Efficient photocatalytic CO_(2)reduction to valuable fuels is an ideal strategy for addressing the energy and environmental crisis.Herein,we developed the Zn-incorporated hollow nanocages,assembled by NiCo-layered dou...Efficient photocatalytic CO_(2)reduction to valuable fuels is an ideal strategy for addressing the energy and environmental crisis.Herein,we developed the Zn-incorporated hollow nanocages,assembled by NiCo-layered double hydroxide ultrathin nanosheets(NiCoZnx-LDH),as highly efficient photocatalysts.Spectroscopic characterization and theoretical calculations demonstrate that Zn doping leads to an upshift of the d-band center of Ni-Co dual sites,increasing unoccupied antibonding orbitals and enhancing the binding strength of adsorbates.Therefore,NiCoZn_(0.10)-LDH with the upgrade of d-band shows a lower·CO_(2)-formation energy,resulting in a more effective stabilization of the rate-limiting·CO_(2)-intermediate.This boosts the overall CO_(2)photoreduction performance over NiCoZn_(0.10)-LDH,resulting in a high CO yield of 158.1μmol·g^(-1)·h^(-1)with 92.1%selectivity.Our findings enrich the fundamental understanding of the CO_(2)activation mechanism and provide additional insights into the d-band center theory to enhance the photocatalytic activity for overall CO_(2)reduction.展开更多
Olefin hydrogenation under mild condition is crucial and challenging for industrial applications. Herein, defective UiO-66(Ce) was constructed by using cyanuric acid as the molecular etching “scissors” and further t...Olefin hydrogenation under mild condition is crucial and challenging for industrial applications. Herein, defective UiO-66(Ce) was constructed by using cyanuric acid as the molecular etching “scissors” and further to synthesize heterogeneous catalyst with highly dispersed RuNi nanoparticles (Ru1Ni1.5@UiO-66(Ce)-12 h). The construction of Ce-O-Ru/Ni heterogeneous interfaces and Ni–Ru bonds provide electron transfer channels from Ce-oxo clusters and Ni species to Ru species. Furthermore, the microenvironment and electronic structure of Ru0 active sites were synergistically regulated by adjusting the content of metal-organic frameworks (MOFs) defects and Ni promoter, thereby enhancing the adsorption and activation ability of H–H and C=C bonds. Therefore, Ru1Ni1.5@UiO-66(Ce)-12 h achieved dicyclopentadiene saturated hydrogenation (100% conversion) to tetrahydrodicyclopentadiene (∼ 100% selectivity) under mild condition (35℃, 1 MPa) with only 25 min. Meanwhile, the sample exhibited excellent structural stability after 6 cycles test. This study provides a promising strategy for the rational design of remarkable noble metal-based catalysts for practical applications.展开更多
基金supported by the Beijing Natural Science Foundation(No.2232053)the National Natural Science Foundation of China(No.52002029)+1 种基金Natural Science Foundation of Guangdong Province(No.2022A1515011918)Research and Development Project of Henan Academy of Sciences China(No.20250618006).
文摘Efficient photocatalytic CO_(2)reduction to valuable fuels is an ideal strategy for addressing the energy and environmental crisis.Herein,we developed the Zn-incorporated hollow nanocages,assembled by NiCo-layered double hydroxide ultrathin nanosheets(NiCoZnx-LDH),as highly efficient photocatalysts.Spectroscopic characterization and theoretical calculations demonstrate that Zn doping leads to an upshift of the d-band center of Ni-Co dual sites,increasing unoccupied antibonding orbitals and enhancing the binding strength of adsorbates.Therefore,NiCoZn_(0.10)-LDH with the upgrade of d-band shows a lower·CO_(2)-formation energy,resulting in a more effective stabilization of the rate-limiting·CO_(2)-intermediate.This boosts the overall CO_(2)photoreduction performance over NiCoZn_(0.10)-LDH,resulting in a high CO yield of 158.1μmol·g^(-1)·h^(-1)with 92.1%selectivity.Our findings enrich the fundamental understanding of the CO_(2)activation mechanism and provide additional insights into the d-band center theory to enhance the photocatalytic activity for overall CO_(2)reduction.
基金supported by the National Key Research and Development Program of China(No.2021YFB3500700)the National Natural Science Foundation of China(No.51972024)the Natural Science Foundation of Guangdong Province(No.2022A1515010185).
文摘Olefin hydrogenation under mild condition is crucial and challenging for industrial applications. Herein, defective UiO-66(Ce) was constructed by using cyanuric acid as the molecular etching “scissors” and further to synthesize heterogeneous catalyst with highly dispersed RuNi nanoparticles (Ru1Ni1.5@UiO-66(Ce)-12 h). The construction of Ce-O-Ru/Ni heterogeneous interfaces and Ni–Ru bonds provide electron transfer channels from Ce-oxo clusters and Ni species to Ru species. Furthermore, the microenvironment and electronic structure of Ru0 active sites were synergistically regulated by adjusting the content of metal-organic frameworks (MOFs) defects and Ni promoter, thereby enhancing the adsorption and activation ability of H–H and C=C bonds. Therefore, Ru1Ni1.5@UiO-66(Ce)-12 h achieved dicyclopentadiene saturated hydrogenation (100% conversion) to tetrahydrodicyclopentadiene (∼ 100% selectivity) under mild condition (35℃, 1 MPa) with only 25 min. Meanwhile, the sample exhibited excellent structural stability after 6 cycles test. This study provides a promising strategy for the rational design of remarkable noble metal-based catalysts for practical applications.
