{Cu_6}簇连接[A-α-SiW_9O_(34)]^(10-)构筑的链状化合物及其催化性能  

Synthesis and catalytic property of a chain-like complex based on the [A-α-SiW_9O_(34)]^(10-) anions connected by {Cu_6} cluster

作　　者：林宏艳[1] 荣兴 曾凌[1] 王青林[1] 田原[1] 林佳凤 LIN Hong-yan RONG Xing ZENG Ling WANG Qing-lin TIAN Yuan LIN Jia-feng(College of Chemistry and Chemical Engineering, Bohai University,Jinzhou 121013,China)

机构地区：[1]渤海大学化学化工学院,辽宁锦州121013

出　　处：《分子科学学报》2017年第3期177-182,共6页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(21501013;21401010)

摘　　要：水热条件下合成了一种新的链状硅钨酸盐簇合物{H[Na(H_2O)_6][Cu_6(H_2O)6(Si_2W_(18)O_(68))][Cu(H_2O)4)]3}·7.72H_2O,通过X-射线单晶衍射方法确定了其晶体结构.结构分析表明该簇合物为单斜晶系,C/2c空间群,晶胞参数a=2.179 26(9)nm,b=1.282 89(5)nm,c=3.147 84(13)nm,α=90°,β=106.961 0(10)°,γ=90°,V=8.417 8(6)nm^3,Mr=5 685.17,D_c=4.435g/cm^3,Z=4,S=1.062,F(000)=9 977,R_1=0.033 8,wR_2=0.079 6.化合物是由六核铜簇连接相邻的三缺位[[A-α-SiW_9O_(34)]^(10-)]10-形成的一维链状结构,配位于一维链两侧的多酸顶端上的Cu^(2+)离子、离散的Cu^(2+)离子和Na^+离子起到平衡电荷的作用.该化合物修饰的碳糊电极对NO_2^-有好的电催化还原活性,此外标题化合物作为光催化剂对亚甲基蓝和甲基橙的降解有明显的催化活性.A new chain-liked tungstosilicate aggregate { H [ Na （ H2 0）6 ] [Cu6 （ H2 0）6 （Si2 Wl8 068 ） ] Cu （H2O）4）]3 } ·7.72H2O has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. The title complex is monoclinic system with space group C2/c,and cell parameters are a= 2. 179 26（9） nm,b=1. 282 89（5） nm,c=3. 147 84（13） nm,α=90° ,β=106. 961 0（10） °,γ=90 °,V= 8. 417 8（6） nm3 ,Mr=5 685.17,Dc=4. 435 g/cm3 ,Z=4,S=1. 062,F（000） =997 7,R1 =0. 033 8,wR2 =0. 079 6. Structure analysis reveals that the tungstosilicate cluster is a 1D chain-liked structure consisting of the adjacent trivacant [-A-α-SiW9O34]^10- units connected by six-nuclear copper cluster. The trivacant tungstosilicates is coordinated to one Cu2＋ ion by its terminal oxygen atom in both sides of the 1D chain. The discrete Cu2＋ ion and Na＋ ion play the role of balancing the charges. This complex bulk-modified carbon paste electrode displays the good electrocatalytic activity toward NO2- reduc- tion. Moreover,the title complex shows the remarkable photocatalytic activities for the degradation of methylene blue and methyl orange.

关 键 词：硅钨酸盐簇 六核铜簇 水热合成 晶体结构 催化性能 

分 类 号：O614[理学—无机化学]