The photoabsorption spectra have been calculated for Sis and SilO （n ≤ 5） clusters using time-dependent density-function theory. Our studies suggest that Sin-1 O clusters are relatively stable than those of corresp...The photoabsorption spectra have been calculated for Sis and SilO （n ≤ 5） clusters using time-dependent density-function theory. Our studies suggest that Sin-1 O clusters are relatively stable than those of corresponding Sis clusters. Moreover, substantial differences are observed among the absorption spectra of different molecules in the energy region （0 - 8 eV）. Comparing two different exchange-correlation potentials, local-density and generalized-gradient approximations, both calculated optical spectra present the same spectral feature.展开更多
A new series of fluorescent arylamino fumarinitrile derivatives was designed and optimized using density function theory at the B3LYP/6-31G^＊ level. Based on the optimized geometries, the electronic, fluorescent and ...A new series of fluorescent arylamino fumarinitrile derivatives was designed and optimized using density function theory at the B3LYP/6-31G^＊ level. Based on the optimized geometries, the electronic, fluorescent and 13C NMR spectra are calculated with INDO/CIS, CIS-ZINDO TD, and B3LYP/6-31G^＊ methods, respectively. Starting with the first of the series, the LUMO-HOMO energy gaps of the derivatives become wider and the fluorescent wavelengths and the main peaks in the electronic spectra are blue-shifted owing to the large steric effect of naphthyl rings. On the contrary, the energy gaps of the derivatives turn narrow, and the fluorescent wavelengths and the main peaks in the electronic spectra are red-shifted since hydroxyl groups improve the symmetry and extend the conjugation system. The chemical shifts of sp^2-C on the phenyl rings are moved upfield, while chemical shifts of carbon atoms on the cyano groups and those connected with the cyano groups are changed downfield in the presence of hydroxyl groups.展开更多
Photocatalytic CO2 reduction holds promise as a future technology for the manufacture of fuels and commodity chemicals.However,factors controlling product selectivity remain poorly understood.Herein,we compared the pe...Photocatalytic CO2 reduction holds promise as a future technology for the manufacture of fuels and commodity chemicals.However,factors controlling product selectivity remain poorly understood.Herein,we compared the performance of a homologous series of Zn-based layered double hydroxide(ZnM-LDH)photocatalysts for CO2 reduction.By varying the trivalent or tetravalent metal cations in the ZnM-LDH photocatalysts(M=Ti4+,Fe3+,Co3+,Ga3+,Al3+),the product selectivity of the reaction could be precisely controlled.ZnTi-LDH afforded CH4 as the main reduction product;ZnFe-LDH and ZnCo-LDH yielded H2 exclusively from water splitting;whilst ZnGa-LDH and ZnAl-LDH generated CO.In-situ diffuse reflectance infrared measurements,valence band XPS and density function theory calculations were applied to rationalize the CO2 reduction selectivities of the different ZnM-LDH photocatalysts.The analyses revealed that the d-band center(ed)position of the M3+or M4+cations controlled the adsorption strength of CO2 and thus the selectivity to carbon-containing products or H2.Cations with d-band centers relatively close to the Fermi level(Ti4+,Ga3+and Al3+)adsorbed CO2 strongly yielding CH4 or CO,whereas metal cations with d-band centers further from the Fermi level(Fe3+and Co3+)adsorbed CO2 poorly,thereby yielding H2 only(from water splitting).Our findings clarify the role of trivalent and tetravalent metal cations in LDH photocatalysts for the selective CO2 reduction,paving new ways for the development of improved LDH photocatalyst with high selectivities to specific products.展开更多
基金supported by the National Natural Science Foundation of China and China Academy of Engineering Physics under Grant No. 10676025 (NSAF)
文摘The photoabsorption spectra have been calculated for Sis and SilO （n ≤ 5） clusters using time-dependent density-function theory. Our studies suggest that Sin-1 O clusters are relatively stable than those of corresponding Sis clusters. Moreover, substantial differences are observed among the absorption spectra of different molecules in the energy region （0 - 8 eV）. Comparing two different exchange-correlation potentials, local-density and generalized-gradient approximations, both calculated optical spectra present the same spectral feature.
文摘A new series of fluorescent arylamino fumarinitrile derivatives was designed and optimized using density function theory at the B3LYP/6-31G^＊ level. Based on the optimized geometries, the electronic, fluorescent and 13C NMR spectra are calculated with INDO/CIS, CIS-ZINDO TD, and B3LYP/6-31G^＊ methods, respectively. Starting with the first of the series, the LUMO-HOMO energy gaps of the derivatives become wider and the fluorescent wavelengths and the main peaks in the electronic spectra are blue-shifted owing to the large steric effect of naphthyl rings. On the contrary, the energy gaps of the derivatives turn narrow, and the fluorescent wavelengths and the main peaks in the electronic spectra are red-shifted since hydroxyl groups improve the symmetry and extend the conjugation system. The chemical shifts of sp^2-C on the phenyl rings are moved upfield, while chemical shifts of carbon atoms on the cyano groups and those connected with the cyano groups are changed downfield in the presence of hydroxyl groups.
基金financial support from the National Key Projects for Fundamental Research and Development of China (2016YFB0600901, 2017YFA0206904, 2017YFA0206900, 2018YFB1502002)the National Natural Science Foundation of China (51825205, 51772305, 51572270, U1662118, 21871279, 21802154, 21902168)+10 种基金the Beijing Natural Science Foundation (2191002, 2182078, 2194089)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17000000)the Royal Society-Newton Advanced Fellowship (NA170422)the International Partnership Program of Chinese Academy of Sciences (GJHZ1819, GJHZ201974)the Beijing Municipal Science and Technology Project (Z181100005118007)the K. C. Wong Education Foundationthe Young Elite Scientist Sponsorship Program by CAST (YESS)the Youth Innovation Promotion Association of the CASthe Energy Education Trust of New Zealandthe Mac Diarmid Institute for Advanced Materials and Nanotechnologythe Dodd Walls Centre for Photonic and Quantum Technologies。
文摘Photocatalytic CO2 reduction holds promise as a future technology for the manufacture of fuels and commodity chemicals.However,factors controlling product selectivity remain poorly understood.Herein,we compared the performance of a homologous series of Zn-based layered double hydroxide(ZnM-LDH)photocatalysts for CO2 reduction.By varying the trivalent or tetravalent metal cations in the ZnM-LDH photocatalysts(M=Ti4+,Fe3+,Co3+,Ga3+,Al3+),the product selectivity of the reaction could be precisely controlled.ZnTi-LDH afforded CH4 as the main reduction product;ZnFe-LDH and ZnCo-LDH yielded H2 exclusively from water splitting;whilst ZnGa-LDH and ZnAl-LDH generated CO.In-situ diffuse reflectance infrared measurements,valence band XPS and density function theory calculations were applied to rationalize the CO2 reduction selectivities of the different ZnM-LDH photocatalysts.The analyses revealed that the d-band center(ed)position of the M3+or M4+cations controlled the adsorption strength of CO2 and thus the selectivity to carbon-containing products or H2.Cations with d-band centers relatively close to the Fermi level(Ti4+,Ga3+and Al3+)adsorbed CO2 strongly yielding CH4 or CO,whereas metal cations with d-band centers further from the Fermi level(Fe3+and Co3+)adsorbed CO2 poorly,thereby yielding H2 only(from water splitting).Our findings clarify the role of trivalent and tetravalent metal cations in LDH photocatalysts for the selective CO2 reduction,paving new ways for the development of improved LDH photocatalyst with high selectivities to specific products.
