Photocatalysis shows great promise in the field of solar energy conversion.One of the reasons for this is because it promotes the development of multi-field-coupled catalysis.In order to explore the principles of mult...Photocatalysis shows great promise in the field of solar energy conversion.One of the reasons for this is because it promotes the development of multi-field-coupled catalysis.In order to explore the principles of multi-field-coupled catalytic reactions,an in situ multi-field-coupled characterization technique is required.In this study,we obtained hydrogenated ST-01 TiO2 and observed enhanced catalytic activity by thermal coupled photocatalysis.In situ photoconductivity was employed to understand the activity enhancement.The effects of the reaction temperature,reaction atmosphere,and oxygen vacancy(Ov)on the photoconductivity of TiO2 were studied.After coupling thermal into photoconductivity measurement,highly active Ov-TiO2 displayed rapid decay of photoconductivity in a CO2 atmosphere and slow decay of photoconductivity in a N2 atmosphere.These phenomena revealed that photothermal coupling assisted the detrapping of electrons at the Ov surface and promoted electron transfer to CO2,which clearly explained the high photothermal catalytic activity of Ov-TiO2.This study demonstrated that photoconductivity is a useful tool to help understand photothermal catalytic phenomena.展开更多
Photothermal catalysis is a widely researched field in which the reaction mechanism is usually investigated based on the photochemical behavior of the catalytic material.Considering that the adsorption of reactants is...Photothermal catalysis is a widely researched field in which the reaction mechanism is usually investigated based on the photochemical behavior of the catalytic material.Considering that the adsorption of reactants is essential for catalytic reactions to occur,in this study,the synergistic effect of photothermal catalysis is innovatively elucidated in terms of the electron transfer behavior of reactant adsorption.For the H_(2)+O2 or CO+H_(2)reaction systems over a ZnO catalyst,UV irradiation at 25°C or heat without UV irradiation did not cause H_(2)oxidation or CO reduction;only photothermal conditions(100 or 150°C+UV light)initiated the two reactions.This result is related to the electron transfer behavior associated with the adsorption of CO or H_(2)on ZnO,in which H_(2)or CO that lost an electron could be oxidized by O2 or hydroxyls.However,the electron‐accepting CO could be reduced by the electron‐donating H_(2)into CH4 under photothermal conditions.Based on the in‐situ characterization and theoretical calculation results,it was established that the synergistic effect of the photothermal conditions acted on the(002)crystal surface of ZnO to stimulate the growth of zinc vacancies,which resulted in the formation of defect energy levels,adsorption sites,and an adjusted Fermi level.As a result,the electron transfer behavior between adsorbed CO or H_(2)and the crystal surface varied,which further affected the photocatalytic behavior.The results show that the effect of photothermal synergy may not only produce the expected kinetic energy,but more importantly,produce energy that can change the activation mode of the reactant gas.This study provides a new understanding of the CO catalytic oxidation and reduction processes over semiconductor materials.展开更多
Thermoelectric devices require thermoelectric materials with high figure-of-merit(ZT)values in the operating temperature range.In recent years,the Zintl phase compound,n-Mg_(3)Sb_(2),has received much attention owing ...Thermoelectric devices require thermoelectric materials with high figure-of-merit(ZT)values in the operating temperature range.In recent years,the Zintl phase compound,n-Mg_(3)Sb_(2),has received much attention owing to its rich chemistry and structural complexity.However,it hardly achieves high ZT values throughout the medium temperature range.Herein,by increasing the sintering temperature as much as possible,we successfully increased the average grain size of the compound by 15 times,and the grain boundary scattering was manipulated to obtain high carrier mobility of up to 180 cm^(2)V^(-1)s^(-1).Simultaneously,we optimized the Mg content for ultralow lattice thermal conductivity.We first doped the Mg_(3)Sb_(2)-based materials with boron for higher sintering temperature,good thermal stability,and higher hardness.The synergistic optimization of electrical and thermal transport resulted in excellent ZT values(0.62 at 300 K,1.81 at 773 K)and an average ZT of 1.4(from300 to 773 K),which are higher than the state-of-the-art values for n-type thermoelectric materials,demonstrating a high potential in device applications.展开更多
基金supported by the Natural Science Foundation of China(51072032,51372036,51102001)the Key Project of Chinese Ministry of Education(113020A)+1 种基金the 111 project(B13013)Jilin Province Science and Technology Development Plan(20180101175JC,20160520170JH)~~
文摘Photocatalysis shows great promise in the field of solar energy conversion.One of the reasons for this is because it promotes the development of multi-field-coupled catalysis.In order to explore the principles of multi-field-coupled catalytic reactions,an in situ multi-field-coupled characterization technique is required.In this study,we obtained hydrogenated ST-01 TiO2 and observed enhanced catalytic activity by thermal coupled photocatalysis.In situ photoconductivity was employed to understand the activity enhancement.The effects of the reaction temperature,reaction atmosphere,and oxygen vacancy(Ov)on the photoconductivity of TiO2 were studied.After coupling thermal into photoconductivity measurement,highly active Ov-TiO2 displayed rapid decay of photoconductivity in a CO2 atmosphere and slow decay of photoconductivity in a N2 atmosphere.These phenomena revealed that photothermal coupling assisted the detrapping of electrons at the Ov surface and promoted electron transfer to CO2,which clearly explained the high photothermal catalytic activity of Ov-TiO2.This study demonstrated that photoconductivity is a useful tool to help understand photothermal catalytic phenomena.
文摘Photothermal catalysis is a widely researched field in which the reaction mechanism is usually investigated based on the photochemical behavior of the catalytic material.Considering that the adsorption of reactants is essential for catalytic reactions to occur,in this study,the synergistic effect of photothermal catalysis is innovatively elucidated in terms of the electron transfer behavior of reactant adsorption.For the H_(2)+O2 or CO+H_(2)reaction systems over a ZnO catalyst,UV irradiation at 25°C or heat without UV irradiation did not cause H_(2)oxidation or CO reduction;only photothermal conditions(100 or 150°C+UV light)initiated the two reactions.This result is related to the electron transfer behavior associated with the adsorption of CO or H_(2)on ZnO,in which H_(2)or CO that lost an electron could be oxidized by O2 or hydroxyls.However,the electron‐accepting CO could be reduced by the electron‐donating H_(2)into CH4 under photothermal conditions.Based on the in‐situ characterization and theoretical calculation results,it was established that the synergistic effect of the photothermal conditions acted on the(002)crystal surface of ZnO to stimulate the growth of zinc vacancies,which resulted in the formation of defect energy levels,adsorption sites,and an adjusted Fermi level.As a result,the electron transfer behavior between adsorbed CO or H_(2)and the crystal surface varied,which further affected the photocatalytic behavior.The results show that the effect of photothermal synergy may not only produce the expected kinetic energy,but more importantly,produce energy that can change the activation mode of the reactant gas.This study provides a new understanding of the CO catalytic oxidation and reduction processes over semiconductor materials.
基金supported by the National Natural Science Foundation of China(51771065 and 51871082)the Natural Science Foundation of Heilongjiang Province of China(ZD2020E003)。
文摘Thermoelectric devices require thermoelectric materials with high figure-of-merit(ZT)values in the operating temperature range.In recent years,the Zintl phase compound,n-Mg_(3)Sb_(2),has received much attention owing to its rich chemistry and structural complexity.However,it hardly achieves high ZT values throughout the medium temperature range.Herein,by increasing the sintering temperature as much as possible,we successfully increased the average grain size of the compound by 15 times,and the grain boundary scattering was manipulated to obtain high carrier mobility of up to 180 cm^(2)V^(-1)s^(-1).Simultaneously,we optimized the Mg content for ultralow lattice thermal conductivity.We first doped the Mg_(3)Sb_(2)-based materials with boron for higher sintering temperature,good thermal stability,and higher hardness.The synergistic optimization of electrical and thermal transport resulted in excellent ZT values(0.62 at 300 K,1.81 at 773 K)and an average ZT of 1.4(from300 to 773 K),which are higher than the state-of-the-art values for n-type thermoelectric materials,demonstrating a high potential in device applications.
