The photoreduction of greenhouse gas CO_(2)using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of C...The photoreduction of greenhouse gas CO_(2)using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of CO_(2)photoreduction remains generally low due to the challenging activation of CO_(2)and the limited light absorption and separation of charge.Defect engineering of catalysts rep-resents a pivotal strategy to enhance the photocatalytic activity for CO_(2),with most research on met-al oxide catalysts focusing on the creation of anionic vacancies.The exploration of metal vacancies and their effects,however,is still underexplored.In this study,we prepared an In2O3 catalyst with indium vacancies(VIn)through defect engineering for CO_(2)photoreduction.Experimental and theo-retical calculations results demonstrate that VIn not only facilitate light absorption and charge sepa-ration in the catalyst but also enhance CO_(2)adsorption and reduce the energy barrier for the for-mation of the key intermediate*COOH during CO_(2)reduction.Through metal vacancy engineering,the activity of the catalyst was 7.4 times,reaching an outstanding rate of 841.32μmol g(-1)h^(-1).This work unveils the mechanism of metal vacancies in CO_(2)photoreduction and provides theoretical guidance for the development of novel CO_(2)photoreduction catalysts.展开更多
The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduc...The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduction of oxygen vacancies(OVs)and Mo dopants into Bi_(5)O_(7)Br nanosheets can significantly increase the activity for photocatalytic N_(2) fixation.The 1 mol% Mo-doped Bi_(5)O_(7)Br nanosheets exhibited an optimal NH_(3) generation rate of 122.9μmol g^(-1) h^(-1) and durable stability,which is attributed to their optimized conduction band position,suitable absorption edge,large number of light-switchable OVs,and improved charge carrier separation.This work provides a promising approach to design photocatalysts with light-switchable OVs for N_(2) reduction to NH_(3) under mild conditions,highlighting the wide application scope of nanostructured BiOBr-based photocatalysts as effective N_(2) fixation systems.展开更多
In order to study the effect mechanism of N-doping on the visible-light photoactivity of TiO2,N-doped and un-doped TiO2 nano-powders were prepared by an acid-catalyzed sol-gel method and characterized by X-ray diffrac...In order to study the effect mechanism of N-doping on the visible-light photoactivity of TiO2,N-doped and un-doped TiO2 nano-powders were prepared by an acid-catalyzed sol-gel method and characterized by X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),electron spin resonance(ESR),UV-Vis diffuse reflection spectra(DRS),and photoluminescence spectra(PL)techniques.Their photoactivities are evaluated by the photocatalytic degradation of methylene blue(MB)in aqueous solution under UV light and visible-light irradiation,respectively.The results reveal that the as-prepared N-doped sample with single anatase exhibits a good visible-light photoactivity,whereas its UV photoactivity decreases slightly,compared with the un-doped sample.The N-doping increases surface hydroxyl groups and forms abundant oxygen vacancies bounding single electrons.The visible-light response of the N-doped sample can be ascribed to a synergetic effect of impurity energy levels due to the substitutional N-doping and defect energy levels owing to the formation of oxygen vacancies.The separation of the photo-generated electron and hole can be promoted by the increase in both oxygen vacancies and surface hydroxyl groups,which are conducive for enhancement of photoactivity.The increase in visible-light photoactivity of the N-doped sample is related with the decrease in its PL spectral intensity in visible-light region.展开更多
The interaction of reactants with catalysts has always been an important subject for catalytic reactions.As a promising catalyst with versatile applications,titania has been intensively studied for decades.In this wor...The interaction of reactants with catalysts has always been an important subject for catalytic reactions.As a promising catalyst with versatile applications,titania has been intensively studied for decades.In this work we have investigated the role of bridge bonded oxygen vacancy(O_(v))in methyl groups and carbon monoxide(CO)adsorption on rutile TiO_(2)(110)(R-TiO_(2)(110))with the temperature programmed desorption technique.The results show a clear different tendency of the desorption of methyl groups adsorbed on bridge bonded oxygen(O_(b)),and CO molecules on the five coordinate Ti^(4+)sites(Ti_(5c))as the Ovconcentration changes,suggesting that the surface defects may have crucial influence on the absorption of species on different sites of R-TiO_(2)(110).展开更多
Exploring efficient and cost-effective electro- catalysts for oxygen evolution reaction (OER) is critical to water splitting. While nickel-iron layered double hydroxide (NiFe LDH) has been long recognized as a pro...Exploring efficient and cost-effective electro- catalysts for oxygen evolution reaction (OER) is critical to water splitting. While nickel-iron layered double hydroxide (NiFe LDH) has been long recognized as a promising non- precious electrocatalyst for OER, its intrinsic activity needs further improvement. Herein, we design a highly-efficient oxygen evolution electrode based on defective NiFe LDH na- noarray. By combing the merits of the modulated electronic structure, more exposed active sites, and the conductive elec- trode, the defective NiFe LDH electrocatalysts show a low onset potential of 1.40 V (vs. RHE). An overpotential of only 200 mV is required for 10 mA cm-2, which is 48 mV lower than that of pristine NiFe-LDH. Density functional theory plus U (DFT+U) calculations are further employed for the origin of this OER activity enhancement. We find the introduction of oxygen vacancies leads to a lower valance state of Fe and the narrowed bandgap, which means the electrons tend to be ea- sily excited into the conduction band, resulting in the lowered reaction overpotential and enhanced OER performance.展开更多
文摘The photoreduction of greenhouse gas CO_(2)using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of CO_(2)photoreduction remains generally low due to the challenging activation of CO_(2)and the limited light absorption and separation of charge.Defect engineering of catalysts rep-resents a pivotal strategy to enhance the photocatalytic activity for CO_(2),with most research on met-al oxide catalysts focusing on the creation of anionic vacancies.The exploration of metal vacancies and their effects,however,is still underexplored.In this study,we prepared an In2O3 catalyst with indium vacancies(VIn)through defect engineering for CO_(2)photoreduction.Experimental and theo-retical calculations results demonstrate that VIn not only facilitate light absorption and charge sepa-ration in the catalyst but also enhance CO_(2)adsorption and reduce the energy barrier for the for-mation of the key intermediate*COOH during CO_(2)reduction.Through metal vacancy engineering,the activity of the catalyst was 7.4 times,reaching an outstanding rate of 841.32μmol g(-1)h^(-1).This work unveils the mechanism of metal vacancies in CO_(2)photoreduction and provides theoretical guidance for the development of novel CO_(2)photoreduction catalysts.
文摘The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduction of oxygen vacancies(OVs)and Mo dopants into Bi_(5)O_(7)Br nanosheets can significantly increase the activity for photocatalytic N_(2) fixation.The 1 mol% Mo-doped Bi_(5)O_(7)Br nanosheets exhibited an optimal NH_(3) generation rate of 122.9μmol g^(-1) h^(-1) and durable stability,which is attributed to their optimized conduction band position,suitable absorption edge,large number of light-switchable OVs,and improved charge carrier separation.This work provides a promising approach to design photocatalysts with light-switchable OVs for N_(2) reduction to NH_(3) under mild conditions,highlighting the wide application scope of nanostructured BiOBr-based photocatalysts as effective N_(2) fixation systems.
基金Research Foundation for Young Academic Core of Harbin Normal University,China(No.08XBSK89)Science and Technology Research Program of Education Bureau of Heilongjiang Province of China(No.11551115)
文摘In order to study the effect mechanism of N-doping on the visible-light photoactivity of TiO2,N-doped and un-doped TiO2 nano-powders were prepared by an acid-catalyzed sol-gel method and characterized by X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),electron spin resonance(ESR),UV-Vis diffuse reflection spectra(DRS),and photoluminescence spectra(PL)techniques.Their photoactivities are evaluated by the photocatalytic degradation of methylene blue(MB)in aqueous solution under UV light and visible-light irradiation,respectively.The results reveal that the as-prepared N-doped sample with single anatase exhibits a good visible-light photoactivity,whereas its UV photoactivity decreases slightly,compared with the un-doped sample.The N-doping increases surface hydroxyl groups and forms abundant oxygen vacancies bounding single electrons.The visible-light response of the N-doped sample can be ascribed to a synergetic effect of impurity energy levels due to the substitutional N-doping and defect energy levels owing to the formation of oxygen vacancies.The separation of the photo-generated electron and hole can be promoted by the increase in both oxygen vacancies and surface hydroxyl groups,which are conducive for enhancement of photoactivity.The increase in visible-light photoactivity of the N-doped sample is related with the decrease in its PL spectral intensity in visible-light region.
基金supported by the National Natural Science Foundation of China (No.21973084 and No.21803056)。
文摘The interaction of reactants with catalysts has always been an important subject for catalytic reactions.As a promising catalyst with versatile applications,titania has been intensively studied for decades.In this work we have investigated the role of bridge bonded oxygen vacancy(O_(v))in methyl groups and carbon monoxide(CO)adsorption on rutile TiO_(2)(110)(R-TiO_(2)(110))with the temperature programmed desorption technique.The results show a clear different tendency of the desorption of methyl groups adsorbed on bridge bonded oxygen(O_(b)),and CO molecules on the five coordinate Ti^(4+)sites(Ti_(5c))as the Ovconcentration changes,suggesting that the surface defects may have crucial influence on the absorption of species on different sites of R-TiO_(2)(110).
基金supported by the National Natural Science Foundation of China,National Key Research and Development Project (2016YFC0801302, 2016YFF0204402)the Program for Changjiang Scholars and Innovative Research Team in the University+2 种基金the Fundamental Research Funds for the Central Universitiesthe longterm subsidy mechanism from the Ministry of Financethe Ministry of Education of China
文摘Exploring efficient and cost-effective electro- catalysts for oxygen evolution reaction (OER) is critical to water splitting. While nickel-iron layered double hydroxide (NiFe LDH) has been long recognized as a promising non- precious electrocatalyst for OER, its intrinsic activity needs further improvement. Herein, we design a highly-efficient oxygen evolution electrode based on defective NiFe LDH na- noarray. By combing the merits of the modulated electronic structure, more exposed active sites, and the conductive elec- trode, the defective NiFe LDH electrocatalysts show a low onset potential of 1.40 V (vs. RHE). An overpotential of only 200 mV is required for 10 mA cm-2, which is 48 mV lower than that of pristine NiFe-LDH. Density functional theory plus U (DFT+U) calculations are further employed for the origin of this OER activity enhancement. We find the introduction of oxygen vacancies leads to a lower valance state of Fe and the narrowed bandgap, which means the electrons tend to be ea- sily excited into the conduction band, resulting in the lowered reaction overpotential and enhanced OER performance.