基于磺酰基杯[4]芳烃的Co16笼簇的合成、 结构及电化学性质

doi:10.7503/cjcu20190236

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (10): 2052.doi: 10.7503/cjcu20190236

• 研究论文: 无机化学 • 上一篇下一篇

基于磺酰基杯[4]芳烃的Co₁₆笼簇的合成、结构及电化学性质

张敏¹,陈梦伟¹,高虹²,毕研峰^1,^*()

^1. 辽宁石油化工大学化学化工与环境学部, 抚顺 113001
^2. 辽宁省分析科学研究院, 沈阳 110015

收稿日期:2019-04-24 出版日期:2019-10-10 发布日期:2019-08-20
通讯作者: 毕研峰 E-mail:biyanfeng@lnpu.edu.cn
基金资助:
辽宁省教育厅基本科研项目-重点项目(No.L2017LZD002);辽宁省‘兴辽英才计划’项目(No.XLYC1807059)

Synthesis, Structure and Electrochemical Properties of Sulfonylcalix[4]arene Supported Co₁₆ Cluster ^†

ZHANG Min¹,CHEN Mengwei¹,GAO Hong²,BI Yanfeng^1,^*()

^1. College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113001, China
^2. Liaoning Academy of Analytical Sciences, Shenyang 110015, China

Received:2019-04-24 Online:2019-10-10 Published:2019-08-20
Contact: BI Yanfeng E-mail:biyanfeng@lnpu.edu.cn
Supported by:
† Supported by the Fundamental Research Project of Key Lab of Educational Bureau of Liaoning Province, China(No.L2017LZD002);the Liaoning Revitalization Talents Program, China.(No.XLYC1807059)

摘要/Abstract

摘要：

以氯化钴、对叔丁基磺酰杯[4]芳烃(H₄TC4A-SO₂)和非对称性3-(1H-四唑-5-基)苯甲酸(H₂L)为原料, 通过溶剂热法合成了一个具有四面体配位笼结构的16核化合物[Co₁₆(TC4A-SO₂)₄(OH)₄(L)₈]·[(C₈H₂₀N)(C₄H₁₂N)₂(C₂H₈N)]·solvent(Co₁₆-TC4A-SO₂). 采用X射线单晶衍射、 X射线粉末衍射、热重分析、红外光谱方法对配合物进行了表征. 将Co₁₆-TC4A-SO₂笼簇直接负载到碳纸上(Co₁₆-TC4A-SO₂/CP)用作工作电极, 其对析氧反应(OER)展现出较好的催化性能. 在1 mol/L KOH中, Co₁₆-TC4A-SO₂/CP在343.8 mV的过电位下达到10.0 mA/cm ²电流密度, Tafel斜率为79.31 mV/dec, 并且在20.0 mA/cm ²电流密度下表现出长达48 h的催化稳定性.

关键词: 磺酰基杯[4]芳烃, 四面体配位笼, 电催化析氧反应

Abstract:

A new sulfonylcalix[4]arene-supported tetrahedral Co₁₆ cage cluster [Co₁₆(TC4A-SO₂)₄(OH)₄·(L)₈][(C₈H₂₀N)(C₄H₁₂N)₂(C₂H₈N)]·solvent(Abbr. Co₁₆-TC4A-SO₂) was synthesized from CoCl₂·6H₂O, p-tert-butylsulfonylcalix[4]arene(H₄TC4A-SO₂) and asymmetric 3-(1H-tetrazol-5-yl)benzoic acid(H₂L) under solvothermal condition. The complex was characterized by single crystal X-ray diffraction(XRD), powder X-ray diffraction(PXRD), thermogravimetric analysis(TGA), and infrared spectroscopy(FTIR). Directly loading Co₁₆-TC4A-SO₂ onto carbon paper(Co₁₆-TC4A-SO₂/CP) as a working electrode exhibited efficient oxygen evolution reaction(OER) catalytic performance. In 1 mol/L KOH, Co₁₆-TC4A-SO₂/CP gained a current density of 10.0 mA/cm ² at a catalytic reaction overpotential of 343.8 mV, a Tafel slope of 79.31 mV/dec, and catalytic stability for 48 h at 20.0 mA/cm ².

Key words: Sulfonylcalix[4]arene, Tetrahedral coordination cage, Electrocatalytic oxygen evolution reaction

中图分类号:

O614

TrendMD:

张敏, 陈梦伟, 高虹, 毕研峰. 基于磺酰基杯[4]芳烃的Co₁₆笼簇的合成、结构及电化学性质. 高等学校化学学报, 2019, 40(10): 2052.

ZHANG Min, CHEN Mengwei, GAO Hong, BI Yanfeng. Synthesis, Structure and Electrochemical Properties of Sulfonylcalix[4]arene Supported Co₁₆ Cluster ^†. Chem. J. Chinese Universities, 2019, 40(10): 2052.

图/表 5

Scheme 1 Synthetic route of Co16-TC4A-SO2

Table 1 Crystal data and structural refinement for Co16-TC4A-SO2

Formula	C₂₄₂H₂₆₄Co₁₆N₃₆O₆₈S₁₆	Volume/nm³	16.2702(19)
Molecular weight	6220.66	Z	2
Crystal system	Triclinic	Temperature/K	150
Space group	P $1 ˉ$	D_c/(g·cm^-3)	1.270
a/nm	2.26250(16)	μ/mm^-1	0.965
b/nm	2.38320(15)	Reflections collected	251116
c/nm	3.0258(2)	Unique data(R_int)	57738(0.059)
α/(°)	89.566(2)	GOF on F²	1.014
β/(°)	87.354(2)	$R 1 a$ [I>2σ(I)]	0.0480
γ/(°)	86.684(2)	w $R 2 b$	0.1366

Table 1 Crystal data and structural refinement for Co16-TC4A-SO2

Formula	C₂₄₂H₂₆₄Co₁₆N₃₆O₆₈S₁₆	Volume/nm³	16.2702(19)
Molecular weight	6220.66	Z	2
Crystal system	Triclinic	Temperature/K	150
Space group	P $1 ˉ$	D_c/(g·cm^-3)	1.270
a/nm	2.26250(16)	μ/mm^-1	0.965
b/nm	2.38320(15)	Reflections collected	251116
c/nm	3.0258(2)	Unique data(R_int)	57738(0.059)
α/(°)	89.566(2)	GOF on F²	1.014
β/(°)	87.354(2)	$R 1 a$ [I>2σ(I)]	0.0480
γ/(°)	86.684(2)	w $R 2 b$	0.1366

Fig.1 Crystal structure of Co16-TC4A-SO2 (A) Molecular structure of Co16-TC4A-SO2; (B) a tetranuclear Co4(TC4A-SO2)(OH) unit with four L ligands; (C) coordination mode of L ligand; (D) tetrahedral packing of tetranuclear units.

Fig.2 OER electrocatalytic activities of the Co16-TC4A-SO2 (A) LSV curves of the Co16-TC4A-SO2/CP with different mass loading; (B) comparison of Co16-TC4A-SO2/CP, Mixture/CP, and pure CP polarization curves; (C) Tafel plots of the electrodes; (D) prolonged chronoamperometric profiles of Co16-TC4A-SO2/CP at 343.8 mV(η10) for 12 h(a) and 373.8 mV(η20) for 48 h(b). Inset: polarization curves before(a) and after(b) 48 h-long electrocatalytic OER.

Fig.3 Nyquist plots of Co16-TC4A-SO2/CP before and after 12 h-long electrocatalytic OER(A) and plots of the charging current density against scan rates of Co16-TC4A-SO2/CP(B) Insets: (A) the equivalent circuit model for electrochemical impedance tests; (B) cyclic voltammetry curves.

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基于磺酰基杯[4]芳烃的Co₁₆笼簇的合成、结构及电化学性质

Synthesis, Structure and Electrochemical Properties of Sulfonylcalix[4]arene Supported Co₁₆ Cluster ^†

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