电沉积制备铜基催化剂及其对CO2电还原的催化性能

doi:10.3969/j.issn.1000-5641.2023.01.013

华东师范大学学报（自然科学版） ›› 2023, Vol. 2023 ›› Issue (1): 129-139.doi: 10.3969/j.issn.1000-5641.2023.01.013

• CO2资源化利用 • 上一篇

电沉积制备铜基催化剂及其对CO₂电还原的催化性能

楚萌恩^1,²(), 陈春俊³, 吴海虹^1,^2,*(), 何鸣元^1,², 韩布兴^1,^2,³

1. 华东师范大学化学与分子工程学院上海市绿色化学和化工过程绿色化重点实验室, 上海　200062
2. 崇明生态研究院, 上海　202162
3. 中国科学院化学研究所胶体、界面与化学热力学重点实验室, 北京　100190

收稿日期:2022-07-15 接受日期:2022-07-15 出版日期:2023-01-25 发布日期:2023-01-07
通讯作者: 吴海虹 E-mail:mengcme@163.com;hhwu@chem.ecnu.edu.cn
作者简介:楚萌恩, 女, 博士研究生, 研究方向为电催化还原二氧化碳. E-mail: mengcme@163.com
基金资助:
国家重点研发项目(2017YFA0403102); 华东师范大学“幸福之花”先导研究基金(2020ST2203)

Electrodeposition performance of a copper-based catalyst for the electroreduction of CO₂

Meng’en CHU^1,²(), Chunjun CHEN³, Haihong WU^1,^2,*(), Mingyuan HE^1,², Buxing HAN^1,^2,³

1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai　200062, China
2. Institute of Eco-Chongming, Shanghai　202162, China
3. CAS Key Laboratory of Colloid and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing　100190, China

Received:2022-07-15 Accepted:2022-07-15 Online:2023-01-25 Published:2023-01-07
Contact: Haihong WU E-mail:mengcme@163.com;hhwu@chem.ecnu.edu.cn

摘要/Abstract

摘要：

为了提高铜基催化剂电还原CO₂的催化性能, 以氮三乙酸(nitrilotriacetic acid, NTA)为添加剂, 通过电沉积法制备了具有三维结构的铜基催化剂, 该催化剂具有优异的电还原CO₂制备多碳(C2+)产物的选择性和活性. 在 –1.26 V vs. RHE (reversible hydrogen electrode)时, 乙烯(C₂H₄)和C2+ 产物的法拉第效率(faradaic efficiency, FE)分别能达到44.0%和61.6%, 此时总电流密度(current density)为12.3 mA·cm^–2. 此外, 在NTA的作用下, 运用电沉积法制备的Pd和Zn基催化剂具有良好的电还原CO₂为CO的性能, 表明NTA作为添加剂在电沉积法制备金属催化剂方面具有一定的普适性.

关键词: 电催化, 二氧化碳, 铜基催化剂, 电沉积

Abstract:

To improve the catalytic performance of copper-based catalysts in the electroreduction of CO₂, nitrotriacetic acid (NTA) was used as an additive to prepare copper-based catalysts having a three-dimensional structure by applying electrodeposition. The prepared catalysts exhibited excellent selectivity and activity for the electroreduction of CO₂ to multi-carbon (C2+) products. At –1.26 V vs. RHE, the faradaic efficiency of C₂H₄ and C2+ products over the Cu-0.5/CP electrode reached 44.0% and 61.6%, respectively, and the total current density reached 12.3 mA·cm^–2. In addition, Pd- and Zn-based catalysts were prepared by employing electrodeposition; the results showed that their selectivity for CO was significantly improved, proving that NTA has a certain universality in the preparation of electrocatalysts by using electrodeposition.

Key words: electroreduction, carbon dioxide, copper-based catalysts, ethylene

中图分类号:

O646

楚萌恩, 陈春俊, 吴海虹, 何鸣元, 韩布兴. 电沉积制备铜基催化剂及其对CO₂电还原的催化性能[J]. 华东师范大学学报（自然科学版）, 2023, 2023(1): 129-139.

Meng’en CHU, Chunjun CHEN, Haihong WU, Mingyuan HE, Buxing HAN. Electrodeposition performance of a copper-based catalyst for the electroreduction of CO₂[J]. Journal of East China Normal University(Natural Science), 2023, 2023(1): 129-139.

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参考文献 32

1	SONG R B, ZHU W L, FU J J, et al. Electrode materials engineering in electrocatalytic CO₂ reduction: Energy input and conversion efficiency . Advanced Materials, 2020, 32 (27): 1903796- 1903820.
2	ZHANG L, ZHAO Z J, GONG J L. Nanostructured materials for heterogeneous electrocatalytic CO₂ reduction and their related reaction mechanisms . Angewandte Chemie-International Edition, 2017, 56 (38): 11326- 11353.
3	WANG Y F, HAN P, LYU X M, et al. Defect and interface engineering for aqueous electrocatalytic CO₂ reduction . Joule, 2018, 2 (12): 2551- 2582.
4	ZHANG W J, HU Y, MA L B, et al. Progress and perspective of electrocatalytic CO₂ reduction for renewable carbonaceous fuels and chemicals . Advanced Science, 2018, 5 (1): 1700275- 1700298.
5	PEI Y H, ZHONG H, JIN F M. A brief review of electrocatalytic reduction of CO₂—Materials, reaction conditions, and devices . Energy Science & Engineering, 2021, 9 (7): 1012- 1032.
6	YE W X, GUO X L, MA T L, et al. A review on electrochemical synthesized copper-based catalysts for electrochemical reduction of CO₂ to C₂₊ products . Chemical Engineering Journal, 2021, 414, 128825- 128840.
7	CHOU T C, CHANG C C, YU H L, et al. Controlling the oxidation state of the Cu electrode and reaction intermediates for electrochemical CO₂ reduction to ethylene . Journal of the American Chemical Society, 2020, 142 (6): 2857- 2867.
8	LYU Z H, ZHU S Q, XIE M H, et al. Controlling the surface oxidation of Cu nanowires improves their catalytic selectivity and stability toward C₂₊ products in CO₂ reduction . Angewandte Chemie-International Edition, 2021, 60 (4): 1909- 1915.
9	TAN Z T, PENG T P, TAN X J, et al. Controllable synthesis of leaf-like CuO nanosheets for selective CO₂ electroreduction to ethylene . ChemElectroChem, 2020, 7 (9): 2020- 2025.
10	LUO H Q, LI B, MA J G, et al. Surface modification of nano-Cu₂O for controlling CO₂ electrochemical reduction to ethylene and syngas . Angewandte Chemie-International Edition, 2022, 61 (11): e202116736.
11	KEERTHIGA G, CHETTY R. Electrochemical reduction of CO₂ on flame annealed Cu . ChemistrySelect, 2021, 6 (12): 2887- 2892.
12	HORI Y, TAKAHASHI I, KOGA O, et al. Selective formation of C₂ compounds from electrochemical reduction of CO₂ at a series of copper single crystal electrodes . The Journal of Physical Chemistry B, 2002, 106 (1): 15- 17.
13	JIAO J Q, LIN R, LIU S J, et al. Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO₂. Nature Chemistry, 2019, 11 (3): 222- 228.
14	ZHAO K, LIU Y M, QUAN X, et al. CO₂ electroreduction at low overpotential on oxide-derived Cu/carbons fabricated from metal organic framework . ACS Applied Materials & Interfaces, 2017, 9 (6): 5302- 5311.
15	GUAN A X, CHEN Z, QUAN Y L, et al. Boosting CO₂ electroreduction to CH₄ via tuning neighboring single-copper sites . ACS Energy Letters, 2020, 5 (4): 1044- 1053.
16	ZHU Q G, YANG D X, LIU H Z, et al. Hollow metal–organic-framework-mediated in situ architecture of copper dendrites for enhanced CO₂ electroreduction . Angewandte Chemie-International Edition, 2020, 59 (23): 8896- 8901.
17	YANG D X, ZHU Q G, SUN X F, et al. Electrosynthesis of a defective indium selenide with 3D structure on a substrate for tunable CO₂ electroreduction to syngas . Angewandte Chemie-International Edition, 2020, 59 (6): 2354- 2359.
18	ZHU Q G, SUN X F, YANG D X, et al. Carbon dioxide electroreduction to C₂ products over copper-cuprous oxide derived from electrosynthesized copper complex . Nature Communications, 2019, 10 (1): 3851- 3861.
19	HOANG T T H, MA S C, GOLD J I, et al. Nanoporous copper films by additive-controlled electrodeposition: CO₂ reduction catalysis . ACS Catalysis, 2017, 7 (5): 3313- 3321.
20	LIU J, FU J J, ZHOU Y, et al. Controlled synthesis of EDTA-modified porous hollow copper microspheres for high-efficiency conversion of CO₂ to multicarbon products . Nano Letters, 2020, 20 (7): 4823- 4828.
21	HAN Z S, HAN D L, CHEN Z, et al. Steering surface reconstruction of copper with electrolyte additives for CO₂ electroreduction . Nature Communications, 2022, 13, 3158- 3167.
22	HENTRICH D, TAUER K, ESPANOL M, et al. EDTA and NTA effectively tune the mineralization of calcium phosphate from bulk aqueous solution. Biomimetics, 2017, 2 (4): 24- 45.
23	FENG R T, ZHU Q G, CHU M E, et al. Electrodeposited Cu-Pd bimetallic catalysts for the selective electroreduction of CO₂ to ethylene . Green Chemistry, 2020, 22, 7560- 7565.
24	JIA S Q, ZHU Q G, CHU M E, et al. Hierarchical metal-polymer hybrids for enhanced CO₂ electroreduction . Angewandte Chemie-International Edition, 2021, 60 (19): 10977- 10982.
25	JUNG H, LEE S Y, LEE C W, et al. Electrochemical fragmentation of Cu₂O nanoparticles enhancing selective C–C coupling from CO₂ reduction reaction . Journal of the American Chemical Society, 2019, 141 (11): 4624- 4633.
26	SRIVASTAVA V, LIU W, JANKE E M, et al. Understanding and curing structural defects in colloidal GaAs nanocrystals. Nano Letters, 2017, 17 (3): 2094- 2101.
27	CHEN C J, YAN X P, WU Y H, et al. Boosting the productivity of electrochemical CO₂ reduction to multi-carbon products by enhancing CO₂ diffusion through a porous organic cage . Angewandte Chemie-International Edition, 2022, 61 (23): e202202607.
28	LI P S, BI J H, LIU J Y, et al. In situ dual doping for constructing efficient CO₂-to-methanol electrocatalysts . Nature Communications, 2022, 13, 1965- 1973.
29	CHU S L, LI X, ALEX W R, et al. Electrocatalytic CO₂ reduction to ethylene over CeO₂-supported Cu nanoparticles: Effect of exposed facets of CeO₂. Chinese Journal of Catalysis, 2021, 37 (5): 2009023.
30	JIANG Y Q, CHANGHYEOK C, HONG S, et al. Enhanced electrochemical CO₂ reduction to ethylene over CuO by synergistically tuning oxygen vacancies and metal doping . Cell Reports Physical Science, 2021, 2 (3): 100356.
31	GENG Z G, KONG X D, CHEN W W, et al. Oxygen vacancies in ZnO nanosheets enhance CO₂ electrochemical reduction to CO . Angewandte Chemie-International Edition, 2018, 57 (21): 6054- 6059.
32	JIA S Q, ZHU Q G, WU H H, et al. Efficient electrocatalytic reduction of carbon dioxide to ethylene on copper-antimony bimetallic alloy catalyst. Chinese Journal of Catalysis, 2020, 41, 1091- 1098.

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电沉积制备铜基催化剂及其对CO₂电还原的催化性能

Electrodeposition performance of a copper-based catalyst for the electroreduction of CO₂

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