A high-nuclear Co-V-O cluster was firstly isolated by lacunary polyoxoanion, resulting in the high-nuclear mixed metal-oxo cluster-containing polyoxometalate (POM), K4Na28[{Co4(O-H)3(VO4)}4(SiW9O34)4]· 66H2O (1)....A high-nuclear Co-V-O cluster was firstly isolated by lacunary polyoxoanion, resulting in the high-nuclear mixed metal-oxo cluster-containing polyoxometalate (POM), K4Na28[{Co4(O-H)3(VO4)}4(SiW9O34)4]· 66H2O (1). In 1, the{Co4(O-H)3(VO4)}4{Co16-V4}core, composed of a{Co4O4}cubane, four{Co4(OH)3}qusi-cubanes and four VO4 units, was stabilized by four lacunary A-α-{SiW9O34} units. Photocatalytic study reveals that 1 exhibits excellent photocatalytic activity for CO2-to-CO conversion with high selectivity under visible light irradiation. The turnover number (TON) and turnover frequency (TOF) reaches as high as 10492 and 0.29 s^-1, respectively. Compound 1 represents the first high nuclear TM cluster-containing POM (TM=transition-metal) with efficient visible light catalytic activity for CO2 reduction, and its photocatalytic activity is much higher than those of most reported molecular catalysts. Photoluminescence spectroscopy study reveals that photoexcitation of Ru-photosensitizer is followed by an efficient electron transfer to POMs to reduce CO2.展开更多
Synthesizing zirconium-oxo clusters(ZrOCs)with precisely defined“mother-daughter”architectures(large clusters containing smaller cluster units)is essential for gaining a profound understanding of their assembly mech...Synthesizing zirconium-oxo clusters(ZrOCs)with precisely defined“mother-daughter”architectures(large clusters containing smaller cluster units)is essential for gaining a profound understanding of their assembly mechanism and precisely controlling their properties.However,owing to considerable synthetic difficulties,achieving this goal remains a formidable challenge.Herein,we report the synthesis of two novel high-nuclearity ZrOCs,namely[Zr_(16)(μ_(3)-O/OH)_(24)(μ_(2)-OH)_(4)(QE)_(4)(PA)_(20)](Zr_(16);H_(2)QE=2,8-quinolinediol;HPA=propanoic acid)and[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(PA)_(20)](Zr20),via a facile solvent-induced synthetic strategy.Surprisingly,we found that Zr16 and Zr20 exhibit a“mother-daughter”relationship,where Zr16,as the“daughter”,is embedded within Zr20,the“mother”,with the PA ligands excluded.Moreover,Zr20 can react with benzoic acid(HBA)via post-synthetic reactions to yield another new cluster,[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(BA)_(20)](Zr20-BA),which retains the metal core and QE ligands of Zr20,with only the peripheral PA ligands replaced by BA ligands,highlighting the framework stability and flexibility of ligand shell of Zr20.Of note,Zr20 exhibited better thermal catalytic cycloaddition of CO_(2)and epoxides performance due to the rich Lewis acidity of Zr sites,achieving near-complete conversion of diverse epoxides.This work not only expands the structural landscape of high-nuclearity Zr OCs but also provides deeper insights into their underlying assembly mechanism.展开更多
基金financial support from Science and Technology Research Foundation of the Thirteenth Five Years of Jilin Educational Committee (No. JJKH20170605KJ)
文摘A high-nuclear Co-V-O cluster was firstly isolated by lacunary polyoxoanion, resulting in the high-nuclear mixed metal-oxo cluster-containing polyoxometalate (POM), K4Na28[{Co4(O-H)3(VO4)}4(SiW9O34)4]· 66H2O (1). In 1, the{Co4(O-H)3(VO4)}4{Co16-V4}core, composed of a{Co4O4}cubane, four{Co4(OH)3}qusi-cubanes and four VO4 units, was stabilized by four lacunary A-α-{SiW9O34} units. Photocatalytic study reveals that 1 exhibits excellent photocatalytic activity for CO2-to-CO conversion with high selectivity under visible light irradiation. The turnover number (TON) and turnover frequency (TOF) reaches as high as 10492 and 0.29 s^-1, respectively. Compound 1 represents the first high nuclear TM cluster-containing POM (TM=transition-metal) with efficient visible light catalytic activity for CO2 reduction, and its photocatalytic activity is much higher than those of most reported molecular catalysts. Photoluminescence spectroscopy study reveals that photoexcitation of Ru-photosensitizer is followed by an efficient electron transfer to POMs to reduce CO2.
基金supported by the National Natural Science Foundation of China(22325105,22201159,22171164,91961105,92361301,52261135637)the Natural Science Foundation of Shandong Province(ZR2021QB077,ZR2024MB120)the Doctoral Program of Liaocheng University(318051944)。
文摘Synthesizing zirconium-oxo clusters(ZrOCs)with precisely defined“mother-daughter”architectures(large clusters containing smaller cluster units)is essential for gaining a profound understanding of their assembly mechanism and precisely controlling their properties.However,owing to considerable synthetic difficulties,achieving this goal remains a formidable challenge.Herein,we report the synthesis of two novel high-nuclearity ZrOCs,namely[Zr_(16)(μ_(3)-O/OH)_(24)(μ_(2)-OH)_(4)(QE)_(4)(PA)_(20)](Zr_(16);H_(2)QE=2,8-quinolinediol;HPA=propanoic acid)and[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(PA)_(20)](Zr20),via a facile solvent-induced synthetic strategy.Surprisingly,we found that Zr16 and Zr20 exhibit a“mother-daughter”relationship,where Zr16,as the“daughter”,is embedded within Zr20,the“mother”,with the PA ligands excluded.Moreover,Zr20 can react with benzoic acid(HBA)via post-synthetic reactions to yield another new cluster,[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(BA)_(20)](Zr20-BA),which retains the metal core and QE ligands of Zr20,with only the peripheral PA ligands replaced by BA ligands,highlighting the framework stability and flexibility of ligand shell of Zr20.Of note,Zr20 exhibited better thermal catalytic cycloaddition of CO_(2)and epoxides performance due to the rich Lewis acidity of Zr sites,achieving near-complete conversion of diverse epoxides.This work not only expands the structural landscape of high-nuclearity Zr OCs but also provides deeper insights into their underlying assembly mechanism.
