Ab initio calculations of the orbital and the ground state energies of some open- and closed-shell atoms over Slater type orbitals with quantum numbers integer and Slater type orbitals with quantum numbers noninteger ...Ab initio calculations of the orbital and the ground state energies of some open- and closed-shell atoms over Slater type orbitals with quantum numbers integer and Slater type orbitals with quantum numbers noninteger have been performed. In order to increase the efficiency of these calculations the atomic two-electron integrals were expressed in terms of incomplete beta function. Results were observed to be in good agreement with the literature.展开更多
Manipulating the assembly,composition,and arrangement of metal atoms is a new concept to control the behavior,coordination environment,and electronic structure of metal atom catalytic systems and represents the develo...Manipulating the assembly,composition,and arrangement of metal atoms is a new concept to control the behavior,coordination environment,and electronic structure of metal atom catalytic systems and represents the development trend of next generation catalysts.Here,we report a method for anchoring copper atoms from individual atoms to the graphdiyne(GDY)surface and nucleating via atomic assembly manipulation under mild conditions,achieving step-by-step fabrication from atoms to clusters,tiny nanosheets,and larger atomic crystal arrangements,and achieving the selective and efficient C–C coupling during CO_(2)conversion.The new idea proposed in this work is to control the growth of the sp-C∼N-Cu structure interface,and produce zero-valent metal atoms,which leads to strong noninteger charge transfer between GDY and metal atoms.The distance between Cu atoms and the coordination environment of Cu metal atoms can be controlled by changing the catalyst structure,which promotes the selective adsorption of CO_(2)/intermediates and greatly activates C–C coupling to obtain C_(2)products.This new catalytic mechanism ensures excellent catalytic selectivity and stability of the catalysis process.In-situ infrared and X-ray absorption fine structure measurements demonstrate the formation and selective adsorption of*COH and*CO on Cu atoms,followed by C–C bond formation through a formyl-bicarbonate coupling pathway.Such a catalyst exhibits a high selectivity for CO_(2)-to-C_(2)conversion with a high C_(2)products Faradaic efficiency(FE)of 62.5%at a high current density of 178 mA cm^(−2)at ambient temperatures and pressures.The high FE and activity were maintained after the 100-h long-term stability test.展开更多
文摘Ab initio calculations of the orbital and the ground state energies of some open- and closed-shell atoms over Slater type orbitals with quantum numbers integer and Slater type orbitals with quantum numbers noninteger have been performed. In order to increase the efficiency of these calculations the atomic two-electron integrals were expressed in terms of incomplete beta function. Results were observed to be in good agreement with the literature.
基金supported by the Basic Science Center Project of the National Natural Science Foundation of China(grant no.22388101)the National Key Research and Development Project of China(grant nos.2022YFA1204500,2022YFA1204501,2022YFA1204503,and 2018YFA0703501)the Key Program of the Chinese Academy of Sciences(grant no.XDPB13).
文摘Manipulating the assembly,composition,and arrangement of metal atoms is a new concept to control the behavior,coordination environment,and electronic structure of metal atom catalytic systems and represents the development trend of next generation catalysts.Here,we report a method for anchoring copper atoms from individual atoms to the graphdiyne(GDY)surface and nucleating via atomic assembly manipulation under mild conditions,achieving step-by-step fabrication from atoms to clusters,tiny nanosheets,and larger atomic crystal arrangements,and achieving the selective and efficient C–C coupling during CO_(2)conversion.The new idea proposed in this work is to control the growth of the sp-C∼N-Cu structure interface,and produce zero-valent metal atoms,which leads to strong noninteger charge transfer between GDY and metal atoms.The distance between Cu atoms and the coordination environment of Cu metal atoms can be controlled by changing the catalyst structure,which promotes the selective adsorption of CO_(2)/intermediates and greatly activates C–C coupling to obtain C_(2)products.This new catalytic mechanism ensures excellent catalytic selectivity and stability of the catalysis process.In-situ infrared and X-ray absorption fine structure measurements demonstrate the formation and selective adsorption of*COH and*CO on Cu atoms,followed by C–C bond formation through a formyl-bicarbonate coupling pathway.Such a catalyst exhibits a high selectivity for CO_(2)-to-C_(2)conversion with a high C_(2)products Faradaic efficiency(FE)of 62.5%at a high current density of 178 mA cm^(−2)at ambient temperatures and pressures.The high FE and activity were maintained after the 100-h long-term stability test.
