Nitrogen vacancies and sulfur co-doped g-C3N4 with outstanding N2 photofixation ability was synthesized via dielectric barrier discharge plasma treatment. X-ray diffraction, ultraviolet–visible spectroscopy, N2 adsor...Nitrogen vacancies and sulfur co-doped g-C3N4 with outstanding N2 photofixation ability was synthesized via dielectric barrier discharge plasma treatment. X-ray diffraction, ultraviolet–visible spectroscopy, N2 adsorption, scanning electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and temperature-programmed desorption were used to characterize the as-prepared catalyst. The results showed that plasma treatment cannot change the morphology of the as-prepared catalyst but introduces nitrogen vacancies and sulfur into g-C3N4 lattice simultaneously. The as-prepared co-doped g-C3N4 displays an ammonium ion production rate as high as 6.2 mg·L^-1·h^-1·gcat^-1, which is 2.3 and 25.8 times higher than that of individual N-vacancy-doped g-C3N4 and neat g-C3N4, respectively, as well as showing good catalytic stability. Experimental and density functional theory calculation results indicate that, compared with individual N vacancy doping, the introduction of sulfur can promote the activation ability of N vacancies to N2 molecules, leading to promoted N2 photofixation performance.展开更多
Solar‐driven conversion of carbon dioxide,water and nitrogen into high value‐added fuels(e.g.H_(2),CO,CH_(4),CH_(3)OH,NH_(3) and so on)is regarded as an environmental‐friendly and ideal route for relieving the gree...Solar‐driven conversion of carbon dioxide,water and nitrogen into high value‐added fuels(e.g.H_(2),CO,CH_(4),CH_(3)OH,NH_(3) and so on)is regarded as an environmental‐friendly and ideal route for relieving the greenhouse gas effect and countering energy crisis,which is an attractive and challenging topic.Hence,various types of photocatalysts have been developed successively to meet the requirements of these photocatalysis.Among them,cobalt‐based heterogeneous catalysts emerge as one of the most promising photocatalysts that open up alluring vistas in the field of solar‐to‐fuels conversion,which can effectively enhance photocatalytic efficiency by extending light absorption range,promoting charge separation,providing active sites,and lowering reaction barrier.In this review,we first present the working principles of cobalt‐based heterogeneous catalysts for photocatalytic water splitting,CO_(2) reduction,and N_(2) fixation.Second,five efficient strategies including surface modification,morphology modulation,crystallinity controlling,crystal engineering and doping,are discussed for improving the photocatalytic performance with different types cobalt‐based catalysts(cobalt nanoparticles and single atom,oxides,sulfides,phosphides,MOFs,COFs,LDHs,carbide,and nitrides).Third,we outline the applications for the state‐of‐the‐art photocatalytic CO_(2) reduction and water splitting,and nitrogen fixation over cobalt‐based heterogeneous catalysts.Finally,the central challenges and possible improvements of cobalt‐based photocatalysis in the future are presented.The purpose of this review is to summarize the past experience and lessons,and provide reference for the further development of cobalt‐based photocatalysis technology.展开更多
In nutrient-limited alpine meadows,nitrogen(N) mineralization is prior to soil microbial immobilization;therefore,increased mineral N supply would be most likely immobilized by soil microbes due to nutrient shortage i...In nutrient-limited alpine meadows,nitrogen(N) mineralization is prior to soil microbial immobilization;therefore,increased mineral N supply would be most likely immobilized by soil microbes due to nutrient shortage in alpine soils.In addition,low temperature in alpine meadows might be one of the primary factors limiting soil organic matter decomposition and thus N mineralization.A laboratory incubation experiment was performed using an alpine meadow soil from the Tibetan Plateau.Two levels of NH4NO3(N) or glucose(C) were added,with a blank without addition of C or N as the control,before incubation at 5,15,or 25 ℃ for 28 d.CO2 efflux was measured during the 28-d incubation,and the mineral N was measured at the beginning and end of the incubation,in order to test two hypotheses:1) net N mineralization is negatively correlated with CO2 efflux for the control and 2) the external labile N or C supply will shift the negative correlation to positive.The results showed a negative correlation between CO2 efflux and net N immobilization in the control.External inorganic N supply did not change the negative correlation.The external labile C supply shifted the linear correlation from negative to positive under the low C addition level.However,under the high C level,no correlation was found.These suggested that the correlation of CO2 efflux to net N mineralization strongly depend on soil labile C and C:N ratio regardless of temperatures.Further research should focus on the effects of the types and the amount of litter components on interactions of C and N during soil organic matter decomposition.展开更多
基金supported by the National Natural Science Foundation of China(41701364)the Liaoning Doctoral Priming Fund Project(201601333,20170520109)+2 种基金the Basic Scientific Research in Colleges and Universities in Heilongjiang Province(KJCXZD201715)the Harbin Science and Technology Bureau Project(2017RAQXJ145)supported by Super Computing Center of Dalian University of Technology~~
文摘Nitrogen vacancies and sulfur co-doped g-C3N4 with outstanding N2 photofixation ability was synthesized via dielectric barrier discharge plasma treatment. X-ray diffraction, ultraviolet–visible spectroscopy, N2 adsorption, scanning electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and temperature-programmed desorption were used to characterize the as-prepared catalyst. The results showed that plasma treatment cannot change the morphology of the as-prepared catalyst but introduces nitrogen vacancies and sulfur into g-C3N4 lattice simultaneously. The as-prepared co-doped g-C3N4 displays an ammonium ion production rate as high as 6.2 mg·L^-1·h^-1·gcat^-1, which is 2.3 and 25.8 times higher than that of individual N-vacancy-doped g-C3N4 and neat g-C3N4, respectively, as well as showing good catalytic stability. Experimental and density functional theory calculation results indicate that, compared with individual N vacancy doping, the introduction of sulfur can promote the activation ability of N vacancies to N2 molecules, leading to promoted N2 photofixation performance.
文摘Solar‐driven conversion of carbon dioxide,water and nitrogen into high value‐added fuels(e.g.H_(2),CO,CH_(4),CH_(3)OH,NH_(3) and so on)is regarded as an environmental‐friendly and ideal route for relieving the greenhouse gas effect and countering energy crisis,which is an attractive and challenging topic.Hence,various types of photocatalysts have been developed successively to meet the requirements of these photocatalysis.Among them,cobalt‐based heterogeneous catalysts emerge as one of the most promising photocatalysts that open up alluring vistas in the field of solar‐to‐fuels conversion,which can effectively enhance photocatalytic efficiency by extending light absorption range,promoting charge separation,providing active sites,and lowering reaction barrier.In this review,we first present the working principles of cobalt‐based heterogeneous catalysts for photocatalytic water splitting,CO_(2) reduction,and N_(2) fixation.Second,five efficient strategies including surface modification,morphology modulation,crystallinity controlling,crystal engineering and doping,are discussed for improving the photocatalytic performance with different types cobalt‐based catalysts(cobalt nanoparticles and single atom,oxides,sulfides,phosphides,MOFs,COFs,LDHs,carbide,and nitrides).Third,we outline the applications for the state‐of‐the‐art photocatalytic CO_(2) reduction and water splitting,and nitrogen fixation over cobalt‐based heterogeneous catalysts.Finally,the central challenges and possible improvements of cobalt‐based photocatalysis in the future are presented.The purpose of this review is to summarize the past experience and lessons,and provide reference for the further development of cobalt‐based photocatalysis technology.
基金Supported by the National Basic Research Program (973 Program) of China (Nos.2010CB951704 and 2010CB833502)the National Natural Science Foundation for Young Scientists of China (No.30600070)the West Light Joint Scholarship of the Chinese Academy of Sciences
文摘In nutrient-limited alpine meadows,nitrogen(N) mineralization is prior to soil microbial immobilization;therefore,increased mineral N supply would be most likely immobilized by soil microbes due to nutrient shortage in alpine soils.In addition,low temperature in alpine meadows might be one of the primary factors limiting soil organic matter decomposition and thus N mineralization.A laboratory incubation experiment was performed using an alpine meadow soil from the Tibetan Plateau.Two levels of NH4NO3(N) or glucose(C) were added,with a blank without addition of C or N as the control,before incubation at 5,15,or 25 ℃ for 28 d.CO2 efflux was measured during the 28-d incubation,and the mineral N was measured at the beginning and end of the incubation,in order to test two hypotheses:1) net N mineralization is negatively correlated with CO2 efflux for the control and 2) the external labile N or C supply will shift the negative correlation to positive.The results showed a negative correlation between CO2 efflux and net N immobilization in the control.External inorganic N supply did not change the negative correlation.The external labile C supply shifted the linear correlation from negative to positive under the low C addition level.However,under the high C level,no correlation was found.These suggested that the correlation of CO2 efflux to net N mineralization strongly depend on soil labile C and C:N ratio regardless of temperatures.Further research should focus on the effects of the types and the amount of litter components on interactions of C and N during soil organic matter decomposition.
