In this text,we present researches on the synthesis of polyoxo-titanium clusters(PTCs)by the use of gadolinium pivalate precursor.During the synthesis process,we discover that solvents play an important role.When acet...In this text,we present researches on the synthesis of polyoxo-titanium clusters(PTCs)by the use of gadolinium pivalate precursor.During the synthesis process,we discover that solvents play an important role.When acetonitrile was used as solvent,Ti8Gd(μ2-O)(μ3-O)5(Sal)5(OPiv)2(μ2-OiPr)3(μ-OiPr)8(PTC-82)(H2Sal=salicylic acid,HOPiv=pivalic acid)was obtained.When N,N-dimethylformamide(DMF)was used as solvent under the same reaction conditions,Ti4Gd2(μ3-O)2(Sal)4(OPiv)4(μ2-OiPr)2(μ-OiPr)4(DMF)2(PTC-83)was synthesized.The solid-state UV absorption spectra revealed that the dopant of lanthanide and the incorporation of salicylic acid ligands have successfully narrowed the bandgap of PTCs.In addition,they exhibited rapid and reproducible photo-responses.展开更多
Crystalline polyoxo-titanium clusters(PTCs),as a molecular model of TiO_(2)nanomaterials,have attracted unprecedented attention due to their designable structure,tunable band gap,catalysis,and photochromic properties....Crystalline polyoxo-titanium clusters(PTCs),as a molecular model of TiO_(2)nanomaterials,have attracted unprecedented attention due to their designable structure,tunable band gap,catalysis,and photochromic properties.A new trinuclear Ti3-oxo cluster,[Ti3(μ2-O)(μ3-O)(abz)_(6)(OiPr)_(2)]·CH_(3)CN·H_(2)O(Ti3),was synthesized by solvothermal method with a yield of 60%by using 4-aminobenzoic acid as ligand.Single-crystal X-ray diffraction shows that it has a[Ti3(μ2-O)(μ3-O)(abz)_(6)(OiPr)_(2)]trinuclear cluster structure.Ti3 crystallizes in monoclinic space group P21/c with a=11.091(1),b=22.837(2),c=22.754(1)Å,β=90.580(6)°,V=5763.0(6)Å3,Z=4,Dc=1.345 g·cm-3,F(000)=2412,μ=2.743 mm^(−1),R=0.0796,and wR=0.2260(I>2σ(I)).Ti3 shows typical semiconductive behavior determined by temperature-dependent conductivity test.The chemiresistive humidity sensor fabricated by Ti3 showed good performance,including high response(four orders of magnitude current change from 0 to 100%RH)and fast response time(160 s)and recovery time(26 s).展开更多
Two inorganic acids decorating titanium-oxo clusters (PTCs),Ti_6O_4(O~iPr)_(10)(O_(3)P-Phen)_(2)(NO_(3))_(2)(PTC-251) and Ti_6O_4(O~iPr)_(10)(O_(3)P-Phen)_(2)(HSO_4)_(2) (PTC-252)(H_(2)O_(3)P-Phen=phenylphosphinic aci...Two inorganic acids decorating titanium-oxo clusters (PTCs),Ti_6O_4(O~iPr)_(10)(O_(3)P-Phen)_(2)(NO_(3))_(2)(PTC-251) and Ti_6O_4(O~iPr)_(10)(O_(3)P-Phen)_(2)(HSO_4)_(2) (PTC-252)(H_(2)O_(3)P-Phen=phenylphosphinic acid) have been synthesized under solvothermal conditions.As a result of the labile coordination sites of the{Ti_6P_(2)}unit,nitrite and sulfate adopt different capping mode.Besides,they also present different space packing.The photocatalytic H_(2)evolution activities of these obtained PTCs have been studied,with sulfate decorating PTC-252 presenting a maximum H_(2) production rate up to 110.95μmol·g^(-1)·h^(-1).展开更多
基金Supported by the National Natural Science Foundation of China (21771181,and 21673238)Youth Innovation Promotion Association CAS (2017345)Shanghai Key Laboratory of Rare Earth Functional Materials and Natural Science Foundation of Fujian Province (2017J05036)。
文摘In this text,we present researches on the synthesis of polyoxo-titanium clusters(PTCs)by the use of gadolinium pivalate precursor.During the synthesis process,we discover that solvents play an important role.When acetonitrile was used as solvent,Ti8Gd(μ2-O)(μ3-O)5(Sal)5(OPiv)2(μ2-OiPr)3(μ-OiPr)8(PTC-82)(H2Sal=salicylic acid,HOPiv=pivalic acid)was obtained.When N,N-dimethylformamide(DMF)was used as solvent under the same reaction conditions,Ti4Gd2(μ3-O)2(Sal)4(OPiv)4(μ2-OiPr)2(μ-OiPr)4(DMF)2(PTC-83)was synthesized.The solid-state UV absorption spectra revealed that the dopant of lanthanide and the incorporation of salicylic acid ligands have successfully narrowed the bandgap of PTCs.In addition,they exhibited rapid and reproducible photo-responses.
基金Supported by the National Natural Science Foundation of China (21975254, 21905280, 21950410532, 2019M662254)Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle Open Research Fund (ES202080085)the Youth Innovation Promotion Association CAS (2018342)
文摘Crystalline polyoxo-titanium clusters(PTCs),as a molecular model of TiO_(2)nanomaterials,have attracted unprecedented attention due to their designable structure,tunable band gap,catalysis,and photochromic properties.A new trinuclear Ti3-oxo cluster,[Ti3(μ2-O)(μ3-O)(abz)_(6)(OiPr)_(2)]·CH_(3)CN·H_(2)O(Ti3),was synthesized by solvothermal method with a yield of 60%by using 4-aminobenzoic acid as ligand.Single-crystal X-ray diffraction shows that it has a[Ti3(μ2-O)(μ3-O)(abz)_(6)(OiPr)_(2)]trinuclear cluster structure.Ti3 crystallizes in monoclinic space group P21/c with a=11.091(1),b=22.837(2),c=22.754(1)Å,β=90.580(6)°,V=5763.0(6)Å3,Z=4,Dc=1.345 g·cm-3,F(000)=2412,μ=2.743 mm^(−1),R=0.0796,and wR=0.2260(I>2σ(I)).Ti3 shows typical semiconductive behavior determined by temperature-dependent conductivity test.The chemiresistive humidity sensor fabricated by Ti3 showed good performance,including high response(four orders of magnitude current change from 0 to 100%RH)and fast response time(160 s)and recovery time(26 s).
基金supported by National Natural Science Foundation of China(21771181,21935010 and 21973096)Youth Innovation Promotion Association CAS(2017345)。
文摘Two inorganic acids decorating titanium-oxo clusters (PTCs),Ti_6O_4(O~iPr)_(10)(O_(3)P-Phen)_(2)(NO_(3))_(2)(PTC-251) and Ti_6O_4(O~iPr)_(10)(O_(3)P-Phen)_(2)(HSO_4)_(2) (PTC-252)(H_(2)O_(3)P-Phen=phenylphosphinic acid) have been synthesized under solvothermal conditions.As a result of the labile coordination sites of the{Ti_6P_(2)}unit,nitrite and sulfate adopt different capping mode.Besides,they also present different space packing.The photocatalytic H_(2)evolution activities of these obtained PTCs have been studied,with sulfate decorating PTC-252 presenting a maximum H_(2) production rate up to 110.95μmol·g^(-1)·h^(-1).
