Keggin型铜取代杂多酸盐的合成、表征及电化学性能
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摘要
在中性水溶液中合成了Keggin型铜取代磷钨杂多阴离子PW11O39Cu(II)(H2O)5-(PW11Cu),并对其进行IR、UV-Vis和循环伏安表征.实验结果表明,PW11Cu在700~1100 cm-1的指纹区内有四个特征振动吸收峰,分别对应于P-Oa、W=Od、W-Ob-W和W-Oc-W的反对称伸缩振动吸收.在200nm和249 nm处有两个很强的紫外吸收,在650~800 nm的可见光区有一个较强的连续吸收带.循环伏安显示W-O骨架波和一对Cu的氧化-还原波.
Keggin-type Cu(II)-substituted heteropolyanion PW11O39Cu(II)(H2O)5-(PW11Cu) was synthesized in neutral aqueous solution and characterized by IR, UV-Vis and cyclic voltammetry. Experimental results showed that in the 700-1100cm-1 fingerprint area PW11 Cu exhibits five characteristic absorption peaks, corresponding to the anti-symmetric stretching vibration of P-Oa, W=Od, W-Ob-W and W-Oc-W, respectively. There are two strong UV absorptions at near 200 nm and249 nm and a continuous visible absorption band in the district of 650~800 nm for PW11 Cu. In addition to W-O skeletonwaves a pair of Cu(II)/Cu(I) redox wave appears in the cyclic voltammograms.
Keggin-type Cu(II)-substituted heteropolyanion PW11O39Cu(II)(H2O)5-(PW11Cu) was synthesized in neutral aqueous solution and characterized by IR, UV-Vis and cyclic voltammetry. Experimental results showed that in the 700-1100cm-1 fingerprint area PW11 Cu exhibits five characteristic absorption peaks, corresponding to the anti-symmetric stretching vibration of P-Oa, W=Od, W-Ob-W and W-Oc-W, respectively. There are two strong UV absorptions at near 200 nm and249 nm and a continuous visible absorption band in the district of 650~800 nm for PW11 Cu. In addition to W-O skeletonwaves a pair of Cu(II)/Cu(I) redox wave appears in the cyclic voltammograms.
引文
[1]王崇太.过渡金属Cr(III)和Fe(III)取代磷钨杂多配合物的制备及电催化氧化性能研究[D].广州:中山大学,2008.
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[14]王彬,王崇太,华英杰,等.Keggin型钴取代杂多阴离子PW11O39Co(II)(H2O)5-的电催化性能[J].电化学,2013,19(5):488-492.
[15]华英杰,王崇太,刘希龙,等.Si W5-11O39Fe(III)(H2O)的电化学性质及电催化还原过氧化氢[J].中山大学学报,2012,51(3):73-78.
[16]华英杰,王崇太,李天略,等.Keggin型铬取代杂多阴离子PW411O39Cr(III)(H2O)-的电化学性质[J].中山大学学报,2011,50(3):68-73.
[17]张红丹,李娜,焦贵省,等.Keggin型PW11O39Mn(II)(H2O)5-的合成、表征及电化学性质[J].海南师范大学学报:自然科学版,2010,23(2):176-180.
[18]王成龙,彭全明,焦贵省,等.Keggin型钴取代杂多酸盐PW11O39Co(II)(H2O)5-的合成与表征[J].海南师范大学学报:自然科学版,2010,23(2):172-175.
[19]Brevard C,Schimpf R,TournéG,et al.Tungsten-183NMR:A complete and unequivocal assignment of the tungsten-tungsten connectives in heteropolytungstates via two-dimensional 183W NMR techniques[J].J Am Chem Soc,1983,105:7059-7063.
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[21]Kozhenikov I V.Advances in catalysis by heteropolyacids[J].Russian Chemical Reviews,1987,56:1417-1443.
[22]巴德,福克纳.电化学方法-原理及应用[M].北京:化学工业出版社,2005.
[23]王秀丽,赵岷.多酸电化学导论[M].北京:中国环境科学出版社,2006.
[24]华英杰,王崇太,李高仁,等.Keggin型缺位磷钨杂多阴离子的电化学性质及电催化还原过氧化氢[J].化学学报,2009,67(8):795-800.
[25]Sadakane M,Steckhan E.Investigation of the manganesesubstitutedα-Keggin-heteropolyanion K6Si W11O39Mn(H2O)by cyclic voltammetry and its application as oxidation catalyst[J].J Mol Catal A:Chemical,1996,114:221-228.
[2]Rong C Y,Pope M T.Lacunary polyoxometalate anions are-acceptor Ligands.Characterization of some tungstoruthenate(II,III,IV,V)heteropolyanions and their atom-transfer reactivity[J].J Am Chem Soc,1992,114:2932-2938.
[3]Khenkint A M,Hill C L.Oxo Transfer from high-valent totally inorganic oxometalloporphyrin analogs,[Xn+W11O39Cr V O](9-n)-(Xn+=P5+,Si4+),to hydrocarbons[J].J Am Chem Soc,1993,115:8178-8186.
[4]Pope M T,Miller A.Polyoxometalate chemistry:An old field with new dimensions in several disciplines[J].Angew Chem,1991,30:34-48.
[5]Hua Y J,Wang C T,Liu J Y,et al.Visible Photocatalytic Degradation of Rhodamine B using Fe(III)-Substituted Phosphotungstic Heteropolyanion[J].Journal of Molecular Catalysis A:Chemical,2012,365:8-14.
[6]华英杰,王崇太,孙振范,等.新颖的PW4-11O39Fe(III)(H2O)/H2O2类光-芬顿体系光催化降解苯胺[J].应用化学,2012,29(1):63-68.
[7]王崇太,华英杰,刘希龙,等.铬取代杂多阴离子PW11O39Cr(III)(H2O)4-可见光催化降解罗丹明B[J].化学学报,2012,70(4):399-404.
[8]Hua Y J,Wang C T,Duan H,et al.Fabrication,characterization and electrocatalytic properties of a solid modified electrode based on PW11O39Fe(III)(H2O)4-and chitosan[J].Electrochimica Acta,2011,58:99-104.
[9]Wang C T,Hua Y J,Tong Y X.A novel Electro-FentonLike system using PW411O39Fe(III)(H2O)-as an electrocatalyst for wastewater treatment[J].Electrochimica Acta,2010,55(22):6755-6760.
[10]王崇太,孙振范,华英杰,等.Keggin型铁取代杂多阴离子PW411O39Fe(III)(H2O)-光催化降解硝基苯[J].化学学报,2010,68(11):1037-1042.
[11]华英杰,王崇太,童叶翔,等.Keggin型杂多阴离子PW4-11O39Fe(III)(H2O)电催化降解硝基苯[J].化学学报,2009,67(23):2650-2654.
[12]Wang C T,Hua Y J,LI G R,et al.Indirect cathodic electrocatalytic degradation of dimethylphthalate with PW11O39Fe(III)(H2O)4-and H2O2in neutral aqueous medium[J].Electrochimica Acta,2008,53(16):5100-5105.
[13]王崇太,华英杰,李高仁,等.Cr(III)-取代磷钨杂多配合物对4-甲基吡啶的电催化氧化作用[J].化学学报,2008,66(8):835-840.
[14]王彬,王崇太,华英杰,等.Keggin型钴取代杂多阴离子PW11O39Co(II)(H2O)5-的电催化性能[J].电化学,2013,19(5):488-492.
[15]华英杰,王崇太,刘希龙,等.Si W5-11O39Fe(III)(H2O)的电化学性质及电催化还原过氧化氢[J].中山大学学报,2012,51(3):73-78.
[16]华英杰,王崇太,李天略,等.Keggin型铬取代杂多阴离子PW411O39Cr(III)(H2O)-的电化学性质[J].中山大学学报,2011,50(3):68-73.
[17]张红丹,李娜,焦贵省,等.Keggin型PW11O39Mn(II)(H2O)5-的合成、表征及电化学性质[J].海南师范大学学报:自然科学版,2010,23(2):176-180.
[18]王成龙,彭全明,焦贵省,等.Keggin型钴取代杂多酸盐PW11O39Co(II)(H2O)5-的合成与表征[J].海南师范大学学报:自然科学版,2010,23(2):172-175.
[19]Brevard C,Schimpf R,TournéG,et al.Tungsten-183NMR:A complete and unequivocal assignment of the tungsten-tungsten connectives in heteropolytungstates via two-dimensional 183W NMR techniques[J].J Am Chem Soc,1983,105:7059-7063.
[20]王恩波,胡长文,许林.多酸化学概论[M].吉林:东北师范大学出版社,2009.
[21]Kozhenikov I V.Advances in catalysis by heteropolyacids[J].Russian Chemical Reviews,1987,56:1417-1443.
[22]巴德,福克纳.电化学方法-原理及应用[M].北京:化学工业出版社,2005.
[23]王秀丽,赵岷.多酸电化学导论[M].北京:中国环境科学出版社,2006.
[24]华英杰,王崇太,李高仁,等.Keggin型缺位磷钨杂多阴离子的电化学性质及电催化还原过氧化氢[J].化学学报,2009,67(8):795-800.
[25]Sadakane M,Steckhan E.Investigation of the manganesesubstitutedα-Keggin-heteropolyanion K6Si W11O39Mn(H2O)by cyclic voltammetry and its application as oxidation catalyst[J].J Mol Catal A:Chemical,1996,114:221-228.