CuO/ZnO复合电催化剂的制备及其还原CO2制合成气

doi:10.15541/jim20210092

无机材料学报 ›› 2021, Vol. 36 ›› Issue (11): 1145-1153.DOI: 10.15541/jim20210092

所属专题：【虚拟专辑】碳中和(2020~2021)；【能源环境】CO2绿色转换

CuO/ZnO复合电催化剂的制备及其还原CO₂制合成气

张清明¹^,²(), 朱敏¹, 周晓霞²()

1.上海理工大学材料科学与工程学院, 上海 200093
2.中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2021-02-13 修回日期:2021-03-30 出版日期:2021-11-20 网络出版日期:2021-03-15
通讯作者: 周晓霞, 副研究员. E-mail: zhouxiaoxia@mail.sic.ac.cn
作者简介:张清明(1995-), 男, 硕士研究生. E-mail: 18271648276@163.com
基金资助:
国家自然科学基金(51961165107);上海国际合作项目(19520761000);上海市自然科学基金(19ZR1464500)

CuO/ZnO Composite Electrocatalyst: Preparation and Reduction of CO₂ to Syngas

ZHANG Qingming¹^,²(), ZHU Min¹, ZHOU Xiaoxia²()

1. School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2021-02-13 Revised:2021-03-30 Published:2021-11-20 Online:2021-03-15
Contact: ZHOU Xiaoxia, associate professor. E-mail: zhouxiaoxia@mail.sic.ac.cn
About author:ZHANG Qingming(1995-), male, Master candidate. E-mail: 18271648276@163.com
Supported by:
National Natural Science Foundation of China(51961165107);Shanghai International Cooperation Project(19520761000);Shanghai Natural Science Foundation(19ZR1464500)

摘要/Abstract

摘要：

二氧化碳(CO₂)还原制备合成气(CO和H₂混合气), 不仅可以实现碳循环降低温室效应, 而且能缓解能源危机。而实现CO₂资源化利用的关键在于催化剂设计。本研究采用金属离子共沉淀法制备了CuO及CuO/ZnO复合氧化物纳米材料, 通过调节催化剂组分, 探究其在不同电势下电化学CO₂还原制备合成气的性能。结果表明: 引入锌(Zn)物种可以减弱中间物CO₂^•-在催化剂上的吸附强度, 导致CO的法拉第效率(FE)降低, 氢气FE增加, 从而实现不同电势下合成气CO/H₂在1/1~1/4范围内的可控调节。尤其是, 当前驱液中铜和锌配比为1 : 2时, 在-0.9 V (vs. RHE)的电势下, CO和H₂总FE高达84%。

关键词: CO₂还原, 合成气, CuO/ZnO, 中间物CO₂^•-

Abstract:

The reduction of carbon dioxide (CO₂) to syngas (a mixture of CO and H₂) can not only realize the carbon cycle and decrease the greenhouse effect but also alleviate the energy crisis. Design of catalyst is the key to realize CO₂ resource utilization. Herein, CuO and CuO/ZnO composite were prepared by metal ion co-precipitation method, and their performance of electrochemical CO₂ reduction to syngas under different potentials was investigated by adjusting the catalyst components. The results show that the introduction of zinc (Zn) species can decrease the adsorption intensity of intermediate CO₂^•- on the catalyst, which leads to the decrease of Faraday efficiency (FE) of CO and the increase of FE of H₂, thus achieving controllable regulation of CO/H₂ in the range of 1/1-1/4 under different applied electrochemical potential. In particular, the total FE of syngas CO/H₂ is up to 84% when the ratio of Cu to Zn in the precursor solution is 1 : 2.

Key words: CO₂ reduction, syngas, CuO/ZnO, intermediate CO₂^•-

中图分类号:

O611

张清明, 朱敏, 周晓霞. CuO/ZnO复合电催化剂的制备及其还原CO₂制合成气[J]. 无机材料学报, 2021, 36(11): 1145-1153.

ZHANG Qingming, ZHU Min, ZHOU Xiaoxia. CuO/ZnO Composite Electrocatalyst: Preparation and Reduction of CO₂ to Syngas[J]. Journal of Inorganic Materials, 2021, 36(11): 1145-1153.

图/表 13

图1 CuO及CuO/ZnO催化剂的制备流程及CO2还原示意图

Fig. 1 Schematic representation of the fabrication of CuO and CuO/ZnO catalyst and CO2 reduction process

图2 电化学CO2还原电解池的(a)实物图和(b)简化模型图

Fig. 2 (a) Physical picture and (b) simplified model diagram for electrolytic cell of electrochemical CO2 reduction

图3 催化剂(a, e) CuO、(b, f) CuO/ZnO-1、(c, g) CuO/ZnO-2和(d, h) CuO/ZnO-3在热解(a~d)前(e~h)后的TEM照片;催化剂CuO/ZnO-2的元素面扫分布图((i) TEM, (j) Cu, (k) O和(l) Zn)

Fig. 3 TEM images of catalysts (a, e) CuO, (b, f) CuO/ZnO-1, (c, g) CuO/ZnO-2 and (d, h) CuO/ZnO-3 (a-d) before and (e-h) after pyrolysis with elemental mapping images of CuO/ZnO-2 ((i) TEM, (j) Cu, (k) O and (l) Zn)

图4 (a) CuO、CuO/ZnO-1、CuO/ZnO-2和CuO/ZnO-3电催化剂的XRD图谱; (b) CuO/ZnO-2催化剂的HRTEM照片; (c) CuO/ZnO-2的XPS全谱谱图; (d) CuO/ZnO-2和CuO的Cu2p XPS分图; (e) CuO/ZnO-2的Zn2p3/2 XPS分图; (f) CuO/ZnO-2与CuO的XPS高分辨O1s谱图

Fig. 4 (a) XRD patterns of CuO, CuO/ZnO-1, CuO/ZnO-2 and CuO/ZnO-3 electrocatalysts, (b) HRTEM image of CuO/ZnO-2, (c) total XPS survey of CuO/ZnO-2, (d) XPS Cu2p spectra of CuO/ZnO-2 and CuO, (e) XPS Zn2p3/2 spectrum of CuO/ZnO-2, and (f) XPS high resolution O1s spectra of CuO/ZnO-2 and CuO Colorful figures are available on website

表1 样品表面元素含量分析

Table 1 Analysis of the surface elemental content

Sample	Atomic percent/%
Sample	Cu	Zn	O	C
CuO	30.77	0	43.90	25.33
CuO/ZnO-1	30.91	6.73	46.34	16.02
CuO/ZnO-2	26.78	10.39	45.98	16.85
CuO/ZnO-3	19.95	12.95	42.22	25.44

图5 CuO和CuO/ZnO催化剂(a)在N2/CO2饱和的KHCO3电解液中的线性扫描伏安曲线(LSVs)和(b)电化学阻抗谱图(EIS)

Fig. 5 (a) Linear sweep voltammetry curves (LSVs) in N2/CO2-saturated KHCO3, (b) electrochemical impedance spectra (EIS) of CuO and CuO/ZnO catalyst Colorful figures are available on website

图6 (a) CuO/ZnO-2催化剂在CO2饱和的KOH溶液(CO2-KOH)和N2饱和的KHCO3溶液(N2-KHCO3)中CO2的还原活性; (b) CuO、(c) CuO/ZnO-1、(d) CuO/ZnO-2和(e) CuO/ZnO-3催化CO2还原产物的法拉第效率及对应的CO/H2的直方图; (f) CuO/ZnO-2的循环稳定性(黑色方形: H2法拉第效率, 红色圆点: CO法拉第效率)

Fig. 6 (a) Reduction activity of CO2 in CO2-saturated KOH solution (CO2-KOH) and N2-saturated KHCO3 solution (N2-KHCO3); Histograms for FE of the CO2 reduction products and the ratios of CO/H2 for (b) CuO, (c) CuO/ZnO-1, (d) CuO/ZnO-2 and (e) CuO/ ZnO-3; (f) Cyclic stability of CuO/ZnO-2 (black square and red dot indicate Faraday efficiencies of H2 and CO, respectively) Colorful figures are available on website

图7 (a) CuO、(b) CuO/ZnO-1、(c) CuO/ZnO-2和(d) CuO/ZnO-3电容ΔJ/2与扫描速率的线性拟合图

Fig. 7 Capacitive ΔJ/2 versus scan rate for (a) CuO, (b) CuO/ZnO-1, (c) CuO/ZnO-2, and (d) CuO/ZnO-3 Colorful figures are available on website

图8 (a) 在0.1 mol/L KOH溶液中, CuO、CuO/ZnO-1、CuO/ZnO-2和CuO/ZnO-3的氧化LSV曲线; (b) CuO/ZnO-2催化剂反应前后的红外光谱图; (c) CO的形成示意图

Fig. 8 (a) Oxidation LSVs of CuO, CuO/ZnO-1, CuO/ZnO-2 and CuO/ZnO-3 in 0.1 mol/L KOH; (b) Infrared spectra of the CuO/ZnO-2 catalyst before and after reaction; (c) Schematic formation process of CO Colorful figures are available on website

图S1 CuO、CuO/ZnO-1、CuO/ZnO-2和CuO/ZnO-3电催化剂的(a) N2吸脱附曲线和(b)孔径分布曲线

Fig. S1 (a) N2 adsorption/desorption curves and (b) pore size distributions of CuO, CuO/ZnO-1, CuO/ZnO-2 and CuO/ZnO-3 electrocatalysts

图S2 (a) CuO、(b) CuO/ZnO-2、(c) CuO/ZnO-2和(d) CuO/ZnO-3的电流-时间曲线

Fig. S2 i-t curves of (a) CuO, (b) CuO/ZnO-2, (c) CuO/ZnO-2 and (d) CuO/ZnO-3

图S3 催化剂CuO/ZnO-2循环稳定性测试后的TEM照片

Fig. S3 TEM image of catalyst CuO/ZnO-2 after cyclic stability test

图S4 (a) CuO、(b) CuO/ZnO-1、(c) CuO/ZnO-2和(d) CuO/ZnO-3在不同扫描速率下的CV曲线

Fig. S4 (a) CV curves for (a) CuO, (b) CuO/ZnO-1, (c) CuO/ZnO-2 and (d) CuO/ZnO-3 at different scan rates

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CuO/ZnO复合电催化剂的制备及其还原CO₂制合成气

CuO/ZnO Composite Electrocatalyst: Preparation and Reduction of CO₂ to Syngas

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