A Hybrid Material Constructed from Phosphomolybdate Anion and Metal/Hydrogen⁃Oxygen⁃Triphenylphosphine Units

doi:10.12422/j.issn.1006-396X.2023.04.007

Abstract

Abstract:

Under the hydrothermal synthesis,an organic?inorganic hybrid compound was prepared through the self?assembly process by using phosphomolybdic acid as a polyoxometallate (polyacid for short) building block and triphenylphosphine as an organic ligand.Its molecular formula was determined by X?ray single?crystal diffraction technique as H₁₅{(PMo₁₂O₄₀)₂[MoO₄?(PPh₃)₄]₂?[NaO₃?(PPh₃)₃][(H₂O?PPh₃)₃]（compound 1),which is a novel inorganic?organic hybrid material formed by electrostatic interactions between [PMo₁₂O₄₀]^3-,[MoO₄?(PPh₃)₄]^2-,[NaO₃?(PPh₃)₃]^5- and H₂O?PPh₃ building blocks.The IR spectrum,luminescence spectra and cyclic voltammetric characteristic curves of compound 1 were also tested,focusing on the photocatalytic degradation of methylene blue(MB).The good ability of compound 1 to degrade organic dyes was demonstrated by photodegradation analysis experiments.

Key words: Polyoxometallate, Hybrid material, Luminescence spectroscopy, Electrochemistry, Photodegradation

摘要：

采用水热合成手段，以磷钼酸为多金属氧酸盐（简称多酸）建筑块，三苯基膦为有机配体，通过自组装的方式制备了一种无机?有机杂化化合物，通过X?射线单晶衍射技术确定其分子式为H₁₅{(PMo₁₂O₄₀)₂[MoO₄?(PPh₃)₄]₂[NaO₃?(PPh₃)₃][(H₂O?PPh₃)₃]（化合物1）。该化合物是由[PMo₁₂O₄₀]^3-、[MoO₄?(PPh₃)₄]^2-、[NaO₃?(PPh₃)₃]^5-和H₂O?PPh₃建筑块之间通过静电作用力形成的一种新型无机?有机杂化材料。测试了该化合物的红外光谱、发光光谱、循环伏安特性曲线，重点研究了该化合物的光催化降解亚甲基蓝(MB)的性质。光降解实验结果表明，该化合物具有良好的降解有机染料的能力。

关键词: 多金属氧酸盐, 杂化材料, 发光光谱, 电化学, 光降解

CLC Number:

TQ050.4

Zhuoyu Ding, Yifan Tan, Kun Zhou, Jiuyu Ji. A Hybrid Material Constructed from Phosphomolybdate Anion and Metal/Hydrogen⁃Oxygen⁃Triphenylphosphine Units[J]. Journal of Petrochemical Universities, 2023, 36(4): 47-52.

丁卓玉, 谭依凡, 周坤, 季久玉. 磷钼酸根和金属/氢⁃氧⁃三苯基膦单元构筑的杂化材料[J]. 石油化工高等学校学报, 2023, 36(4): 47-52.

Figures/Tables 10

Table 1 Main reagents and solvent

试剂	化学式	产地	级别
氯化铜	CuCl₂	阿拉丁试剂有限公司	质量分数为99%
磷钼酸	H₃PMO₁₂O₄₀·12H₂O	天津精细化工试剂厂	分析纯
三苯基膦	C₁₈H₁₅P	天津市大茂化学试剂厂	分析纯
氢氧化钠	NaOH	阿拉丁试剂有限公司	质量分数为98%
去离子水	H₂O	自制	分析纯

Table 2 Crystallographic parameters and structural refinement results of compound 1

晶体学参数	数据
分子式	C₂₅₂H₂₃₁Mo₂₆Na₁O₉₄P₁₆
相对分子质量	7 776.30
晶系	Triclinic
空间群	P⁃1
a/nm	1.794 24(7)
b/nm	1.815 63(7)
c/nm	4.827 40(2)
α/nm	8.598 40(10)
β/（°）	88.388 0(10)
γ/（°）	60.591 0(10)
体积/nm³	13 665.5(9)
温度/K Z	296(2) 2
密度/（g $⋅$ cm^-3）	1.890
μ/mm^-1	1.328
F(000)	7 676
总衍射点数	24 004
R_int	0.049 4
可观测衍射点S值	1.037
R₁(可观测衍射点)	0.083 6
wR₂(总衍射点)	0.263 1

Table 2 Crystallographic parameters and structural refinement results of compound 1

晶体学参数	数据
分子式	C₂₅₂H₂₃₁Mo₂₆Na₁O₉₄P₁₆
相对分子质量	7 776.30
晶系	Triclinic
空间群	P⁃1
a/nm	1.794 24(7)
b/nm	1.815 63(7)
c/nm	4.827 40(2)
α/nm	8.598 40(10)
β/（°）	88.388 0(10)
γ/（°）	60.591 0(10)
体积/nm³	13 665.5(9)
温度/K Z	296(2) 2
密度/（g $⋅$ cm^-3）	1.890
μ/mm^-1	1.328
F(000)	7 676
总衍射点数	24 004
R_int	0.049 4
可观测衍射点S值	1.037
R₁(可观测衍射点)	0.083 6
wR₂(总衍射点)	0.263 1

Fig.1 Ball?and?stick model diagram of compound

Fig.2 Ball?and?stick model diagram of the [PMo12O40]3-,[MoO4?(PPh3)4]2-,[NaO3?(PPh3)3]5-,H2O?PPh3 part

Fig.3 FT?IR spectrum of compound 1

Fig.4 The solid?state excitation and emission spectra of compound 1

Fig.5 Cyclic voltammograms of CPE?1 at different scan rates350、400、450、500 mV/s

Fig.6 Effect of cathode peak and anode peak current on CPE?1 scanning rate

Fig.7 Absorption curve of photodegraded MB of compound 1

Fig.8 Degradation rate of compound 1 and blank experiment

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