TiO2纳米管电极上电化学还原CO2生成CH3OH

引用本文: 裘建平, 童怡雯, 赵德明, 何志桥, 陈建孟, 宋爽. TiO₂纳米管电极上电化学还原CO₂生成CH₃OH[J]. 物理化学学报, 2017, 33(7): 1411-1420. doi: 10.3866/PKU.WHXB201704078 shu

Citation: QIU Jian-Ping, TONG Yi-Wen, ZHAO De-Ming, HE Zhi-Qiao, CHEN Jian-Meng, SONG Shuang. Electrochemical Reduction of CO₂ to Methanol at TiO₂ Nanotube Electrodes[J]. Acta Physico-Chimica Sinica, 2017, 33(7): 1411-1420. doi: 10.3866/PKU.WHXB201704078 shu

TiO₂纳米管电极上电化学还原CO₂生成CH₃OH

1.
浙江工业大学环境学院, 杭州 310032;
2.
金华职业技术学院, 浙江金华 321007;
3.
浙江工业大学化学工程学院, 杭州 310032
基金项目:
国家自然科学基金（21477117）和浙江省自然科学基金（LR14E080001，LQ15E080007，LY15B070005）资助项目

摘要: 采用原位阳极氧化-煅烧法制备TiO₂纳米管（TiO₂NTs）电极，运用X射线衍射（XRD）、电场发射扫描电子显微镜（FESEM）、X射线光电子能谱（XPS）、双电位阶跃测试等对制备电极进行表征，考察了其在0.1 mol·L^-1 KHCO₃水溶液中电化学还原CO₂的催化活性。结果表明TiO₂NTs电极上电化学还原CO₂的主产物为CH₃OH，CH₃OH由HCOOH和HCHO进一步还原而来。电极制备的最佳煅烧温度为450℃（TiO₂NTs-450），电解电位-0.56 V（vs RHE （可逆氢电极））时反应120 min后，生成CH₃OH的法拉第效率和分电流密度分别为85.8%和0.2 mA·cm^-2。与550和650℃煅烧的电极相比，TiO₂NTs-450电极具有更高的催化活性，归因于电极表面更多的三价钛活性位，有利于CO₂吸附，从而对·CO₂^-起到稳定的作用，速率控制步骤转变为·CO₂^-的质子化反应。

关键词:

English

Electrochemical Reduction of CO₂ to Methanol at TiO₂ Nanotube Electrodes

1.
College of Environment, Zhejiang University of Technology, Hangzhou 310032, P. R. China;
2.
Jinhua Polytechnic, Jinhua 321007, Zhejiang Province, P. R. China;
3.
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. China
Received Date: 21 December 2016
Revised Date: 24 March 2017
Available Online: 13 April 2017
Fund Project:
The project was supported by the National Natural Science Foundation of China (21477117) and Natural Science Foundation of Zhejiang Province, China (LR14E080001, LQ15E080007, LY15B070005).

Abstract: A series of highly ordered TiO₂ nanotube (TiO₂NTs) electrodes are prepared via potentiostatic anodization of Ti foil followed by calcining in air. X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and potential steps determination are used to characterize the electrodes. The electrochemical reduction of CO₂ on these three TiO₂NTs electrodes is investigated by cyclic voltammetry and potentiostatic electrolysis in 0.1 mol·L^-1 KHCO₃ aqueous solution. Methanol is found to be the major product in electrochemical CO₂ reduction, while formic acid, formaldehyde, methane, and CO are formed as minor products. Compared with the electrodes sintered at 550 and 650℃, the optimal TiO₂NTs electrode is found to be the one calcined at 450℃ (TiO₂NTs-450). After 120 min of reaction, the Faradaic efficiency and partial current density of methanol is 85.8% and 0.2 mA·cm^-2 at -0.56 V vs. reversible hydrogen electrode (RHE), respectively. The trivalent titanium in TiO₂ serves as an efficient site for adsorption of CO₂ and stabilization of the adsorbed ·CO₂^- radical. Consequently, the reduction of CO₂ on TiO₂NTs electrodes involves a fast first electron and proton transfer followed by a slow second proton transfer as the rate-limiting step.

Key words:

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TiO₂纳米管电极上电化学还原CO₂生成CH₃OH

English

Electrochemical Reduction of CO₂ to Methanol at TiO₂ Nanotube Electrodes

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