调控CuO表面性质选择性电催化还原CO2制HCOOH

doi:10.15541/jim20210547

无机材料学报 ›› 2022, Vol. 37 ›› Issue (1): 29-37.DOI: 10.15541/jim20210547

所属专题：【能源环境】CO2绿色转换； 2022年度中国知网高下载论文

• 专栏: CO ₂ 绿色转化(特邀编辑: 欧阳述昕, 王文中) • 上一篇下一篇

调控CuO表面性质选择性电催化还原CO₂制HCOOH

郭李娜(), 何雪冰, 吕琳, 吴丹, 原弘()

华中师范大学化学学院, 农药与化学生物学教育部重点实验室, 武汉 430079

收稿日期:2021-09-04 修回日期:2021-10-22 出版日期:2022-01-20 网络出版日期:2021-11-01
通讯作者: 原弘, 教授. E-mail: yuanhong@mail.ccnu.edu.cn
作者简介:郭李娜(1998-), 女, 硕士研究生. E-mail: gln@mails.ccnu.edu.cn
基金资助:
软物质材料化学与功能制造重庆市重点实验室开放经费(20191002)

Modulation of CuO Surface Properties for Selective Electrocatalytic Reduction of CO₂ to HCOOH

GUO Lina(), HE Xuebing, LYU Lin, WU Dan, YUAN Hong()

Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China

Received:2021-09-04 Revised:2021-10-22 Published:2022-01-20 Online:2021-11-01
Contact: YUAN Hong, professor. E-mail: yuanhong@mail.ccnu.edu.cn
About author:GUO Lina (1998-), female, Master candidate. E-mail: gln@mails.ccnu.edu.cn
Supported by:
Chongqing Key Laboratory of Soft-Matter Material Chemistry and Function Manufacturing(20191002)

摘要/Abstract

摘要：

电催化二氧化碳还原反应可将温室气体二氧化碳转化为化工原料或者有机燃料, 为克服全球变暖和电能向化学能转化提供了一条可行途径。该技术的主要挑战是产物分布广, 导致单一产物选择性低, 而调控催化剂的表面性质是解决这一难题的可行策略。本研究通过对氧化亚铜、硫化亚铜进行氧化制备表面性质不同的氧化铜, 其中, 氧化硫化亚铜制得的CuO-FS催化剂提高了电还原二氧化碳的活性和还原产物甲酸的选择性。该催化剂表现出较高的总电流密度, 而且在一个较大的测试电压范围(-0.8 ~ -1.1 V)内, 甲酸的法拉第效率可以保持在70%以上, 在-0.9 V时达到最大值78.4%。反应机理探究表明, CuO-FS优异的电还原二氧化碳性能归因于其较大的电化学活性表面积提供了大量表面活性位点, 产生较高的总电流密度; 而且电催化过程中催化剂表面产生较少的零价Cu, 减少了乙烯的生成, 使产物更集中于甲酸。

关键词: 电还原二氧化碳, 铜基催化剂, 表面性质, 产物选择性, 甲酸

Abstract:

The electrocatalytic carbon dioxide reduction reaction can convert the greenhouse gas carbon dioxide into chemical raw materials or organic fuels, providing a feasible way to overcome global warming and the conversion of electrical energy to chemical energy. The main challenge of this technology is the wide product distribution, resulting in low selectivity of a single product, however, modulating the surface properties of the catalyst is an efficient strategy to solve this problem. In this study, the precursors of Cu₂O and Cu₂S were oxidized to the CuO catalysts with different surface properties. The CuO-FS catalyst derived from Cu₂S delivered the improved activity of electro-reduction of carbon dioxide and selectivity for formic acid product. This catalyst exhibited a higher total current density and the Faraday efficiency of formic acid > 70% in a wide test voltage range of -0.8 - -1.1 V; the Faraday efficiency for formic acid could reach a maximum of 78.4% at -0.9 V. The mechanism study indicated that the excellent performance of CuO-FS for electro-reduction of carbon dioxide could be attributed to the large electrochemically active surface area, which provided a large number of surface active sites, resulting in a higher total current density; moreover, the less zero-valent Cu was produced over the surface of CuO-FS during the electrocatalytic process, which reduced the production of ethylene and thus promoted the production of formic acid.

Key words: CO₂ electroreduction, Cu-based catalyst, surface properties, product selectivity, formic acid

中图分类号:

TQ151

郭李娜, 何雪冰, 吕琳, 吴丹, 原弘. 调控CuO表面性质选择性电催化还原CO₂制HCOOH[J]. 无机材料学报, 2022, 37(1): 29-37.

GUO Lina, HE Xuebing, LYU Lin, WU Dan, YUAN Hong. Modulation of CuO Surface Properties for Selective Electrocatalytic Reduction of CO₂ to HCOOH[J]. Journal of Inorganic Materials, 2022, 37(1): 29-37.

图/表 9

图1 样品的形貌与元素组成

Fig. 1 Morphologies and element composition of samples FESEM images of (a) Cu2O, (b) Cu2S, (c) CuO-FO and (d) CuO-FS; (e) TEM image of CuO-FS; (f) HAADF image of the CuO-FS; (g, h) Corresponding EDS elemental mapping

图2 Cu2O、Cu2S、CuO-FS和CuO-FO的XRD图谱

Fig. 2 XRD patterns of Cu2O, Cu2S, CuO-FS and CuO-FO

图3 CuO-FS和CuO-FO的XPS图谱

Fig. 3 XPS spectra of CuO-FS and CuO-FO (a, b) Survey spectrum; (c) High resolution XPS spectra of Cu2p; (d) High resolution XPS spectra of O1s

图4 (a)CuO-FO和CuO-FS在注入CO2/Ar饱和的0.1 mol/L KHCO3电解液中的阴极极化曲线; (b)Cu2S、(c)Cu2O、(d)CuO-FO和 (e)CuO-FS上所有产物的法拉第效率和电流密度; (f)CuO-FS在不同测试电压下所有产物的法拉第效率

Fig. 4 (a) Cathodic polarization curves of CuO-FO and CuO-FS in 0.1 mol/L KHCO3 electrolyte saturated with CO2/Ar, FE of all products and current density over (b) Cu2S, (c) Cu2O, (d) CuO-FO, and (e) CuO-FS, and (f) FE of all products of CuO-FS tested at different voltages Colorful figures are available on website

图5 Cu2S、Cu2O、CuO-FO和CuO-FS上HCOOH的 (a) 法拉第效率, (b) 部分电流密度和(c) Tafel曲线; (d) CuO-FS和(e) CuO-FO在不同测试电压扫描速率下的CV曲线; (f) 四种样品在不同测试电压扫描速率的电流密度

Fig. 5 (a) FE, (b) partial current densities, (c) Tafel plots of HCOOH over Cu2S, Cu2O, CuO-FO and CuO-FS; (d,e) CV curves of (d) CuO-FO and (e) CuO-FS at various test voltage scan rates, and (f) current density of four samples at various test voltage scan rates Colorful figures are available on website

图6 CuO-FS在-0.9 V下的长期稳定性测试以及不同产物对应的法拉第效率

Fig. 6 Long-term stability test at the voltage of -0.9 V for the CuO-FS and corresponding FE of different products

图7 CuO-FS和CuO-FO的N2吸附等温曲线

Fig. 7 N2 adsorption isotherms of CuO-FS and CuO-FO

图8 CuO-FS及CuO-FO进行 (a) 3 min和 (b) 20 h测试后的XRD图谱

Fig. 8 XRD patterns of CuO-FS and CuO-FO after (a) 3 min and (b) 20 h test

图9 电化学测试1 h后的CuO-FS及CuO-FO的EPR谱图

Fig. 9 EPR spectra of CuO-FS and CuO-FO after electrochemistry test for 1 h

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调控CuO表面性质选择性电催化还原CO₂制HCOOH

Modulation of CuO Surface Properties for Selective Electrocatalytic Reduction of CO₂ to HCOOH

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