Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)...Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.展开更多
Exploring high-performance and cost-effective electrocatalysts that are applicable in oxygen evolution reaction(OER)is crucial for water splitting and energy storage.In this work,a facile and scalable chemical reducti...Exploring high-performance and cost-effective electrocatalysts that are applicable in oxygen evolution reaction(OER)is crucial for water splitting and energy storage.In this work,a facile and scalable chemical reduction strategy is developed to synthesize FeCoNiPB non-noble metal-based amorphous high-entropy oxides for the OER in alkaline media.The FeCoNiPB oxides exhibit overpotentials of 235 and 306 mV at current densities of 10 and 100 mA/cm^(2),respectively,as well as a small Tafel slope of 53 mV/dec in 1.0 M KOH solution,outperforming the performance of FeCoPB,FeNiPB,and CoNiPB oxides and the commercial RuO_(2),while maintaining excellent stability with negligible overpotential amplification over 40 h.The superior OER electrocatalytic efficiency and stability of the FeCoNiPB catalyst is primarily attributed to its unique amorphous high-entropy nanostructure,synergistic effect of the multiple components,and in situ-formed amorphous sheets with a thin(FeCoNi)OOH crystalline layer on the edge during long-term OER.This work provides new insights to design and prepare low-cost,highly efficient,and durable OER electrocatalysts.展开更多
基金financial support from the National Natural Science Foundation of China(No.22272038)the Science and Technology Planning Project of Guangzhou City(No.2023A03J0026)。
文摘Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.
基金supported by the National Natural Science Foundation of China(No.51631003)the Natural Science Foundation of Jiangsu Province(No.BK20191269).
文摘Exploring high-performance and cost-effective electrocatalysts that are applicable in oxygen evolution reaction(OER)is crucial for water splitting and energy storage.In this work,a facile and scalable chemical reduction strategy is developed to synthesize FeCoNiPB non-noble metal-based amorphous high-entropy oxides for the OER in alkaline media.The FeCoNiPB oxides exhibit overpotentials of 235 and 306 mV at current densities of 10 and 100 mA/cm^(2),respectively,as well as a small Tafel slope of 53 mV/dec in 1.0 M KOH solution,outperforming the performance of FeCoPB,FeNiPB,and CoNiPB oxides and the commercial RuO_(2),while maintaining excellent stability with negligible overpotential amplification over 40 h.The superior OER electrocatalytic efficiency and stability of the FeCoNiPB catalyst is primarily attributed to its unique amorphous high-entropy nanostructure,synergistic effect of the multiple components,and in situ-formed amorphous sheets with a thin(FeCoNi)OOH crystalline layer on the edge during long-term OER.This work provides new insights to design and prepare low-cost,highly efficient,and durable OER electrocatalysts.
