吡啶鎓盐配体构筑的多钼酸基配合物的合成、结构及光催化性能

人工晶体学报 ›› 2022, Vol. 51 ›› Issue (7): 1227-1232.

吡啶鎓盐配体构筑的多钼酸基配合物的合成、结构及光催化性能

王静怡, 张众, 王梓兰, 于鑫颖, 由君颐, 朱君怡, 杨琳

渤海大学化学与材料工程学院,辽宁省全谱太阳能电池转光材料专业技术创新中心,锦州 121013

收稿日期:2022-04-11 出版日期:2022-07-15 发布日期:2022-08-11
通讯作者: 张众,博士,讲师。E-mail:zhangz@bhu.edu.cn
作者简介:王静怡(2002—),女,辽宁省人。E-mail:wjy20020829@126.com
基金资助:
国家自然科学基金青年科学基金(21901018);渤海大学博士启动基金(0520bs027)

Synthesis, Structure and Photocatalytic Properties of Polymolybdate-Based Complex Constructed by Pyridinium Ligand

WANG Jingyi, ZHANG Zhong, WANG Zilan, YU Xinying, YOU Junyi, ZHU Junyi, YANG Lin

Professional Technology Innovation Center of Liaoning Province for Conversion Materials of Solar Cell, College of Chemistry and Materials Engineering, Bohai University, Jinzhou 121013, China

Received:2022-04-11 Online:2022-07-15 Published:2022-08-11

摘要/Abstract

摘要： 本文在水热条件下合成了一例同多钼酸阴离子[δ-Mo₈O₂₆]^4-基配合物[Co(bipbc)(δ-Mo₈O₂₆)_0.5(H₂O)₃] (bipbc=4,4-双[(4-羧基吡啶)甲基]联苯),其为一维链状结构,包含环型双核钴配合物[Co₂(bipbc)₂]⁴⁺和[δ-Mo₈O₂₆]^4-簇。该配合物结晶于单斜晶系,P2₁/n空间群,a=1.147 9(8) nm,b=1.440 9(11) nm,c=2.082 9(16) nm,β=93.469(2)°,V=3.438 8(4) nm³,Z=4,M_r=1 129.18,F(000)=2 204,μ=1.979 mm^-1,D_c=2.181 mg·m^-3,S=1.019,R₁=0.056 2,wR₂=0.137 7。光催化性质研究表明,在可见光、近红外光和全光谱的光照条件下,标题配合物对龙胆紫(GV)和亚甲基蓝(MB)的降解,表现出一定的光催化活性。

关键词: 多金属氧酸盐, 水热合成, 吡啶鎓盐配体, 钴配合物, 有机染料, 光催化降解

Abstract: In this paper, a new isopolymolybdate anion [δ-Mo₈O₂₆]^4--based complex [Co(bipbc)(δ-Mo₈O₂₆)_0.5(H₂O)₃] (bipbc=4,4′-bis[(4-carboxypyridino)methyl]biphenyl) was synthesized under hydrothermal conditions. The title complex shows a 1D chain, which consists of the cyclic dinuclear cobalt complexes [Co₂(bipbc)₂]⁴⁺ and [δ-Mo₈O₂₆]^4-clusters, and crystallizes in the monoclinic system, space group P2₁/n with a=1.147 9 (8) nm, b=1.440 9 (11) nm, c=2.082 9 (16) nm, β=93.469(2)°, V=3.438 8(4) nm³, Z=4, M_r=1 129.18, F(000)=2 204, μ=1.979 mm^-1, D_c=2.181 mg·m^-3, S=1.019, R₁=0.056 2, wR₂=0.137 7. The investigations on photocatalytic properties show that the title complex has photocatalytic activities toward the degradation of gentian violet (GV) and methylene blue (MB) under visible, even near-infrared and full spectrum light irradiation.

Key words: polyoxometalate, hydrothermal synthesis, pyridinium ligand, cobalt complex, organic dye, photocatalytic degradation

中图分类号:

王静怡, 张众, 王梓兰, 于鑫颖, 由君颐, 朱君怡, 杨琳. 吡啶鎓盐配体构筑的多钼酸基配合物的合成、结构及光催化性能[J]. 人工晶体学报, 2022, 51(7): 1227-1232.

WANG Jingyi, ZHANG Zhong, WANG Zilan, YU Xinying, YOU Junyi, ZHU Junyi, YANG Lin. Synthesis, Structure and Photocatalytic Properties of Polymolybdate-Based Complex Constructed by Pyridinium Ligand[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(7): 1227-1232.

参考文献

[1] WANG S S, YANG G Y. Recent advances in polyoxometalate-catalyzed reactions[J]. Chemical Reviews, 2015, 115(11): 4893-4962.
[2] LIU Z J, WANG X L, QIN C, et al. Polyoxometalate-assisted synthesis of transition-metal cubane clusters as artificial mimics of the oxygen-evolving center of photosystem Ⅱ[J]. Coordination Chemistry Reviews, 2016, 313: 94-110.
[3] ZHANG Z, LI H L, WANG Y L, et al. Syntheses, structures, and electrochemical properties of three new acetate-functionalized zirconium-substituted germanotungstates: from dimer to tetramer[J]. Inorganic Chemistry, 2019, 58(4): 2372-2378.
[4] 张众,杨琳,李晓慧,等.草酸配体修饰的锆取代型硅钨-氧簇合物的合成、结构和电化学性质研究[J].人工晶体学报,2021,50(5):884-888.
ZHANG Z, YANG L, LI X H, et al. Synthesis, crystal structure, and electrochemical properties of a ox-functionalized zirconium(Ⅳ) substituted tungsten-oxo cluster[J]. Journal of Synthetic Crystals, 2021, 50(5): 884-888(in Chinese).
[5] WANG X L, ZHANG J Y, CHANG Z H, et al. α-γ-type[Mo₈O₂₆]^4--containing metal-organic complex possessing efficient catalytic activity toward the oxidation of thioether derivatives[J]. Inorganic Chemistry, 2021, 60(5): 3331-3337.
[6] CHEN Y H, CHANG S Z, AN H Y, et al. Two polymorphic polyoxometalate-based metal-organic frameworks for the efficient synthesis of functionalized sulfoxides and detoxification of mustard gas simulants[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(46): 15683-15693.
[7] HUANG Y R, LIN X L, CHEN B, et al. Thermal-responsive polyoxometalate-metalloviologen hybrid: reversible intermolecular three-component reaction and temperature-regulated resistive switching behaviors[J]. Angewandte Chemie, 2021, 60(31): 16911-16916.
[8] ZHANG Z, WANG Y L, LI H L, et al. Syntheses, structures and properties of three organic-inorganic hybrid polyoxotungstates constructed from{Ni₆PW₉}building blocks: from isolated clusters to 2-D layers[J]. CrystEngComm, 2019, 21(16): 2641-2647.
[9] 刘国成,迟杰,刘湘湘,等.紫罗碱衍生物基化合物的晶体结构和性能研究[J].渤海大学学报(自然科学版),2021,42(1):8-13.
LIU G C, CHI J, LIU X X, et al. A review of the crystal structure and properties of compounds derived from viologen derivatives[J]. Journal of Bohai University (Natural Science Edition), 2021, 42(1): 8-13(in Chinese).
[10] SUN X J, ZHANG J, TAN A D, et al. A highly efficient near-infrared-activated photocatalyst based on an electron-deficient copper-viologen-polyoxometalate framework with a copper{Cu3}cluster decorated phosphotungstate as a building block[J]. Crystal Growth & Design, 2019, 19(12): 6845-6849.
[11] SUN X J, ZHANG J, FU Z Y. Polyoxometalate cluster sensitized with copper-viologen framework for efficient degradation of organic dye in ultraviolet, visible, and near-infrared light[J]. ACS Applied Materials & Interfaces, 2018, 10(42): 35671-35675.
[12] YANG L, ZHANG Z, XU N, et al. A new[δ-Mo₈O₂₆]₄: based NiⅡ-coordination polymer constructed from a pyridinum ligand as a full spectrum responsive photocatalyst and its electrocatalytic properties[J]. Inorganic Chemistry Communications, 2021, 132: 108819.
[13] DING J J, ZHENG C N, WANG L X, et al. Viologen-inspired functional materials: synthetic strategies and applications[J]. Journal of Materials Chemistry A, 2019, 7(41): 23337-23360.
[14] SHELDRICK G M. SHELXL-97, Program for crystal structure refinement, University of Göttingen, Germany, 1997.
[15] PAN X, WANG X L, WANG X, et al. Various types of isopolymolybdate-based metal-organic complexes formed in different conditions: synthesis, structures, luminescence, electrochemical, and photocatalytic performances[J]. CrystEngComm, 2019, 21: 6472-6481.
[16] WANG X L, CUI Z W, LIN H Y, et al. The rational design of four multifunctional octamolybdate-based complexes for detecting different ions and removing organic dyes from aqueous solution[J]. CrystEngComm, 2021, 23(10): 2113-2121.
[17] ALLEN F. Acta crystallographica section B: structural science[J]. Acta Crystallographica Section A, 2002, 58: 64.
[18] KORMALI P, DIMOTICALI D, TSIPI D, et al. Photolytic and photocatalytic decomposition of fenitrothion by PW₁₂O^3-₄₀ and TiO₂: a comparative study[J]. Applied Catalysis B: Environmental, 2004, 48(3): 175-183.
[19] CHEN Y Q, LI G R, QU Y K, et al. Water-insoluble heterometal-oxide-based photocatalysts effective for the photo-decomposition of methyl orange[J]. Crystal Growth & Design, 2013, 13(2): 901-907.
[20] YANG H X, LIU T F, CAO M N, et al. A water-insoluble and visible light induced polyoxometalate-based photocatalyst[J]. Chemical Communications, 2010, 46(14): 2429.