Organometallic nanosheets are a versatile platform for design of efficient electrocatalyst materials due to their high surface area and uniform dispersion of metal active sites.In this paper,we systematically investig...Organometallic nanosheets are a versatile platform for design of efficient electrocatalyst materials due to their high surface area and uniform dispersion of metal active sites.In this paper,we systematically investigate the electrocatalytic performance of the first transition metal series TM3–C12S12 monolayers on CO2 using spin-polarized density functional theory.The calculations show that M3–C12S12 exhibits excellent catalytic activity and selectivity in the catalytic reduction in CO2.The main reduction products of Sc,Ti,and Cr are CH4.V,Mn,Fe and Zn mainly produce HCOOH,and Co produces HCHO,while CO is the main product for Ni and Cu.For Sc,Ti,and Cr,the overpotentials are>0.7 V,while for V,Mn,Fe,Co,Ni,Cu,Zn,the overpotentials are very low and range from 0.27 to 0.47 V.Therefore,our results indicate that many of the M3–C12S12 monolayers are expected to be excellent and efficient CO2 reduction catalysts.展开更多
Novel,hierarchical,flower-like Ag/Cu2O and Au/Cu2O nanostructures were successfully fabricated and applied as efficient electrocatalysts for the electrochemical reduction of CO2.Cu2O nanospheres with a uniform size of...Novel,hierarchical,flower-like Ag/Cu2O and Au/Cu2O nanostructures were successfully fabricated and applied as efficient electrocatalysts for the electrochemical reduction of CO2.Cu2O nanospheres with a uniform size of^180 nm were initially synthesized.Thereafter,Cu2O was used as a sacrificial template to prepare a series of Ag/Cu2O composites through galvanic replacement.By varying the Ag/Cu atomic ratio,Ago.12/Cu2O,having a hierarchical,flower-like nanostructure with intersecting Ag nanoflakes encompassing an inner Cu2O sphere,was prepared.The as-prepared Ag/Cu2O samples presented higher Faradaic efficiencies(FE)for CO and relatively suppressed H2 evolution than the parent Cu2O nanospheres due to the combination of Ag with Cu2O in the former.Notably,the highest CO evolution rate was achieved with Ago.12/Cu2O due to the larger electroactive surface area furnished by the hierarchical structure.The same hier-archical flower-like structure was also obtained for the Auo./Cu2O composite,where the FEco(10%)was even higher than that of Ago.12/Cu2O.Importantly,the results reveal that Ago.12/Cu2O and Auo./Cu2O both exhibit remarkably improved stability relative to Cu2O.This study presents a facile method of developing hierarchical metal-oxide composites as fficient and stable electrocatalysts for the electrochemical reduction of CO2.展开更多
Regulating the selectivity of CO2 photoreduction is particularly challenging. Herein, we propose ideal models of atomic layers with/without element doping to investigate the effect of doping engineering to tune the se...Regulating the selectivity of CO2 photoreduction is particularly challenging. Herein, we propose ideal models of atomic layers with/without element doping to investigate the effect of doping engineering to tune the selectivity of CO2 photoreduction. Prototypical ZnCo2O4 atomic layers with/without Ni-doping were first synthesized. Density functional theory calculations reveal that introducing Ni atoms creates several new energy levels and increases the density-of-states at the conduction band minimum. Synchrotron radiation photoemission spectroscopy demonstrates that the band structures are suitable for CO2 photoreduction, while the surface photovoltage spectra demonstrate that Ni doping increases the carrier separation efficiency. In situ diffuse reflectance Fourier transform infrared spectra disclose that the CO2^- radical is the main intermediate, while temperature-programed desorption curves reveal that the ZnCo2O4 atomic layers with/without Ni doping favor the respective CO and CH4 desorption. The Ni-doped ZnCo2O4 atomic layers exhibit a 3.5-time higher CO selectivity than the ZnCo2O4 atomic layers. This work establishes a clear correlation between elemental doping and selectivity regulation for CO2 photoreduction, opening new possibilities for tailoring solar-driven photocatalytic behaviors.展开更多
Photocatalytic reduction of CO2 was carried out on villiform spherical catalysts of Pd-TiO2 in isopropanol solution.The catalysts were synthesized by hydrothermal method,their structures,morphologies and optical absor...Photocatalytic reduction of CO2 was carried out on villiform spherical catalysts of Pd-TiO2 in isopropanol solution.The catalysts were synthesized by hydrothermal method,their structures,morphologies and optical absorption properties were characterized by X-ray diffraction（XRD）,energy dispersive X-ray spectroscopy（EDS）,scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,highresolution transmission electron microscopy（HRTEM）and UV-vis absorption spectroscopy（UV-vis）.The photocatalytic activities with different loading amounts and morphologies were evaluated for determining the dominant effect and optimizing the catalyst preparation.Based on a villiform spherical TiO2 with the largest specific surface area in our experiments,we prepared a set of catalysts with various loading amounts of palladium and tested them by bubbling CO2 through the slurry of catalyst and isopropanol.The highest formation rate of isopropyl formate was 276.6μmol/g？cat/h.Eventually we proposed the reaction mechanism.展开更多
ZnFe2O4-BiOC1 composites were prepared by both hydrothermal and direct precipitation processes and the structures and properties of the samples were characterized by various instrumental techniques. The samples were t...ZnFe2O4-BiOC1 composites were prepared by both hydrothermal and direct precipitation processes and the structures and properties of the samples were characterized by various instrumental techniques. The samples were then used as catalysts for the photocatalytic reduction of CQ in cyclohexanol under ultraviolet irradiation to give cyclohexanone （CH） and cyclohexyl formate （CF）. The photocatalytic CO2 reduction activities over the hydrothermally prepared ZnFeaO4-BiOCl composites were higher than those over the directly-precipitated composites. This is because compared to the direct-precipitation sample, the ZnFe2O4 nanoparticles in the hydrothermal sample were smaller and more uniformly distributed on the surface of BiOCl and so more heterojunctions were formed. Higher CF and CH yields were obtained for the pure BiOCl and BiOCl composite samples with more exposed （001） facets than for the samples with more exposed （010） facets. This is due to the higher density of oxygen atoms in the exposed （001） facets, which creates more oxygen vacancies, and thereby improves the separation efficiency of the electron-hole pairs. More importantly, irradiation of the （001） facets with ultraviolet light produces photo-generated electrons which is helpful for the reduction of CO2 to -CO2^-. The mechanism for the photocatalytic reduction of CO2 in cyclohexanol over ZnFe204-BiOCl composites with exposed （001） facets involves electron transfer and carbon radical formation.展开更多
The chemical reduction of carbon dioxide(CO2) has always drawn intensive attentions as it can not only remove CO2 which is the primary greenhouse gas but also produce useful fuels. Industrial synthesis of methanol uti...The chemical reduction of carbon dioxide(CO2) has always drawn intensive attentions as it can not only remove CO2 which is the primary greenhouse gas but also produce useful fuels. Industrial synthesis of methanol utilizing copper-based catalysts is a commonly used process for CO2 hydrogenation. Despite extensive efforts on improving its reaction mechanism by identifying the active sites and optimizing the operating temperature and pressure, it is still remains completely unveiled. The selectivities of CO2 electroreduction at copper electrode could mainly be towards carbon monoxide(CO), formic acid(HCOOH), methane(CH4) or ethylene(C2H4), which depends on the chemical potentials of hydrogen controlled by the applied potential. Interestingly, methanol could hardly be produced electrochemically despite utilizing metallic copper as catalysts in both processes. Moreover, the mechanistic researches have also been performed aiming to achieve the higher selectivity towards more desirable higher hydrocarbons. In this work, we review the present proposals of reaction mechanisms of copper catalyzing CO2 reduction in industrial methanol synthesis and electrochemical environment in terms of density functional theory(DFT) calculations, respectively. In addition, the influences of the simulation methods of solvation and electrochemical model at liquid-solid interface on the selectivity are discussed and compared.展开更多
A rare-earth free upconversion luminescent material, 10BaF2：NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light （550 nm-610 nm） into ...A rare-earth free upconversion luminescent material, 10BaF2：NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light （550 nm-610 nm） into ultraviolet light （290 nm 350 nm）, and two emission peaks at 304 nm and 324 nm are observed under the excitation of 583 nm at room temperature. Subsequently, 10BaF2：NaF, Na3AIF6/TiO2 composite photocatalyst is prepared and its catalytic activity is evaluated by the photocatalytic reduction of CO2 under visible light irradiation （λ〉 515 nm）. The results show that 10BaF2：NaF, Na3AIF6/TiO2 is a more effective photocatalyst for CO2 reduction than pure TiO2, their corresponding methanol yields are 179 and 0 μmol/g-cat under the same conditions. Additionally, the mechanism of photocatalytic reduction of CO2 on 10BaF2：NaF, Na3AIF6/TiO2 is proposed.展开更多
With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Zeng Jie(曾杰)and Prof.Yang Jinlong(杨金龙),both from Hefei National Laboratory for Physica...With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Zeng Jie(曾杰)and Prof.Yang Jinlong(杨金龙),both from Hefei National Laboratory for Physical Sciences at the Microscale,University of Science and Technology of China,展开更多
基金support from the National Natural Science Foundation of China(21673087 and 21873032)startup fund(2006013118 and 3004013105)from Huazhong University of Science and Technologythe Fundamental Research Funds for the Central Universities(2019kfy R CPY116)
文摘Organometallic nanosheets are a versatile platform for design of efficient electrocatalyst materials due to their high surface area and uniform dispersion of metal active sites.In this paper,we systematically investigate the electrocatalytic performance of the first transition metal series TM3–C12S12 monolayers on CO2 using spin-polarized density functional theory.The calculations show that M3–C12S12 exhibits excellent catalytic activity and selectivity in the catalytic reduction in CO2.The main reduction products of Sc,Ti,and Cr are CH4.V,Mn,Fe and Zn mainly produce HCOOH,and Co produces HCHO,while CO is the main product for Ni and Cu.For Sc,Ti,and Cr,the overpotentials are>0.7 V,while for V,Mn,Fe,Co,Ni,Cu,Zn,the overpotentials are very low and range from 0.27 to 0.47 V.Therefore,our results indicate that many of the M3–C12S12 monolayers are expected to be excellent and efficient CO2 reduction catalysts.
基金We are grateful to the Analysis and Test Center of Tianjin University for providing XRD,SEM,and TEM characterization.We also acknowledge the National Natural Science Foundation of China(Grant Nos.21576204 and 21206117)for financial support.
文摘Novel,hierarchical,flower-like Ag/Cu2O and Au/Cu2O nanostructures were successfully fabricated and applied as efficient electrocatalysts for the electrochemical reduction of CO2.Cu2O nanospheres with a uniform size of^180 nm were initially synthesized.Thereafter,Cu2O was used as a sacrificial template to prepare a series of Ag/Cu2O composites through galvanic replacement.By varying the Ag/Cu atomic ratio,Ago.12/Cu2O,having a hierarchical,flower-like nanostructure with intersecting Ag nanoflakes encompassing an inner Cu2O sphere,was prepared.The as-prepared Ag/Cu2O samples presented higher Faradaic efficiencies(FE)for CO and relatively suppressed H2 evolution than the parent Cu2O nanospheres due to the combination of Ag with Cu2O in the former.Notably,the highest CO evolution rate was achieved with Ago.12/Cu2O due to the larger electroactive surface area furnished by the hierarchical structure.The same hier-archical flower-like structure was also obtained for the Auo./Cu2O composite,where the FEco(10%)was even higher than that of Ago.12/Cu2O.Importantly,the results reveal that Ago.12/Cu2O and Auo./Cu2O both exhibit remarkably improved stability relative to Cu2O.This study presents a facile method of developing hierarchical metal-oxide composites as fficient and stable electrocatalysts for the electrochemical reduction of CO2.
文摘Regulating the selectivity of CO2 photoreduction is particularly challenging. Herein, we propose ideal models of atomic layers with/without element doping to investigate the effect of doping engineering to tune the selectivity of CO2 photoreduction. Prototypical ZnCo2O4 atomic layers with/without Ni-doping were first synthesized. Density functional theory calculations reveal that introducing Ni atoms creates several new energy levels and increases the density-of-states at the conduction band minimum. Synchrotron radiation photoemission spectroscopy demonstrates that the band structures are suitable for CO2 photoreduction, while the surface photovoltage spectra demonstrate that Ni doping increases the carrier separation efficiency. In situ diffuse reflectance Fourier transform infrared spectra disclose that the CO2^- radical is the main intermediate, while temperature-programed desorption curves reveal that the ZnCo2O4 atomic layers with/without Ni doping favor the respective CO and CH4 desorption. The Ni-doped ZnCo2O4 atomic layers exhibit a 3.5-time higher CO selectivity than the ZnCo2O4 atomic layers. This work establishes a clear correlation between elemental doping and selectivity regulation for CO2 photoreduction, opening new possibilities for tailoring solar-driven photocatalytic behaviors.
基金Funded by the National Natural Science Foundation of China(No.21176192 and 21776220)
文摘Photocatalytic reduction of CO2 was carried out on villiform spherical catalysts of Pd-TiO2 in isopropanol solution.The catalysts were synthesized by hydrothermal method,their structures,morphologies and optical absorption properties were characterized by X-ray diffraction（XRD）,energy dispersive X-ray spectroscopy（EDS）,scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,highresolution transmission electron microscopy（HRTEM）and UV-vis absorption spectroscopy（UV-vis）.The photocatalytic activities with different loading amounts and morphologies were evaluated for determining the dominant effect and optimizing the catalyst preparation.Based on a villiform spherical TiO2 with the largest specific surface area in our experiments,we prepared a set of catalysts with various loading amounts of palladium and tested them by bubbling CO2 through the slurry of catalyst and isopropanol.The highest formation rate of isopropyl formate was 276.6μmol/g？cat/h.Eventually we proposed the reaction mechanism.
基金This work was financially supported by the National Natural Science Foundation of China （Grant No. 21176192）.
文摘ZnFe2O4-BiOC1 composites were prepared by both hydrothermal and direct precipitation processes and the structures and properties of the samples were characterized by various instrumental techniques. The samples were then used as catalysts for the photocatalytic reduction of CQ in cyclohexanol under ultraviolet irradiation to give cyclohexanone （CH） and cyclohexyl formate （CF）. The photocatalytic CO2 reduction activities over the hydrothermally prepared ZnFeaO4-BiOCl composites were higher than those over the directly-precipitated composites. This is because compared to the direct-precipitation sample, the ZnFe2O4 nanoparticles in the hydrothermal sample were smaller and more uniformly distributed on the surface of BiOCl and so more heterojunctions were formed. Higher CF and CH yields were obtained for the pure BiOCl and BiOCl composite samples with more exposed （001） facets than for the samples with more exposed （010） facets. This is due to the higher density of oxygen atoms in the exposed （001） facets, which creates more oxygen vacancies, and thereby improves the separation efficiency of the electron-hole pairs. More importantly, irradiation of the （001） facets with ultraviolet light produces photo-generated electrons which is helpful for the reduction of CO2 to -CO2^-. The mechanism for the photocatalytic reduction of CO2 in cyclohexanol over ZnFe204-BiOCl composites with exposed （001） facets involves electron transfer and carbon radical formation.
基金supported by the National Natural Science Foundation of China(21333003,21303051)Shanghai Natural Science Foundation(13ZR1453000)the Recruitment Program of Global Experts(B08021)
文摘The chemical reduction of carbon dioxide(CO2) has always drawn intensive attentions as it can not only remove CO2 which is the primary greenhouse gas but also produce useful fuels. Industrial synthesis of methanol utilizing copper-based catalysts is a commonly used process for CO2 hydrogenation. Despite extensive efforts on improving its reaction mechanism by identifying the active sites and optimizing the operating temperature and pressure, it is still remains completely unveiled. The selectivities of CO2 electroreduction at copper electrode could mainly be towards carbon monoxide(CO), formic acid(HCOOH), methane(CH4) or ethylene(C2H4), which depends on the chemical potentials of hydrogen controlled by the applied potential. Interestingly, methanol could hardly be produced electrochemically despite utilizing metallic copper as catalysts in both processes. Moreover, the mechanistic researches have also been performed aiming to achieve the higher selectivity towards more desirable higher hydrocarbons. In this work, we review the present proposals of reaction mechanisms of copper catalyzing CO2 reduction in industrial methanol synthesis and electrochemical environment in terms of density functional theory(DFT) calculations, respectively. In addition, the influences of the simulation methods of solvation and electrochemical model at liquid-solid interface on the selectivity are discussed and compared.
基金supported by the National Natural Science Foundation of China (Grant No. 20876125)the Research Fund for the Doctoral Program of Higher Education, China (Grant No. 20096101110013)the Northwest University Graduate Interdisciplinary Funds, China (Grant Nos. 09YJC24 and 09YJC27)
文摘A rare-earth free upconversion luminescent material, 10BaF2：NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light （550 nm-610 nm） into ultraviolet light （290 nm 350 nm）, and two emission peaks at 304 nm and 324 nm are observed under the excitation of 583 nm at room temperature. Subsequently, 10BaF2：NaF, Na3AIF6/TiO2 composite photocatalyst is prepared and its catalytic activity is evaluated by the photocatalytic reduction of CO2 under visible light irradiation （λ〉 515 nm）. The results show that 10BaF2：NaF, Na3AIF6/TiO2 is a more effective photocatalyst for CO2 reduction than pure TiO2, their corresponding methanol yields are 179 and 0 μmol/g-cat under the same conditions. Additionally, the mechanism of photocatalytic reduction of CO2 on 10BaF2：NaF, Na3AIF6/TiO2 is proposed.
文摘With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Zeng Jie(曾杰)and Prof.Yang Jinlong(杨金龙),both from Hefei National Laboratory for Physical Sciences at the Microscale,University of Science and Technology of China,
