Synthesis，Characterization and Electrochemical Properties of FeⅡ Modified Hourglass Phosphomolybdate

doi:10.12422/j.issn.1672-6952.2023.04.007

Journal of Liaoning Petrochemical University ›› 2023, Vol. 43 ›› Issue (4): 45-50.DOI: 10.12422/j.issn.1672-6952.2023.04.007

• Material Science and New Energy（Synthesis and Properties of Crystalline Materials） • Previous Articles Next Articles

Synthesis，Characterization and Electrochemical Properties of Fe^Ⅱ Modified Hourglass Phosphomolybdate

Xiaohui Liu(), Muzi Li, Hui Li, Na Xu()

College of Chemistry and Materials Engineering，Bohai University，Jinzhou Liaoning 121013，China

Received:2023-06-20 Revised:2023-07-03 Published:2023-08-25 Online:2023-09-04
Contact: Na Xu

Fe^Ⅱ修饰的沙漏型磷钼酸盐的合成、表征与电化学性能研究

刘晓慧(), 李沐子, 李慧, 徐娜()

渤海大学化学与材料工程学院，辽宁锦州 121013

通讯作者: 徐娜
作者简介:刘晓慧（1998⁃），女，硕士研究生，从事多酸基晶态材料的设计合成与性能等方面的研究；E⁃mail：1986858556@qq.com。
基金资助:
国家自然科学基金项目(22101030);辽宁省博士启动基金项目(2021?BS?255);渤海大学博士生科研基金项目(0520bs022)

Abstract

Abstract:

Using Fe(NO₃)₃·9H₂O, H₃PO₄, Na₂MoO₄·2H₂O, 3?aminomethylpyridine as raw materials, a complex 1 based on the hourglass phosphomolybdate modified with Fe^Ⅱ was successfully synthesized by hydrothermal synthesis method. The molecular formula is (C₆H₁₀N₂)₆{Fe[Mo₆O₁₂(OH)₃(PO₄)₂(H₂PO₄)₂]₂}·3.5H₂O. The single crystal X?ray diffraction infrared spectroscopy(FT?IR) powder X?ray diffraction(PXRD) and thermogravimetric analysis(TGA) were used to prove its structure and composition which was analyzed at the same time The results show that complex 1 has a three?dimensional supramolecular framework, which connected {Fe[P₄Mo $6 V$ O₃₁]₂} $22 -$ (denoted as {Fe(P₄Mo₆)₂}) and protonated 3?aminomethylpyridine by five hydrogen bond interactions of N(6)—H(6B) ···O(15) ，N(6)—

H(6A)···O(8)， N(2)—H(2C)···O(23)， N(2)—H(2B) ···O(19) and N(1)—H(1A) ···O(30). Besides, the electrochemical detection of furaltadone hydrochloride was further studied by using complex modified carbon paste electrode(1?CPE). The experimental results show that 1?CPE has good stability and high selectivity for furaltadone hydrochloride.

Key words: Hourglass phosphomolybdate, Crystal structure, Electrochemical detection

摘要：

以Fe(NO₃)₃·9H₂O、H₃PO₄、Na₂MoO₄·2H₂O、3?氨甲基吡啶为原料，利用水热合成法成功合成了一例Fe^Ⅱ修饰的沙漏型磷钼酸基配合物1（分子式为(C₆H₁₀N₂)₆{Fe[Mo₆O₁₂(OH)₃(PO₄)₂(H₂PO₄)₂]₂}·3.5H₂O），并对配合物1进行了单晶X?射线衍射、红外光谱（FT?IR）、粉末X射线衍射（PXRD）和热重（TG）等分析，以证明其结构和组成，同时进行了结构分析。结果表明，配合物1呈一个三维超分子框架，是通过N(6)—H(6B)???O(15)、N(6)—H(6A)???O(8)、N(2)—H(2C)???O(23)、N(2)—H(2B)???O(19)和N(1)—H(1A)???O(30)等五种氢键，将{Fe[P₄Mo $6 V$ O₃₁]₂}^22-（记为{Fe(P₄Mo₆)₂}）和质子化的3?氨甲基吡啶连接而形成的。此外，利用配合物1修饰的碳糊电极（1?CPE）对盐酸呋喃它酮进行了电化学检测。结果表明，1?CPE具有良好的稳定性以及对盐酸呋喃它酮的高选择性。

关键词: 沙漏型磷钼酸盐, 晶体结构, 电化学检测

CLC Number:

TQ138.1

Xiaohui Liu, Muzi Li, Hui Li, Na Xu. Synthesis，Characterization and Electrochemical Properties of Fe^Ⅱ Modified Hourglass Phosphomolybdate[J]. Journal of Liaoning Petrochemical University, 2023, 43(4): 45-50.

刘晓慧, 李沐子, 李慧, 徐娜. Fe^Ⅱ修饰的沙漏型磷钼酸盐的合成、表征与电化学性能研究[J]. 辽宁石油化工大学学报, 2023, 43(4): 45-50.

Figures/Tables 13

References 16

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参数	数值	参数	数值
CCDC号	2268803	晶胞体积/nm³	2.139 8(5)
相对分子质量	3 111.88	单位晶胞中所含分子个数	1
晶系	三斜	单胞密度/(g·cm^－3)	2.415
空间群	Pī	吸收系数/mm^－1	2.125
温度/K	296.15	单胞中的电子数目	1 510.0
a/nm	1.216 65(15)	衍射点收集	15 644/10 463[R(int)=0.017 8]^*
b/nm	1.390 19(18)	数据限制性参数	10 463/18/597
c/nm	1.409 96(17)	基于F² 的GOF值	1.040
α/(°)	74.876(2)	可观测衍射点的残差因子R值	R₁=0.025 5,wR₂=0.067 2
β/(°)	76.338(2)	全部衍射点的残差因子R值	R₁=0.029 0,wR₂=0.069 2
γ/(°)	70.416(2)

参数	数值	参数	数值
CCDC号	2268803	晶胞体积/nm³	2.139 8(5)
相对分子质量	3 111.88	单位晶胞中所含分子个数	1
晶系	三斜	单胞密度/(g·cm^－3)	2.415
空间群	Pī	吸收系数/mm^－1	2.125
温度/K	296.15	单胞中的电子数目	1 510.0
a/nm	1.216 65(15)	衍射点收集	15 644/10 463[R(int)=0.017 8]^*
b/nm	1.390 19(18)	数据限制性参数	10 463/18/597
c/nm	1.409 96(17)	基于F² 的GOF值	1.040
α/(°)	74.876(2)	可观测衍射点的残差因子R值	R₁=0.025 5,wR₂=0.067 2
β/(°)	76.338(2)	全部衍射点的残差因子R值	R₁=0.029 0,wR₂=0.069 2
γ/(°)	70.416(2)

氢键（D－H∙∙∙A）	d(D－H)/nm	d(H∙∙∙A)/nm	d(D∙∙∙A)/nm	∠(D－H∙∙∙A)/（˚）
N(6)－H(6B)∙∙∙O(15)	0.089 0	0.187 0	0.274 9(3)	171
N(6)－H(6A)∙∙∙O(8)	0.089 0	0.189 0	0.277 8(3)	175
N(2)－H(2C)∙∙∙O(23)	0.089 0	0.216 0	0.288 1(4)	138
N(2)－H(2B)∙∙∙O(19)	0.089 0	0.185 0	0.268 2(3)	155
N(1)－H(1A)∙∙∙O(30)	0.086 0	0.170 0	0.255 3(4)	170

氢键（D－H∙∙∙A）	d(D－H)/nm	d(H∙∙∙A)/nm	d(D∙∙∙A)/nm	∠(D－H∙∙∙A)/（˚）
N(6)－H(6B)∙∙∙O(15)	0.089 0	0.187 0	0.274 9(3)	171
N(6)－H(6A)∙∙∙O(8)	0.089 0	0.189 0	0.277 8(3)	175
N(2)－H(2C)∙∙∙O(23)	0.089 0	0.216 0	0.288 1(4)	138
N(2)－H(2B)∙∙∙O(19)	0.089 0	0.185 0	0.268 2(3)	155
N(1)－H(1A)∙∙∙O(30)	0.086 0	0.170 0	0.255 3(4)	170

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