Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied ...Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.展开更多
Cu electrocatalysts have been demonstrated to have unique ability to reduce CO_(2)to various high value-added C_(2) products like ethylene and alcohols.However,realizing high selectivity of C_(2) products are still a ...Cu electrocatalysts have been demonstrated to have unique ability to reduce CO_(2)to various high value-added C_(2) products like ethylene and alcohols.However,realizing high selectivity of C_(2) products are still a main challenge due to complex CO_(2)electroreduction pathways and small opportunity of Csingle bondC coupling reactions.Here,we found the origin of enhanced CO_(2)electroreduction reaction activity and product selectivity towards C_(2) products and Csingle bondC coupling mechanism at halogen atoms-adsorbed Cu/H_(2)O interfaces,the corresponding CO_(2)electroreduction evolution mechanisms at the halogen atoms-modified Cu/H_(2)O interfaces are systematically studied via theoretical modeling and calculations.The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer,especially Cl^(-)-adsorbed Cu(111)/H_(2)O interface has the optimum activity and selectivity towards OCCO dimer,subsequent Cl-adsorbed Cu(111)/H_(2)O interface can selectively reduce CO_(2)into C_(2)H_(4) product.The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl^(-)can enhance selectivity of C_(2)H_(4) product.The determinations of onset potentials indicate that electroreduction pathways of CO_(2)towards C_(2)H_(4) product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C_(2)H_(4) product selectivity.This work on selective realization of CO_(2)electroreduction towards C_(2)H_(4) product via Cl^(-)-modified Cu(111)/H_(2)O interface provide a theoretical guideline for how to selectively realize other high value-added C_(2) products.展开更多
基金financially supported by the National Natural Science Foundation of China(No.22172144 and 22272151)Key Research and Development Program of Zhejiang Province(2023C03148).
文摘Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.
基金supported by the Natural Science Foundation of Hunan Province(No.2025JJ50059)Key Program of Hunan University of Arts and Science(No.23ZZ03)Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province and National Natural Science Foundation of China(No.21303048).
文摘Cu electrocatalysts have been demonstrated to have unique ability to reduce CO_(2)to various high value-added C_(2) products like ethylene and alcohols.However,realizing high selectivity of C_(2) products are still a main challenge due to complex CO_(2)electroreduction pathways and small opportunity of Csingle bondC coupling reactions.Here,we found the origin of enhanced CO_(2)electroreduction reaction activity and product selectivity towards C_(2) products and Csingle bondC coupling mechanism at halogen atoms-adsorbed Cu/H_(2)O interfaces,the corresponding CO_(2)electroreduction evolution mechanisms at the halogen atoms-modified Cu/H_(2)O interfaces are systematically studied via theoretical modeling and calculations.The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer,especially Cl^(-)-adsorbed Cu(111)/H_(2)O interface has the optimum activity and selectivity towards OCCO dimer,subsequent Cl-adsorbed Cu(111)/H_(2)O interface can selectively reduce CO_(2)into C_(2)H_(4) product.The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl^(-)can enhance selectivity of C_(2)H_(4) product.The determinations of onset potentials indicate that electroreduction pathways of CO_(2)towards C_(2)H_(4) product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C_(2)H_(4) product selectivity.This work on selective realization of CO_(2)electroreduction towards C_(2)H_(4) product via Cl^(-)-modified Cu(111)/H_(2)O interface provide a theoretical guideline for how to selectively realize other high value-added C_(2) products.
