Recent advances in the electroreduction of carbon dioxide to formic acid over carbon-based materials
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摘要: 基于可再生、间歇性的能源驱动的二氧化碳（CO2）电还原制甲酸（HCOOH）技术是二氧化碳转化利用的重要途径。本文详细介绍了CO2的物理化学性质及其电还原生成HCOOH的反应机理；综述了近年来碳基材料在电还原CO2制HCOOH中的研究进展，包括无金属的碳催化剂和碳负载型催化剂。在此基础上，总结和评述了电化学反应器的设计和优化策略。以CO2电还原耦合甲醇电氧化反应为例，分析了CO2杂化电解技术的优势。最后，提出了目前电还原CO2制HCOOH的关键科学技术问题和未来的发展方向，以期为该技术的进一步发展提供新的思路和指导。Abstract: The electroreduction of carbon dioxide (CO2) driven by renewable energy is an important route for CO2 conversion and utilization. Formic acid (HCOOH), as an important chemical and safe hydrogen storage material, is one of the main and promising materials for CO2 electroreduction. The physical and chemical properties of CO2 and the reaction mechanisms for its electroreduction to HCOOH are outlined and the recent development of carbon-based catalysts, including metal-free carbon catalysts and carbon-supported catalysts, for CO2 electroreduction to HCOOH is reviewed. The design of reactors for HCOOH production and strategies for their optimization are summarized and discussed. Hybrid CO2 electrolysis technology is analyzed, such as electroreduction coupled with the methanol electrooxidation reaction. Lastly, key challenges and development trends for CO2 electroreduction to HCOOH are presented, which are expected to provide guidance for the development of this technique.
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Key words:
- Carbon-based materials /
- CO2 electroreduction /
- Formic acid /
- Reactor
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Figure 1. Two possible mechanisms for electroreduction of CO2 to HCOO−, where the C, O, H atoms and catalyst are represented by red, gray, blue, yellow colors.
Figure 2. (a) Linear sweep voltammetry curves over different GNDs catalysts for CO2RR. (b) FEHCOO− over different GNDs catalysts for CO2RR. (c) Models of carbon catalysts with different configurations containing oxygen functional groups. (d) Gibbs free energy of CO2RR and HER over carbon catalysts with different configurations of oxygen-containing functional groups[31]. Reprinted with permission by American Chemical Society.
Figure 3. (a) Fabrication of DEA-SnOx/C catalyst. (b) Mechanism diagram of electrochemical CO2RR to HCOO-[33]. Reprinted with permission by American Chemical Society. (c) Schematic illustration of the preparation of VO-SnOx/CF catalyst. (d, e) SEM images of VO-SnOx/CF[34]. Reprinted with permission by Royal Society of Chemistry. (f) Schematic diagram of electrochemical CO2RR on Cu@C catalyst. (g) Electrochemical performance over the Cu@C catalyst covering FEHCOOH and HCOOH formation rate[35]. Reprinted with permission by Elsevier.
Figure 4. (a) Schematic fabrication process for S-doped Bi2O3-CNT. (b) FEHCOOH over a series of catalysts at different applied voltages. (c) Schematic diagram of the S species-promoted effects on CO2RR to HCOOH[36]. Reprinted with permission by American Chemical Society. (d) Mechanism diagram for CO2RR to HCOOH over N, S-doped SnO2/NSC[37]. Reprinted with permission by American Chemical Society. (e) Schematic fabrication process for In-N-C[38]. Reprinted with permission by American Chemical Society.
Figure 5. (a) Preparation diagram of carbon nanorods-encapsulated Bi2O3 (Bi2O3@C). (b) TEM image of Bi2O3@C. (c) FEHCOOH over catalyst at different potentials vs. RHE[40]. Reprinted with permission by WILEY-VCH. (d) Schematic fabrication process for CuBi-C. (e) FEHCOOH over different catalysts under various voltages[41]. Reprinted with permission by Elsevier.
Figure 6. Scheme and comparison of four different reactors for producing HCOOH via CO2RR.
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