用于电催化合成过氧化氢的碳电极综述

HUANG Xian-huai; YANG Xin-ke; GUI Ling; LIU Shao-gen; WANG Kun; RONG Hong-wei; WEI Wei

doi:10.1016/S1872-5805(24)60846-2

用于电催化合成过氧化氢的碳电极综述

doi: 10.1016/S1872-5805(24)60846-2

黄显怀^1,,
杨鑫科¹,
桂玲¹,
刘绍根¹,
王坤¹,
荣宏伟^{2, 3},
韦伟^1, ,

1.
安徽建筑大学环境与能源工程学院市政工程系，安徽合肥 230601
2.
广州大学土木工程学院市政工程系，广东广州 51000606
3.
珠江三角洲水质安全与保护教育部重点实验室，广东广州 510006

基金项目: 国家自然科学基金（52370001）；安徽省重点研发开发项目（2023T07020011）；珠江三角洲水质安全与保护教育部重点实验室开放基金资助项目（KLWQCPRD-202306）；安徽省科技重大专项（202203a07020019）

详细信息

通讯作者:
韦　伟，博士，讲师. E-mail：weiw@ahjzu.edu.cn

中图分类号: TQ127.1⁺1
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- 被引次数: 0
出版历程
- 收稿日期: 2023-11-10
- 录用日期: 2024-02-27
- 修回日期: 2024-02-26
- 网络出版日期: 2024-02-28
- 刊出日期: 2024-04-20

Carbon electrodes for the electrocatalytic synthesis of hydrogen peroxide: A review

1.
Department of Municipal Engineering, School of Environment and Energy Engineering, Anhui Jianzhu University, Hefei 230601, China
2.
Department of Municipal Engineering, School of Civil Engineering, Guangzhou University, Guangzhou 510006, China
3.
Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education，Guangzhou 510006, China

Funds: This work was funded by the National Natural Science Foundation of China (52370001), the Anhui Provincial Key Research and Development Project (2023t07020011), the Opening Fund of Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education (KLWQCPRD-202306), and the Science and Technology Major Project of Anhui Province (202203a07020019)

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Author Bio:
黄显怀，博士，教授. E-mail：xhhuang@ahjzu.edu.cn

Corresponding author: WEI Wei, Ph.D, Lecturer. E-mail: weiw@ahjzu.edu.cn

摘要

摘要: 通过双电子（2e⁻）途径的电催化氧还原方式能够即时合成过氧化氢（H₂O₂），远超传统的蒽醌工艺。近年来，碳电极因具有良好的催化效果和优越的稳定性在电催化合成H₂O₂方面受到越来越多的关注。本综述结合材料改性与润湿性调整，从三相界面的角度考虑与H₂O₂合成速率及使用寿命的关系。介绍了碳电极的结构与电催化合成H₂O₂的原理，包括单质炭材料、无金属催化剂、贵金属催化剂与非贵金属催化剂4种主流催化剂；金属阳极与电解液对于三相界面的影响；碳电极润湿性与三相界面的关系，指出侧重于提高2e⁻途径选择性的改性方式也会对电极润湿性造成影响。此外，合理地设计电器原件与提升碳电极合成H₂O₂功效的关系。最后，讨论了当前碳电极电催化合成H₂O₂所面临的问题与未来的研究方向。
- 原位合成 /
- 过氧化氢 /
- 碳电极 /
- 固液气三相界面 /
- 润湿性
Abstract: Electrocatalytic oxygen reduction by a 2e⁻ pathway enables the instantaneous synthesis of H₂O₂, a process that is far superior to the conventional anthraquinone process. In recent years, the electrocatalytic synthesis of H₂O₂ using carbon electrodes has attracted more and more attention because of its excellent catalytic performance and superior stability. The relationship between material modification, wettability and the rate of H₂O₂ synthesis and service life is considered together with the three-phase interface. The structure of the carbon electrodes and the principles of electrocatalytic H₂O₂ synthesis are first introduced, and four major catalysts are reviewed, namely, monolithic carbon materials, metal-free catalysts, noble metal catalysts and non-precious metal catalysts. The effects of the metal anode and the electrolyte on the three-phase interface are described. The relationship between carbon electrode wettability and the three-phase interface is described, pointing out that modification focusing on improving the selectivity of the 2e⁻ pathway can also impact electrode wettability. In addition, the relationship between the design of the components in the electrochemical system and their effect on the efficiency of H₂O₂ synthesis is discussed for carbon electrodes. Finally, we present our analysis of the current problems in the electrocatalytic synthesis of H₂O₂ for carbon electrodes and future research directions.
- In situ synthesis /
- H₂O₂ /
- Carbon electrodes /
- Solid-liquid-gas three-phase interface /
- Wettability

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FIG. 3061. FIG. 3061.

FIG. 3061.. FIG. 3061.

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Figure 1. Schematic structure of the carbon electrode in the electrochemical synthesis of hydrogen peroxide^[15]. Reprinted with permission from Elsevier

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Figure 2. ORR mechanism of oxygen at the air cathode surface in an acidic medium (ORR mechanism at the air cathode surface under alkaline conditions is shown in parentheses)^[16]. Reprinted with permission from Elsevier

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Figure 3. Volcano plot of oxygen reduction activity of different metals as a function of oxygen binding energy(ΔE_O)^[43]. Reprinted with permission from Elsevier

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Figure 4. Concept for developing electrocatalysts with appropriate density of active sites: schematic representation of the different parameters controlling the catalytic performance of two-electron ORR catalysts^[88]. Reprinted with permission from Elsevier

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Figure 5. (a) Membrane-free electrolyser^[115]. Reprinted with permission from The Royal Society of Chemistry. (b) Conventional polymer electrolyser^[116]. Reprinted with permission from American Chemical Society. (c) Double-layer polymer electrolyser^[117]. Reprinted with permission from The American Association for the Advancement of Science. (d) Phase transfer device^[119]. Reprinted with permission from Elsevier

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Table 1. Effect of catalyst engineering on the synthesis of H₂O₂ from carbon electrodes

	Technique	Subtrate	Electrolytes/pH	Wettability	H₂O₂ yield	Selectiveness	Durability	Ref.
Monolithic carbon material	1000 °C 1% O₂	Porous carbon	0.5 mol·L⁻¹ Na₂SO₄	89.9°→0°	7.9→24.9 mg·L⁻¹	/	20 h	[61]
	600 °C calcination in air	Carbon black	0.1 mol·L⁻¹ Na₂SO₄	100°→79°	65.3→517.7 mg·L⁻¹	47.1%→56.1%	/	[62]
	Coated by electrochemically exfoliated graphene	Carbon cloth	0.05 mol·L⁻¹ K₂SO₄	138.4°→73.2°	251.4→450.8 mg·L⁻¹	/	/	[63]
Metal-free carbon-based catalysts	Heteroatom doping	P-CNTs	0.1 mol·L⁻¹ Na₂SO₄	/	419.5–1291.3 mg·L⁻¹·h⁻¹	88.5%	/	[64]
		N-Graphite (N 60.7%)	0.1 mol·L⁻¹ KOH	/	1286.9 mmol·g⁻¹·h⁻¹	~75%	/	[52]
		N-CMK3-IL	0.1 mol·L⁻¹ KOH	/	/	86%	/	[65]
		F-mrGO	0.1 mol·L⁻¹ KOH	/	430.8 mmol·g⁻¹·h⁻¹	~100%	/	[66]
	Introducing oxygen-containing functional groups	Carbon black	0.1 mol·L⁻¹ Na₂SO₄	57°→45°	83→120 mg·L⁻¹	50% increase		[67]
		O-CNTs	0.1 mol·L⁻¹ KOH		~3950 mg·L⁻¹·h⁻¹	~90%		[68]
		rGO-KOH	0.1 mol·L⁻¹ KOH		/	~100%		[69]
Precious metal catalysts		Pt-Hg	0.1 mol·L⁻¹ HClO₄	/	/	~90%		[70]
		Au-Pd	0.1 mol·L⁻¹ HClO₄	/	/	~95%		[71]
		Au-Pd-Ni	0.1 mol·L⁻¹ KOH	/	0.0591 mmol·g⁻¹·h⁻¹	/		[72]
		h-Pt1-CuS_x	0.1 mol·L⁻¹ HClO₄	/	~546 mmo·g⁻¹·h⁻¹	92%–96%	/	[73]
Non-precious metal catalysts		Co-N-C	0.1 mol·L⁻¹ HClO₄	/	80–275 mmol·g⁻¹·h⁻¹	~90%	/	[74]
		Ni-N₂O₂/C	0.1 mol·L⁻¹ KOH	/	5.9 mmol·g⁻¹·h⁻¹	96%	/	[75]
		Ni-O-C	0.1 mol·L⁻¹ KOH	/	59.3 mg·L⁻¹	82%	200 h	[76]
		Co1-NG(O)	0.1 mol·L⁻¹ KOH	/	~418 mmol·g⁻¹·h⁻¹	90%	/	[58]

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Table 2. Improvement of H₂O₂ production by wettability modification of carbon electrode

Objective	Technique	Substrate	Detail	Wetting angle	H₂O₂ yield	Ref.
Hydrophilic improvement	Functionalization	Porous carbon	Fabricate honeycomb carbon nanofibers with abundent OFGs	37.7°→ 0°	6 mmol L⁻¹	[106]
	Physical method	Graphite sheet	Alternating current glow discharge	/	35 → 119 µmol L⁻¹	[63]
	Chemical modification	Graphite felt	H₂SO₄, NaNO₃, KMnO₄ solution treatment followed by 900 °C NH₃ activation	120.3° → 61.5°	277 → 479 mg·L⁻¹	[107]
	Chemical modification	Graphite felt	0.5 mol L⁻¹ NaOH treatment followed by NaOH activated at 400 °C	127.3° → 0°	50 → 100 mg·L⁻¹	[108]
	Electrochemical techniques	Graphite felt	0–2 V (vs SCE) cyclical polarization	/	85 → 235 mg·L⁻¹	[109]
	Electrochemical techniques	Reticulated vitreous carbon	0–2 V (vs. Ag/AgCl) cyclical	/	18 → 64 mg·L⁻¹	[110]
Hydrophobic improvement	Using hydrophobic auxiliary materials or treatments	Graphite felt	Loaded with NPC carbonized by ZIF-8 nanocrystals as precursor	112.0° → 125.0°	11 → 113 mg·L⁻¹	[111]
		CB + graphite + PTFE	Decrease PTFE content in CL	107.1° → 141.1°	2131 → 3005 mg·L⁻¹	[112]
		Graphite felt	Modified by CB + PTFE followed by 360 °C calcination	68.4° → 141.0°	25 → 31 mg·cm⁻² h⁻¹	[93]
Constructing amphiphilic interface	Constrcting hydrophobic GSL and hydrophilic CL	Graphite felt	CB + PVDF facilitate hydrophilic; PTFE + 350 °C calcination facilitate hydrophobic	CL: 81.2° → 74.4° GSL: 81.2° → 137.7°	3 → 62 mg·L⁻¹	[113]
Constructing amphiphilic interface	Fabricating Janus electrode	Graphite felt	PTFE immersion to realize Hydrophobic; galvanostatic anodization to realize hydrophilic	CA increased after hydrophobic treatment and decreased after hydrophilic treatment	7 → 50 mg·L⁻¹	[114]

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