电化学二氧化碳还原制甲酸催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2022-1533

摘要/Abstract

摘要：

随着日益增长的能源需求，人类社会对于传统碳基化石能源过度依赖，不仅加速了地球上有限能源储备的消耗，还导致大气中二氧化碳（CO₂）不断累积。如何对二氧化碳进行可持续的捕获再利用，实现高效的零碳网络循环，已成为人类亟需解决的重大挑战之一。近年来，使用绿色可持续电力的电化学二氧化碳还原反应（CO₂RR）生产增值化学品成为研究热点。本文首先介绍了CO₂RR的基本电化学反应原理；然后总结了电化学还原CO₂制备甲酸/甲酸盐的主要金属基催化剂，着重介绍了Bi、Sn、In三类金属基催化剂的设计调控策略；进一步概括了电化学相关的原位表征手段，分别介绍了原位光谱技术和原位X射线表征技术；最后对电催化二氧化碳还原研究领域的未来发展进行了展望。

关键词: 二氧化碳, 电化学还原, 甲酸, 金属基催化剂, 原位表征

Abstract:

With the ever-increasing energy demand, human society is over-reliant on traditional carbon-based fossil energy, which not only accelerates the consumption of the earth's limited energy reserves, but also leads to the continuous accumulation of carbon dioxide (CO₂) in the atmosphere. How to sustainably capture and reuse CO₂and achieve an efficient zero-carbon network cycle has become one of the major challenges that human beings urgently need to solve. In recent years, electrocatalytic CO₂ reduction reaction (CO₂RR) production of value-added chemicals using green sustainable electricity has become a research hotspot. In this review, we firstly introduce the basic electrochemical reaction principle of CO₂RR. Then we summarize the main metal-based catalysts for the electrochemical reduction of CO₂ to prepare formic acid/formate, and focus on the design and regulation strategies of three metal-based (Bi, Sn and In) catalysts. In addition, we generalize the in situ characterization methods related to CO₂RR, including in situ spectroscopic techniques and in situ X-ray characterization technique. Finally, the future opportunities and challenges for the electrocatalytic CO₂ reduction are prospected.

Key words: carbon dioxide, electrocatalytic reduction, formic acid, metal-based catalyst, in situ characterization

中图分类号:

O646

李喆, 李泽洋, 杨宇森, 卫敏. 电化学二氧化碳还原制甲酸催化剂的研究进展[J]. 化工进展, 2023, 42(1): 53-66.

LI Zhe, LI Zeyang, YANG Yusen, WEI Min. Research progress on catalysts for electrocatalytic reduction of carbon dioxide to formic acid[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 53-66.

图/表 12

图1 二氧化碳电化学还原示意图

表1 CO2物理化学性质[6,15]

物理/化学性质	数值
熔点/℃	-78.5
沸点/℃	-56.6
溶解度/g·L^-1	1.45
第一电离能/eV	13.79
电子结合能/eV	38

图2 部分产物的热力学电化学半反应及其对应电位（常温常压，pH=7的水溶液，V vs. RHE）

图3 CO2还原至甲酸反应途径示意图

图4 多种Bi基催化剂的调控设计[28,30-32]

图5 酸性电解质中的的CO2RR示意图及其性能[39]

图6 分别使用*COOH、*OCHO结合能作为描述符绘制火山型曲线（-0.9V vs. RHE）[41]

图7 Sn基金属氧化物催化剂及不同价态的影响[43,46-47]

图8 两种In基催化剂设计思路[56,58]

图9 饱和0.1mol/L KHCO3 D2O中，ED-Cu和P-Cu的原位ATR–SEIRAS分析[71]

图10 Bi2O3 NPs电化学转换过程的原位拉曼光谱[75]

图11 SnO2和F掺杂SnO2（FTO）的原位Sn k-edge XANES光谱及线性分析[47]

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