不同预处理的氧化亚铜纳米线电极诱导的晶面效应提升电化学CO2还原为多碳产物

doi:10.1016/S1872-2067(21)63981-5

催化学报 ›› 2022, Vol. 43 ›› Issue (4): 1066-1073.DOI: 10.1016/S1872-2067(21)63981-5

不同预处理的氧化亚铜纳米线电极诱导的晶面效应提升电化学CO₂还原为多碳产物

付阳, 谢起贤, 武琳晓, 罗景山^*()

南开大学光电子薄膜器件与技术研究所, 天津市光电子薄膜器件与技术重点实验室, 教育部薄膜光电子技术工程研究中心, 新能源转化与存储交叉科学中心, 天津300350

收稿日期:2021-09-14 接受日期:2021-09-14 出版日期:2022-03-05 发布日期:2022-03-01
通讯作者: 罗景山
基金资助:
国家重点研发计划(2019YFE0123400);天津杰出青年基金(20JCJQJC00260);111工程(B16027);南开大学启动经费

Crystal facet effect induced by different pretreatment of Cu₂O nanowire electrode for enhanced electrochemical CO₂ reduction to C₂₊products

Yang Fu, Qixian Xie, Linxiao Wu, Jingshan Luo^*()

Institute of Photoelectronic Thin Film Devices and Technology, Key Laboratory of Photoelectronic Thin Film Devices and Technology of Tianjin, Ministry of Education Engineering Research Center of Thin Film Photoelectronic Technology, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300350, China

Received:2021-09-14 Accepted:2021-09-14 Online:2022-03-05 Published:2022-03-01
Contact: Jingshan Luo
Supported by:
National Key Research and Development Program of China(2019YFE0123400);Tianjin Distinguished Young Scholars Fund(20JCJQJC00260);“111” Project(B16027);Startup Funding from Nankai University

摘要/Abstract

摘要：

近年来, 由于化石燃料不断消耗造成的二氧化碳气体过量排放, 对人类生活环境造成越来越大的威胁. 电催化二氧化碳还原反应是一种很有前景的解决方法, 可回收废弃的二氧化碳并通过将其转化为可再生的燃料和化学品来最终实现碳循环. 在各种还原产物中, 多碳化学产物因其具有高能量密度和高商业价值而备受青睐. 然而, 由于涉及多个复杂的反应途径, 设计对多碳产物高活性的催化剂仍然是一个关键挑战. 铜是目前最有前途的催化剂之一, 它具有独特的电子结构来吸附CO中间体, 从而促进后续C‒C偶联成多碳产物. 虽然Cu基催化剂在电催化二氧化碳还原过程中取得了很大的进展, 但其内在的构效关系尚不清楚.
本文对氧化亚铜纳米线进行不同处理, 制备了纳米颗粒和纳米片形貌的预催化剂, 并发现了预还原过程中形貌和晶面发生了重构, 对多碳产物的产生表现出最好的选择性, 其法拉第效率为67.5%. X射线衍射结果表明, 纳米片衍生的铜催化剂在预还原后发生了晶面的重构, 其中铜(100)晶面相对于其他两个晶面呈现大量暴露. 采用循环伏安法测试二氧化碳还原实验后三种电极的OH^-吸附曲线, 结果进一步证实了铜(100)晶面在预还原后大量暴露. 由于丰富的铜(100)晶面的选择性暴露可以增强CO的吸附并提高表面*CO的覆盖率, 进一步促进C‒C的二聚, 从而提高催化生成多碳产物的活性. X射线光电子能谱结果表明, 三种催化剂预还原后, 表面铜均呈现零价和一价, 没有二价铜的存在. 本文还比较了三种催化剂的双层电容, 并计算了它们的电化学活性面积, 以研究三种催化剂的粗糙度效应对二氧化碳还原产物的影响. 结果表明, 三种催化剂有着相似的粗糙度, 从而排除了由于粗糙度不同引起的二氧化碳还原产物不同分布的影响. 此外, 成功合成了铜(100)、铜(110)和铜(111)单晶电极, 并在相同条件下分别进行电催化二氧化碳还原研究. 结果表明, 铜(100)晶面更有利于电催化二氧化碳还原中多碳产物的生成. 综上可见, 预处理和结构演变对铜基电催化剂催化二氧化碳还原的产物分布影响显著, 为合理设计高效的二氧化碳还原电催化剂提供了一种新的策略.

关键词: 电催化, 二氧化碳还原, 氧化亚铜, 多碳产物, 晶面重构, 形貌

Abstract:

Electrocatalytic CO₂ conversion has been considered as a promising way to recycle CO₂ and produce sustainable fuels and chemicals. However, the efficient and highly selective electrochemical reduction of CO₂ directly into multi-carbon (C₂₊) products remains a great challenge. Herein, we synthesized three type catalysts with different morphologies based on Cu₂O nanowires, and studied their morphology and crystal facet reconstruction during the pre-reduction process. Benefiting from abundant exposure of Cu (100) crystal facet, the nanosheet structure derived Cu catalyst showed a high faradaic efficiency (FE) of 67.5% for C₂₊ products. Additionally, electrocatalytic CO₂ reduction studies were carried out on Cu(100), Cu(110), and Cu(111) single crystal electrodes, which verified that Cu(100) crystal facets are favorable for the C₂₊products in electrocatalytic CO₂ reduction. Our work showed that catalysts would reconstruct during the CO₂ reduction process and the importance in morphology and crystal facet control to obtain desired products.

Key words: Electrocatalytic CO₂ reduction, Cu₂O, Multi-carbon products, Crystal facet reconstruction, Morphology

付阳, 谢起贤, 武琳晓, 罗景山. 不同预处理的氧化亚铜纳米线电极诱导的晶面效应提升电化学CO₂还原为多碳产物[J]. 催化学报, 2022, 43(4): 1066-1073.

Yang Fu, Qixian Xie, Linxiao Wu, Jingshan Luo. Crystal facet effect induced by different pretreatment of Cu₂O nanowire electrode for enhanced electrochemical CO₂ reduction to C₂₊products[J]. Chinese Journal of Catalysis, 2022, 43(4): 1066-1073.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63981-5

https://www.cjcatal.com/CN/Y2022/V43/I4/1066

图/表 6

Fig. 1. (a) Schematic illustration of the preparation process of Cu-based nanowire, nanoparticle and nanosheet pre-catalysts. SEM images of NW (b-d), NP (e-g), NS (h-j) with different magnifications.

Fig. 2. (a) SEM image of NW-D Cu; TEM (b) and HRTEM (c) images of NW-D Cu with corresponding enlarged HRTEM image in the top right; (d) SEM image of NP-D Cu; (e) TEM image and the corresponding HRTEM image of NP-D Cu; (g) SEM image of NS-D Cu; (h,i) TEM and corresponding HRTEM of NS-D Cu with the enlarged HRTEM image in the top right.

Fig. 3. (a) XRD patterns of the NW-D Cu, NP-D Cu, and NS-D Cu; (b) Cu 2p1/2 and Cu 2p3/2 XPS spectra of the NW-D Cu, NP-D Cu, and NS-D Cu.

Fig. 4. CO2 reduction reaction performance in H-Cell. Faradaic efficiency of NW-D Cu (a), NP-D Cu (b) and NS-D Cu (c) in CO2-saturated 0.1 mol/L KHCO3 aqueous solution; Total current densities (d) and current densities of C1 (e), C2+ (f) and H2 (g) for NW, NP and NS; (h) The ratio of the C2+/C1 for NW-D Cu, NP-D Cu and NS-D Cu; (i) Long term stability and FE (C2H4) at -1.4 V (vs. RHE) of NS-D Cu electrode. All potential data were without iR-corrected.

Fig. 5. (a) CV curves in Ar-saturated 1.0 mol/L KOH of NW-D Cu, NP-D Cu and NS-D Cu at the scan rates of 50 mV s-1; Fitted OH-adsorption peaks of the NW-D Cu (b), NP-D Cu (c) and NS-D Cu (d) with the corresponding proportion of crystal planes in the inset.

Fig. 6. (a) XRD spectrum of the Cu (111), (200) and (220) single facets; Faradaic efficiency of Cu (111) (b), Cu (200) (c) and Cu (220) (d) in CO2-saturated 0.1 mol/L KHCO3 aqueous solution; (e) Faradaic efficiency of C2+ and C1 for Cu(111), Cu(220) and Cu(200) single facets; (f) The ratio of the C2+/C1 for Cu(111), Cu(220) and Cu(200) single facets.

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不同预处理的氧化亚铜纳米线电极诱导的晶面效应提升电化学CO₂还原为多碳产物

Crystal facet effect induced by different pretreatment of Cu₂O nanowire electrode for enhanced electrochemical CO₂ reduction to C₂₊products

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