Photocatalytic carbon dioxide reduction is considered an important strategy to solve environmental problems,such as greenhouse gases,but designing and synthesizing effective photocatalysts is a challenge.In recent yea...Photocatalytic carbon dioxide reduction is considered an important strategy to solve environmental problems,such as greenhouse gases,but designing and synthesizing effective photocatalysts is a challenge.In recent years,photocatalytic carbon dioxide reduction by polyoxometalates(POMs)has attracted increasing research interest.Herein,the first purely inorganic ruthenium–germanium–molybdenum–oxygen cluster,Na_(12)Rb_(2)[Ru_(2)O_(2)(GeMo_(10)O_(3)6)_(2)]·44H_(2)O(Ru_(2)Ge_(2)Mo_(2)0),was synthesized by hydrothermal and volatilization methods and applied to photocatalytic carbon dioxide reduction.The yield of CH_(4) reached 547.84μmol g^(−1) in the heterogeneous photocatalytic reaction system with an electron selectivity of 96.86%with respect to CO(71.08μmol g^(−1))after 6 h.The reaction mechanism was confirmed by UV-Vis diffuse reflection spectroscopy,ultraviolet photoelectron spectroscopy(UPS),electrochemical measurements,and steady-state fluorescence quenching experiments.This work provides a reference for the design of Ru-containing polyoxometalates for photocatalytic CO_(2) reduction.展开更多
The binary cluster ions Ge2Cn+/Ge2Cn? and GeCn+ have been produced by laser ablation. The parity ef- fect is present in the negative ions Ge2Cn?, though it is not very prominent. While the experiments tell that the pa...The binary cluster ions Ge2Cn+/Ge2Cn? and GeCn+ have been produced by laser ablation. The parity ef- fect is present in the negative ions Ge2Cn?, though it is not very prominent. While the experiments tell that the parity effect is totally not shown in the positive ions Ge2Cn+. An extensive theoretical investigation on GeCn/GeCn+/GeCn?(n = 1?10) and Ge2Cn/Ge2Cn+/Ge2Cn?(n = 1?9) has been carried out by density functional theory at B3LPY level. The calcula- tion shows that the low-lying states of GeCn/GeCn+/GeCn?(n = 1?10) and Ge2Cn/Ge2Cn+/Ge2Cn? (n = 1?9) are linear structure with germanium atoms locating at terminals respectively. The electronic distributions, ionization potential (IPad), elec- tron affinity (EA) and increasing bonding energy reveal that the parity effect of neutral species is much stronger than that of ions, which is attributed to the valence π-electrons. It is explained that the differences between experiments and cal- culations are due to the kinetic factor in the formation of Ge2Cn±.展开更多
基金supported by the National Natural Science Foundation of China(NSFC,No.21571050,22071044,21771054,and 22171071).
文摘Photocatalytic carbon dioxide reduction is considered an important strategy to solve environmental problems,such as greenhouse gases,but designing and synthesizing effective photocatalysts is a challenge.In recent years,photocatalytic carbon dioxide reduction by polyoxometalates(POMs)has attracted increasing research interest.Herein,the first purely inorganic ruthenium–germanium–molybdenum–oxygen cluster,Na_(12)Rb_(2)[Ru_(2)O_(2)(GeMo_(10)O_(3)6)_(2)]·44H_(2)O(Ru_(2)Ge_(2)Mo_(2)0),was synthesized by hydrothermal and volatilization methods and applied to photocatalytic carbon dioxide reduction.The yield of CH_(4) reached 547.84μmol g^(−1) in the heterogeneous photocatalytic reaction system with an electron selectivity of 96.86%with respect to CO(71.08μmol g^(−1))after 6 h.The reaction mechanism was confirmed by UV-Vis diffuse reflection spectroscopy,ultraviolet photoelectron spectroscopy(UPS),electrochemical measurements,and steady-state fluorescence quenching experiments.This work provides a reference for the design of Ru-containing polyoxometalates for photocatalytic CO_(2) reduction.
基金supported by the National Natural Science Foundation of China(Grant No.20302020)
文摘The binary cluster ions Ge2Cn+/Ge2Cn? and GeCn+ have been produced by laser ablation. The parity ef- fect is present in the negative ions Ge2Cn?, though it is not very prominent. While the experiments tell that the parity effect is totally not shown in the positive ions Ge2Cn+. An extensive theoretical investigation on GeCn/GeCn+/GeCn?(n = 1?10) and Ge2Cn/Ge2Cn+/Ge2Cn?(n = 1?9) has been carried out by density functional theory at B3LPY level. The calcula- tion shows that the low-lying states of GeCn/GeCn+/GeCn?(n = 1?10) and Ge2Cn/Ge2Cn+/Ge2Cn? (n = 1?9) are linear structure with germanium atoms locating at terminals respectively. The electronic distributions, ionization potential (IPad), elec- tron affinity (EA) and increasing bonding energy reveal that the parity effect of neutral species is much stronger than that of ions, which is attributed to the valence π-electrons. It is explained that the differences between experiments and cal- culations are due to the kinetic factor in the formation of Ge2Cn±.
