乙炔电催化氧化制备草酸的机理研究

doi:10.13208/j.electrochem.150211

电化学（中英文） ›› 2015, Vol. 21 ›› Issue (4): 353-361. doi: 10.13208/j.electrochem.150211

乙炔电催化氧化制备草酸的机理研究

宋秀丽^1,2，贾瑞龙¹，董文燕¹，梁镇海^1*

1. 太原理工大学化学化工学院，山西太原 030024；2. 太原师范学院化学系，山西太原 030031

收稿日期:2015-02-11 修回日期:2015-04-13 出版日期:2015-08-28 发布日期:2015-08-28
通讯作者: 梁镇海 E-mail:liangzhenhai@tyut.edu.cn
基金资助:
国家自然科学基金委员会和神华集团有限公司联合资助项目（No. U1261103）和中国科学院山西煤炭化学研究所煤转化国家重点实验室开放基金项目（No. J12-13-913）资助

Mechanism Study on the Electrocatalytic Oxidation of Acetylene to Oxalic Acid

SONG Xiu-li^1,2, JIA Rui-long¹, DONG Wen-yan¹, LIANG Zhen-hai^1*

1. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China; Department of Chemistry, Taiyuan Normal University, Taiyuan 030031, China

Received:2015-02-11 Revised:2015-04-13 Published:2015-08-28 Online:2015-08-28
Contact: LIANG Zhen-hai E-mail:liangzhenhai@tyut.edu.cn

摘要/Abstract

摘要： 选择铂为电极电催化乙炔合成草酸，通过紫外-可见分光光度法和红外光谱法对产品进行表征，利用第一性原理计算方法探讨乙炔在催化剂Pt(111)表面的吸附情况，采用循环伏安法（CV）研究铂电极在硫酸钠溶液中氧化乙炔的电极过程，重点测定电极的稳态极化曲线并根据极化曲线推算塔菲尔斜率，结合表观传递系数及反应级数对拟定的乙炔电催化氧化制备草酸的反应机理进行验证. 实验结果表明，乙炔分子在Pt(111)面上呈平行桥键构型时吸附最稳定；铂电极在含体积分数为2%丙酮的0.4 mol·L^-1硫酸钠溶液中可将乙炔电催化氧化为草酸；反应的速率控制步骤为.

关键词: 乙炔, 草酸, 循环伏安法, 电催化机理, 第一性原理, 速控步骤

Abstract: A new method of electrocatalytic synthesis oxalic acid from acetylene was explored and the synthesized oxalic acid was characterized by Ultraviolet-visible spectrophotometry (Uv-vis) and Infrared spectroscopy (IR). First-principles calculations were carried out to examine the adsorption of acetylene over the Pt(111) surface. The electrocatalytic oxidation behavior of acetylene has been investigated on a Pt electrode by cyclic voltammetry (CV) and steady-state polarization in Na₂SO₄ solution. The formation mechanism of oxalic acid in the Na₂SO₄ solution was proposed and the transfer coefficients of the reaction were calculated. The results show that acetylene molecule tends to adsorb through the threefold parallel-bridge configuration that is computed to be the most stable because of its lowest adsorption energy. is the rate-determining step during the electrolysis process. The rate of this step obtained from the assumed process agrees well with that from the experiment.

Key words: acetylene, oxalic acid, cyclic voltammetry, electrocatalytic mechanism, first-principles, rate-determining step

中图分类号:

O646

宋秀丽, 贾瑞龙, 董文燕, 梁镇海. 乙炔电催化氧化制备草酸的机理研究[J]. 电化学（中英文）, 2015, 21(4): 353-361.

SONG Xiu-li, JIA Rui-long, DONG Wen-yan, LIANG Zhen-hai. Mechanism Study on the Electrocatalytic Oxidation of Acetylene to Oxalic Acid[J]. Journal of Electrochemistry, 2015, 21(4): 353-361.

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乙炔电催化氧化制备草酸的机理研究

Mechanism Study on the Electrocatalytic Oxidation of Acetylene to Oxalic Acid

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