Deactivation of copper electrocatalysts during CO2 reduction occurs via dissolution and selective redeposition mechanism†

IF 10.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL
Blaž Tomc, Marjan Bele, Mohammed Azeezulla Nazrulla, Primož Šket, Matjaž Finšgar, Angelja Kjara Surca, Ana Rebeka Kamšek, Martin Šala, Jan Šiler Hudoklin, Matej Huš, Blaž Likozar and Nejc Hodnik
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Abstract

As electrochemical CO2 reduction (ECR) nears industrialisation levels, addressing the uncontrolled stability, restructuring, and deactivation of copper (Cu) catalysts during operation becomes as crucial as achieving high activity and selectivity for a single product. This study used a high-surface area Cu catalyst that exhibited changes in ECR product selectivity over prolonged operation. The detection of dissolved Cu species during electrolysis confirmed an intermediates-mediated Cu dissolution mechanism at ECR potentials (−0.8 to −1.1 V vs. reversible hydrogen electrode). The findings suggest that the electrodeposition of dissolved Cu species is biased towards Cu catalyst sites with lower reaction intermediates coverage, e.g. adsorbed CO (*CO). A dynamic equilibrium between dissolution and subsequent selective redeposition gradually led to morphological restructuring, resulting in a shift in selectivity away from ECR and towards hydrogen production. With the obtained extensive experimental results, theoretical modelling, and literature data, four interconnected parameters governing restructuring and selectivity shifts were recognised: (i) size and (ii) crystallographic orientation of facets of the nanoparticles, (iii) *CO coverage and (iv) CObridgevs. COatop ratio.

Abstract Image

铜电催化剂在CO2还原过程中通过溶解和选择性再沉积机理失活
随着电化学二氧化碳还原技术(ECR)接近工业化水平,解决铜催化剂在操作过程中不受控制的稳定性、重组和失活问题变得与实现单一产物的高活性和选择性同样重要。本研究使用了一种高表面积的Cu催化剂,该催化剂在长时间的操作中表现出ECR产物选择性的变化。电解过程中溶解的Cu物质的检测证实了在ECR电位(-0.8到-1.1 V vs可逆氢电极)下中间体介导的Cu溶解机制。研究结果表明,电沉积中溶解的Cu偏向于Cu催化剂位点,这些位点具有较低的反应中间体覆盖率,例如吸附的CO (*CO)。溶解和随后的选择性再沉积之间的动态平衡逐渐导致形态重构,导致选择性从ECR转向产氢。通过广泛的实验结果、理论模型和文献数据,我们识别出了四个相互关联的参数,这些参数控制着重构和选择性的变化:(i)纳米颗粒的尺寸和(ii)表面的晶体取向,(iii) *CO覆盖率和(iv) CObridge / cotop比。
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来源期刊
Journal of Materials Chemistry A
Journal of Materials Chemistry A CHEMISTRY, PHYSICAL-ENERGY & FUELS
CiteScore
19.50
自引率
5.00%
发文量
1892
审稿时长
1.5 months
期刊介绍: The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.
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