The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limit...The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limited by sluggish water oxidation kinetics,poor photogenerated charge separation,and insufficient O_(2)adsorption and activation capabilities.Herein,uniformly dispersed single-atom catalysts(SACs)with a Co-N_(4)coordination structure have been synthesized by thermally transforming cobalt phthalocyanine(CoPc)assemblies pre-anchored on phosphate functionalized reduced graphene oxide(Co@rGO-P),and then used to construct heterojunctions with perylenetetracarboxylic acid(PTA)nanosheets for photocatalytic H_(2)O_(2)production by an in-situ growth method.The optimized Co@rGO-P/PTA achieved an H_(2)O_(2)production rate of 1.4 mmol g^(-1)h^(-1)in pure water,with a 12.9-fold enhancement compared to pristine PTA nanosheets exhibiting competitive photoactivity among reported perylene-based materials.Femtosecond transient absorption spectra,in-situ diffuse reflectance infrared Fourier transform spectra and theoretical calculations reveal that the exceptional performance is attributed to the enhanced electron transfer from PTA to rGO via the phosphate bridge and then to the Co-N_(4),and to the promoted O_(2)adsorption and activation at Co-N_(4)active sites.This work provides a feasible and effective strategy for designing highly efficient single-atom semiconductor heterojunction photocatalysts for H_(2)O_(2)production.展开更多
This experiment was conducted in Xinxiang, Henan from June 2013 to June 2014. Total four treatments were designed including farmers ’ common practice （F, 250 kg/hm^2）, 80% F （LF, 200 kg/hm^2）, 80% F＋biochar （LF...This experiment was conducted in Xinxiang, Henan from June 2013 to June 2014. Total four treatments were designed including farmers ’ common practice （F, 250 kg/hm^2）, 80% F （LF, 200 kg/hm^2）, 80% F＋biochar （LFC） and no fertilizer （CK） to measure the dynamic emissions of CO2 and N2O from a summer maize-winter wheat field by static chamber-gas chromatography method. The results showed that the soil CO2 emission was 21.8-1 022.7 mg/（m^2·h）, and was mainly influenced by soil temperature and moisture content. During the growth of summer maize, the soil CO2 emission was more significantly affected by soil moisture con-tent; and in winter wheat growing season, it was more significantly affected by soil temperature in the top 5 cm. The LF and LFC treatments significantly reduced the soil cumulative CO2 emission, especial y during the growth of winter wheat. Fertiliza-tion and irrigation were the main factors influencing the soil N2O emission. The soil N2O emission during the fertilization period accounted for 73.9%-74.5% and 40.5%-43.6% of the soil cumulative N2O emission during the summer maize-and winter wheat-growing season, respectively. The peak of emission fluxes was determined by fertilization amount, while the occurrence time of emission peak and emission re-duction effect were influenced by irrigation. The LF treatment reduced the soil cu-mulative N2O emission by 15.7%-16.8% and 18.1%-18.5% during the growth period of summer maize and winter wheat, respectively. Reduced nitrogen fertilization is an effective way for reducing N2O emission in intensive high-yielding farmland. Under a suitable nitrogen level （200 kg/hm^2）, the application of biochar showed no significant effect on the soil N2O emission in a short term. The N2O emission factors of the L and LF treatments were 0.60% and 0.56%, respectively. ln the intensive high-yield-ing farmland of North China, reducing the nitrogen application amount is an appro-priate measure to mitigate greenhouse gas emissions without crop yield loss.展开更多
文摘The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limited by sluggish water oxidation kinetics,poor photogenerated charge separation,and insufficient O_(2)adsorption and activation capabilities.Herein,uniformly dispersed single-atom catalysts(SACs)with a Co-N_(4)coordination structure have been synthesized by thermally transforming cobalt phthalocyanine(CoPc)assemblies pre-anchored on phosphate functionalized reduced graphene oxide(Co@rGO-P),and then used to construct heterojunctions with perylenetetracarboxylic acid(PTA)nanosheets for photocatalytic H_(2)O_(2)production by an in-situ growth method.The optimized Co@rGO-P/PTA achieved an H_(2)O_(2)production rate of 1.4 mmol g^(-1)h^(-1)in pure water,with a 12.9-fold enhancement compared to pristine PTA nanosheets exhibiting competitive photoactivity among reported perylene-based materials.Femtosecond transient absorption spectra,in-situ diffuse reflectance infrared Fourier transform spectra and theoretical calculations reveal that the exceptional performance is attributed to the enhanced electron transfer from PTA to rGO via the phosphate bridge and then to the Co-N_(4),and to the promoted O_(2)adsorption and activation at Co-N_(4)active sites.This work provides a feasible and effective strategy for designing highly efficient single-atom semiconductor heterojunction photocatalysts for H_(2)O_(2)production.
基金Supported by National Key Technology Research and Development Program(2013BAD11B03)National Natural Science Foundation(31272249,31071865,41505100)~~
文摘This experiment was conducted in Xinxiang, Henan from June 2013 to June 2014. Total four treatments were designed including farmers ’ common practice （F, 250 kg/hm^2）, 80% F （LF, 200 kg/hm^2）, 80% F＋biochar （LFC） and no fertilizer （CK） to measure the dynamic emissions of CO2 and N2O from a summer maize-winter wheat field by static chamber-gas chromatography method. The results showed that the soil CO2 emission was 21.8-1 022.7 mg/（m^2·h）, and was mainly influenced by soil temperature and moisture content. During the growth of summer maize, the soil CO2 emission was more significantly affected by soil moisture con-tent; and in winter wheat growing season, it was more significantly affected by soil temperature in the top 5 cm. The LF and LFC treatments significantly reduced the soil cumulative CO2 emission, especial y during the growth of winter wheat. Fertiliza-tion and irrigation were the main factors influencing the soil N2O emission. The soil N2O emission during the fertilization period accounted for 73.9%-74.5% and 40.5%-43.6% of the soil cumulative N2O emission during the summer maize-and winter wheat-growing season, respectively. The peak of emission fluxes was determined by fertilization amount, while the occurrence time of emission peak and emission re-duction effect were influenced by irrigation. The LF treatment reduced the soil cu-mulative N2O emission by 15.7%-16.8% and 18.1%-18.5% during the growth period of summer maize and winter wheat, respectively. Reduced nitrogen fertilization is an effective way for reducing N2O emission in intensive high-yielding farmland. Under a suitable nitrogen level （200 kg/hm^2）, the application of biochar showed no significant effect on the soil N2O emission in a short term. The N2O emission factors of the L and LF treatments were 0.60% and 0.56%, respectively. ln the intensive high-yield-ing farmland of North China, reducing the nitrogen application amount is an appro-priate measure to mitigate greenhouse gas emissions without crop yield loss.
