Ferrihydrite)Eh0'=0 m V,赤铁矿(Fe2O3)Eh0'=-287 m V,磁铁矿(Fe3O4)Eh0'=-314 m V及溶解性铁铁氰化钾Eh0'(Ferricyanide=+430 m V)的氧化还原反应,结合Eh-p H计的实验体系,分析腐殖质分子氧化还原官能团的分布规律.磁铁矿同时拥有二价和三价铁离子,具有与腐殖质发生氧化或者还原反应的条件.不同土壤腐殖酸与磁铁矿反应表现的还原/氧化能力不同,这是由于腐殖酸的不同Eh引起,在此基础上测量显示原态下腐殖酸Eh值大约为245 m V,H2还原后,Eh值降低至-620 m V,表明腐殖酸的氧化还原Eh是不同种类和数量的氧化还原官能团Eh叠加值.分析标准腐殖酸在不同氧化还原Eh下的氧化/还原能力显示原态下标准腐殖酸的氧化还原Eh分布比较均匀,还原态腐殖酸在Eh>0范围存在易于被氢气还原的官能团,具有显著的还原能力.展开更多
In this paper,MnO2 nanorods were successfully synthesized firstly by solid-state redox reaction in the presence of a nonionic surfactant(PEG-400).The obtained samples were further characterized by XRD and TEM measurem...In this paper,MnO2 nanorods were successfully synthesized firstly by solid-state redox reaction in the presence of a nonionic surfactant(PEG-400).The obtained samples were further characterized by XRD and TEM measurements.The results showed that samples were α-MnO2,its average diameter were 8 nm and its average length were about 100 nm.The samples dispersed well and there was no obvious hard aggromeration.展开更多
文摘The photoconversion of CO_(2) to carbon-containing fuels,splitting water into H_(2),selective organic synthesis,reduction of N_(2) to NH3,and hazardous organic contaminant degradation represent feasible schemes for solving environmental and energy issues.In 1972,TiO_(2) was applied for decomposing water into H_(2) and O_(2) via photocatalysis.Owing to its the low visible-light utilization,fast charge recombination,and high energy barrier for water oxidation,overall photocatalytic water-splitting efficiency is extremely low.Because H_(2) is more economically valuable than O_(2),sacrificial agent-assisted photocatalytic H_(2) evolution has been extensively investigated.Because the sacrificial agent can quickly consume photoexcited holes and effectively reduce the water oxidation energy barrier,photocatalytic H_(2) evolution efficiency can be increased by 3-4 orders of magnitude compared to photocatalytic water splitting.However,the overuse of sacrificial agents contributes to wasted photoexcited holes and expensive processes,while presenting potential environmental issues.Recently,overall charge utilization and improved redox efficiency have been achieved by coupling photocatalytic reduction with oxidation reactions.Moreover,overall charge utilization can boost charge separation and increase photocatalyst durability.However,the photocatalytic mechanism of the overall redox reactions remains unclear,owing to the complex reaction processes and design difficulties.Herein,the basic principles of photocatalysis are discussed from the perspective of light harvesting,photoexcited charge separation,thermodynamics,and redox reaction kinetics.Photocatalytic redox reactions,including overall water photodecomposition,photocatalytic H_(2) evolution coupled with organic oxidation,photocatalytic CO_(2) reduction coupled with organic oxidation,photocatalytic H_(2)O_(2) production coupled with organic oxidation,photocatalytic N_(2) reduction coupled with N_(2) oxidation,and photocatalytic organic reduction coupled with organic oxidation,can be systematically classified according to the coupling of photocatalytic oxidation reactions with photocatalytic reduction reactions.Subsequently,the design of photocatalytic redox reactions is considered in terms of the modulation of photocatalyst materials,reaction conditions,and diversity of reactants and products.In addition,the vital role of density functional theory(DFT)calculations for unveiling photoexcited charge transfer,rate-determining steps,and redox reaction barriers are discussed in the context of the work function,electron density difference,Bader charge,and variation in the intermediate adsorption free energy profiles.The activity and mechanism of various photocatalytic redox reactions were elaborately analyzed through in situ characterizations and DFT calculations using representative cases.Finally,the overall photocatalytic redox reactions were summarized with a focus on the construction of an S-scheme heterojunction photocatalyst,reasonable loading of cocatalysts,photocatalyst morphology regulation,novel photocatalyst development,reasonable selection of the oxidation half-reaction and reduction half-reaction for coupling,and combined in situ characterization and DFT calculations.This work provides a reference for promising design strategies and insight into the mechanism of overall photocatalytic redox reactions.
基金国家自然科学基金委中国石油化工集团公司联合资助重大基金项目 (No 2 9792 0 70 )~~
文摘The roles of adsorbed oxygen and lattice oxygen on the surface of VPO catalyst for n butane selective oxidation were experimentally studied by using on line mass spectroscopy (MS) transient response measurement in a fixed bed micro reactor. The results showed that the lattice oxygen led to selective oxidation,while adsorbed oxygen led to deep oxidation. Gaseous oxygen could be adsorbed on the surface of the VPO catalyst and transformed to lattice oxygen but did not directly participate in selective oxidation. The diffusion of lattice oxygen from the bulk phase to the surface might be the rate controlling step of unsteady state oxidation when n butane selective oxidation and VPO catalyst re oxidation were performed separately.Increasing the diffusion rate of the lattice oxygen and usable lattice oxygen capacity in VPO catalyst could remarkably improve the reaction performance in a fixed bed reactor.
文摘本实验以土壤提纯腐殖酸及国际标准腐殖酸(Pahokee Peat Humic Acid,PPHA)为研究对象,测定腐殖酸与3种不同氧化还原Eh的铁矿物(水铁矿(Ferrihydrite)Eh0'=0 m V,赤铁矿(Fe2O3)Eh0'=-287 m V,磁铁矿(Fe3O4)Eh0'=-314 m V及溶解性铁铁氰化钾Eh0'(Ferricyanide=+430 m V)的氧化还原反应,结合Eh-p H计的实验体系,分析腐殖质分子氧化还原官能团的分布规律.磁铁矿同时拥有二价和三价铁离子,具有与腐殖质发生氧化或者还原反应的条件.不同土壤腐殖酸与磁铁矿反应表现的还原/氧化能力不同,这是由于腐殖酸的不同Eh引起,在此基础上测量显示原态下腐殖酸Eh值大约为245 m V,H2还原后,Eh值降低至-620 m V,表明腐殖酸的氧化还原Eh是不同种类和数量的氧化还原官能团Eh叠加值.分析标准腐殖酸在不同氧化还原Eh下的氧化/还原能力显示原态下标准腐殖酸的氧化还原Eh分布比较均匀,还原态腐殖酸在Eh>0范围存在易于被氢气还原的官能团,具有显著的还原能力.
文摘In this paper,MnO2 nanorods were successfully synthesized firstly by solid-state redox reaction in the presence of a nonionic surfactant(PEG-400).The obtained samples were further characterized by XRD and TEM measurements.The results showed that samples were α-MnO2,its average diameter were 8 nm and its average length were about 100 nm.The samples dispersed well and there was no obvious hard aggromeration.
