The synergistic effect of H_3PMo_(12)O_(40) or H_3PW_(12)O_(40) polyoxometalate solution(POM) and TiO_2 to catalyze formic acid oxidation was investigated. Under UV irradiation, hole and electron were photogenerated b...The synergistic effect of H_3PMo_(12)O_(40) or H_3PW_(12)O_(40) polyoxometalate solution(POM) and TiO_2 to catalyze formic acid oxidation was investigated. Under UV irradiation, hole and electron were photogenerated by TiO_2. Formic acid was oxided by the photogenerated hole and photogenerated electron was transferred to reduce polyoxometalate. With this design, formic acid can be converted into electricity in the fuel cell and hydrogen can be generated in the electrolysis cell without noble metal catalyst. Unlike other noble metal catalysts applied in the fuel cells and electrolysis cell, POM and TiO_2 are stable and low cost. The maximum output power density of liquid formic acid fuel cell after 12 h UV irradiation is 5.21 mW/cm^2 for phosphmolybdic acid and 22.81 m W/cm^2 for phosphotungstic acid respectively. The applied potential for the hydrogen evolution is as low as 0.8 V for phosphmolybdic acid and 0.6 V for phosphotungstic acid.展开更多
A new inorganic–organic hybrid 4-Ti-added polyoxometalate:[H_(2)N(CH_(3))_(2)]_(2)Na_(3)H_(5)[{Ti(C_(2)O_(4))(H_(2)O)}_(2){Ti(C_(2)O_(4))}_(2)(B-β-SbW_(9)O_(33))_(2)]·22H_(2)O(1)has been successfully made and f...A new inorganic–organic hybrid 4-Ti-added polyoxometalate:[H_(2)N(CH_(3))_(2)]_(2)Na_(3)H_(5)[{Ti(C_(2)O_(4))(H_(2)O)}_(2){Ti(C_(2)O_(4))}_(2)(B-β-SbW_(9)O_(33))_(2)]·22H_(2)O(1)has been successfully made and further characterized by infrared spectroscopy,thermogravimetric analysis,powder X-ray diff raction and single-crystal X-ray diff raction.The polyoxoanion of 1 exhibits a Krebs-type structure that is constructed from two[B-β-SbW_(9)O_(33)]^(9)−fragments fused together by a belt of four additional Ti atoms decorated by oxalate ligands.Furthermore,1 as a heterogeneous catalyst exhibits high activity for Knoevenagel condensation under mild reaction conditions.展开更多
The electrochemical behavior of monomolybdenum-substituted Keggin-type polyoxometalates [XW11MoO40]^n- （X=P, Si, Ge with n=3, 4） was studied in aqueous and N,N-dimethylformamide （DMF） solution. These anionic clus...The electrochemical behavior of monomolybdenum-substituted Keggin-type polyoxometalates [XW11MoO40]^n- （X=P, Si, Ge with n=3, 4） was studied in aqueous and N,N-dimethylformamide （DMF） solution. These anionic clusters showed different electrochemical behaviors in two kinds of media. The initial potentials of [XW11MoO40]^n- in DMF were more negative than those in aqueous solution, showing a lower oxidation ability of [XW11MoO40]^n- in DMF. The investigation results suggested that the redox properties of polyoxometalates be tuned by the substitutions of Mo for W and by replacing aqueous solution with organic solvent, which provided valuable information to rationally choose polyoxometalates （POM） in preparation of POM-based organic/inorganic hybrid materials.展开更多
文摘The synergistic effect of H_3PMo_(12)O_(40) or H_3PW_(12)O_(40) polyoxometalate solution(POM) and TiO_2 to catalyze formic acid oxidation was investigated. Under UV irradiation, hole and electron were photogenerated by TiO_2. Formic acid was oxided by the photogenerated hole and photogenerated electron was transferred to reduce polyoxometalate. With this design, formic acid can be converted into electricity in the fuel cell and hydrogen can be generated in the electrolysis cell without noble metal catalyst. Unlike other noble metal catalysts applied in the fuel cells and electrolysis cell, POM and TiO_2 are stable and low cost. The maximum output power density of liquid formic acid fuel cell after 12 h UV irradiation is 5.21 mW/cm^2 for phosphmolybdic acid and 22.81 m W/cm^2 for phosphotungstic acid respectively. The applied potential for the hydrogen evolution is as low as 0.8 V for phosphmolybdic acid and 0.6 V for phosphotungstic acid.
基金supported by the NSFC(No.21571016,91122028 and 21831001)the NSFC for Distinguished Young scholars(No.20725101).
文摘A new inorganic–organic hybrid 4-Ti-added polyoxometalate:[H_(2)N(CH_(3))_(2)]_(2)Na_(3)H_(5)[{Ti(C_(2)O_(4))(H_(2)O)}_(2){Ti(C_(2)O_(4))}_(2)(B-β-SbW_(9)O_(33))_(2)]·22H_(2)O(1)has been successfully made and further characterized by infrared spectroscopy,thermogravimetric analysis,powder X-ray diff raction and single-crystal X-ray diff raction.The polyoxoanion of 1 exhibits a Krebs-type structure that is constructed from two[B-β-SbW_(9)O_(33)]^(9)−fragments fused together by a belt of four additional Ti atoms decorated by oxalate ligands.Furthermore,1 as a heterogeneous catalyst exhibits high activity for Knoevenagel condensation under mild reaction conditions.
基金Project supported by the National Natural Science Foundation of China （No. 20371010）, the State Key Laboratory for Structural Chemistry of Unstable and Stable Species at Peking University （No. 03-12） and the Natural Science Foundation of Jilin Technology 0ffice of China （No. 20030512-1）.
文摘The electrochemical behavior of monomolybdenum-substituted Keggin-type polyoxometalates [XW11MoO40]^n- （X=P, Si, Ge with n=3, 4） was studied in aqueous and N,N-dimethylformamide （DMF） solution. These anionic clusters showed different electrochemical behaviors in two kinds of media. The initial potentials of [XW11MoO40]^n- in DMF were more negative than those in aqueous solution, showing a lower oxidation ability of [XW11MoO40]^n- in DMF. The investigation results suggested that the redox properties of polyoxometalates be tuned by the substitutions of Mo for W and by replacing aqueous solution with organic solvent, which provided valuable information to rationally choose polyoxometalates （POM） in preparation of POM-based organic/inorganic hybrid materials.
