It is important for environmental protection to search for catalysts with excellent performance and cost-effective to reduce SO2 by CO. In this work, using first-principles calculation, we have studied the catalytic p...It is important for environmental protection to search for catalysts with excellent performance and cost-effective to reduce SO2 by CO. In this work, using first-principles calculation, we have studied the catalytic performance of Au5Mn（M = Ni, Pd, Pt, Cu, Ag, Au; n = 1, 0,-1） clusters, and showed that, by giving a negative charge to the Au5M（M = Cu,Ag, Au, Pd） clusters, we could improve the selectivity of SO2 and avoid effectively catalyst CO poisoning simultaneously.At the same time, the catalytic reaction rate for the reduction of SO2 by CO with Au5M-（M = Cu, Ag, Au, Pd） clusters is greatly improved when the Au5M clusters are charged. These advantages can be well explained by the charge transfer between the clusters and adsorbed molecules, which means that we can effectively control the performance of the catalyst.The equilibrium structures of Au5Mn（M = Ni, Pd, Pt, Cu, Ag, Au; n = 1, 0,-1） clusters without or with adsorbed SO2 or CO molecule are also discussed, and the most stable geometrical structures of Aun5 M-ML（ML = SO2, CO, SO, and COS）can be explained very well by the match of orbitals symmetry and density of electron cloud through their frontier molecular orbitals. Considering the catalyst cost（Cu is much cheaper than Ag and Au）, selectivity of SO2, and effectively avoiding the catalyst CO poisoning, we propose that Au5Cu-is an ideal catalyst for getting rid of SO2 and CO simultaneously.展开更多
Geometric and electronic properties of Pdn–1Pb and Pdn （n≤8） clusters have been studied by using density functional theory with effective core potentials, focusing on the differences between mono- and bimetallic c...Geometric and electronic properties of Pdn–1Pb and Pdn （n≤8） clusters have been studied by using density functional theory with effective core potentials, focusing on the differences between mono- and bimetallic clusters. The average bond length of Pdn–1Pb （n≤8） bimetallic clusters is longer than that of pure palladium clusters except for n = 2 and 3. The most stable structure of Pdn–1Pb （n≤7） is the singlet where there is at least a Pd or Pb atom on its excited state. The energy gaps of Pd–Pb binary clusters are narrower than those of Pdn clusters, and then the chemical activity is strengthened when Pdn clusters are doped with Pb.展开更多
A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]?2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in ...A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]?2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 21.680(4), b = 20.680(4), c = 26.120(5) ?, V = 11711(4) ?3, Dc = 3.972 g/cm3, Z = 8, μ(MoKa) = 24.661 mm?1, F(000) = 12440, the final R = 0.0527 and wR = 0.1416 for 11527 observed reflec- tions with I > 2σ(I). The crystal structure is composed of [{Cu(en)2}HPW12O40]2? anions, discrete [Cu(en)2H2O]+ complex cations and crystal water molecules, which are held together into a three- dimensional network through hydrogen-bonding interactions. The anionic [{Cu(en)2}HPW12O40]2? is formed by the mixed valance {HPWVI11WVO40}3? Keggin unit covalently linked by a {Cu(en)2}+ group.展开更多
Structural and electronic properties of bimetallic clusters AlnCom with n=1～7 and m=1～2 have been investigated using the B3LYP-DFT method.Structural optimization and frequency analysis were performed at the CEP-121G...Structural and electronic properties of bimetallic clusters AlnCom with n=1～7 and m=1～2 have been investigated using the B3LYP-DFT method.Structural optimization and frequency analysis were performed at the CEP-121G level.The charge-induced structural changes in these anions were discussed.In addition,the corresponding total energies,binding energies,adiabatic electron affinities and vertical electron affinity were also presented and discussed.Our predicted vertical ionization potentials are in reasonable agreement with the experimental ionization potentials.Among different AlnCom and AlnCom-anions （n=1～7,m=1～2）,Al4Co,Al6Co,Al4Co-,Al6Co-and Al4Co2-are predicted to be species with high stabilities.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant No.11375091)the Natural Science Foundation of Zhejiang,China(Grant No.LY18A040003)+1 种基金the Natural Science Foundation of Ningbo,China(Grant No.2018A610220)the K.C.Wong Magna Fund in Ningbo University,China
文摘It is important for environmental protection to search for catalysts with excellent performance and cost-effective to reduce SO2 by CO. In this work, using first-principles calculation, we have studied the catalytic performance of Au5Mn（M = Ni, Pd, Pt, Cu, Ag, Au; n = 1, 0,-1） clusters, and showed that, by giving a negative charge to the Au5M（M = Cu,Ag, Au, Pd） clusters, we could improve the selectivity of SO2 and avoid effectively catalyst CO poisoning simultaneously.At the same time, the catalytic reaction rate for the reduction of SO2 by CO with Au5M-（M = Cu, Ag, Au, Pd） clusters is greatly improved when the Au5M clusters are charged. These advantages can be well explained by the charge transfer between the clusters and adsorbed molecules, which means that we can effectively control the performance of the catalyst.The equilibrium structures of Au5Mn（M = Ni, Pd, Pt, Cu, Ag, Au; n = 1, 0,-1） clusters without or with adsorbed SO2 or CO molecule are also discussed, and the most stable geometrical structures of Aun5 M-ML（ML = SO2, CO, SO, and COS）can be explained very well by the match of orbitals symmetry and density of electron cloud through their frontier molecular orbitals. Considering the catalyst cost（Cu is much cheaper than Ag and Au）, selectivity of SO2, and effectively avoiding the catalyst CO poisoning, we propose that Au5Cu-is an ideal catalyst for getting rid of SO2 and CO simultaneously.
文摘Geometric and electronic properties of Pdn–1Pb and Pdn （n≤8） clusters have been studied by using density functional theory with effective core potentials, focusing on the differences between mono- and bimetallic clusters. The average bond length of Pdn–1Pb （n≤8） bimetallic clusters is longer than that of pure palladium clusters except for n = 2 and 3. The most stable structure of Pdn–1Pb （n≤7） is the singlet where there is at least a Pd or Pb atom on its excited state. The energy gaps of Pd–Pb binary clusters are narrower than those of Pdn clusters, and then the chemical activity is strengthened when Pdn clusters are doped with Pb.
基金This work was supported by the Natural Science Foundation of Fujian Province (No. E0420001) and the Science Foundation of Huaqiao University (No. 03HZR9)
文摘A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]?2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 21.680(4), b = 20.680(4), c = 26.120(5) ?, V = 11711(4) ?3, Dc = 3.972 g/cm3, Z = 8, μ(MoKa) = 24.661 mm?1, F(000) = 12440, the final R = 0.0527 and wR = 0.1416 for 11527 observed reflec- tions with I > 2σ(I). The crystal structure is composed of [{Cu(en)2}HPW12O40]2? anions, discrete [Cu(en)2H2O]+ complex cations and crystal water molecules, which are held together into a three- dimensional network through hydrogen-bonding interactions. The anionic [{Cu(en)2}HPW12O40]2? is formed by the mixed valance {HPWVI11WVO40}3? Keggin unit covalently linked by a {Cu(en)2}+ group.
基金supported by the National Natural Science Foundation of China (20603021)Youth Foundation of Shanxi Province (2007021009)
文摘Structural and electronic properties of bimetallic clusters AlnCom with n=1～7 and m=1～2 have been investigated using the B3LYP-DFT method.Structural optimization and frequency analysis were performed at the CEP-121G level.The charge-induced structural changes in these anions were discussed.In addition,the corresponding total energies,binding energies,adiabatic electron affinities and vertical electron affinity were also presented and discussed.Our predicted vertical ionization potentials are in reasonable agreement with the experimental ionization potentials.Among different AlnCom and AlnCom-anions （n=1～7,m=1～2）,Al4Co,Al6Co,Al4Co-,Al6Co-and Al4Co2-are predicted to be species with high stabilities.
