CO2还原和HCHO氧化耦合电催化反应系统高效益生产高附加值产物

doi:10.3866/PKU.WHXB202305028

物理化学学报 >> 2024, Vol. 40 >> Issue (5): 2305028.doi: 10.3866/PKU.WHXB202305028

CO₂还原和HCHO氧化耦合电催化反应系统高效益生产高附加值产物

吕旭东, 邵涛, 刘均炎, 叶萌, 刘升卫*()

中山大学, 环境科学与工程学院, 广东省环境污染控制与修复技术重点实验室, 广州 510006

收稿日期:2023-05-15 修回日期:2023-05-27 录用日期:2023-05-27 发布日期:2023-06-25
通讯作者: Email: liushw6@mail.sysu.edu.cn; Tel.: +86-15622151604 (刘升卫)
基金资助:
国家自然科学基金(51872341); 广东省“特支计划”科技创新青年拔尖人才项目(2019TQ05L196); 广东省科技计划项目(2021A1515010147)

Paired Electrochemical CO₂ Reduction and HCHO Oxidation for the Cost-Effective Production of Value-Added Chemicals

Xudong Lv, Tao Shao, Junyan Liu, Meng Ye, Shengwei Liu*()

Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou 510006, China

Received:2023-05-15 Revised:2023-05-27 Accepted:2023-05-27 Published:2023-06-25
Contact: Email: liushw6@mail.sysu.edu.cn; Tel.: +86-15622151604 (Shengwei Liu)
Supported by:
the National Natural Science Foundation of China(51872341); the Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program, China(2019TQ05L196); the Science and Technology Planning Project of Guangdong Province, China(2021A1515010147)

1. WHXB202305028-SI-5p.pdf(1120KB)

摘要/Abstract

摘要：

传统电化学CO₂还原(CO₂RR)系统中阳极发生的水氧化半反应(WOR)具有动力学缓慢、过电位大、能耗高等缺点，限制了CO₂RR系统的经济效益和应用。因此，本研究引入MnO₂阳极进行甲醛氧化半反应(FOR)以代替WOR，构建了一种新型CO₂RR/FOR耦合系统。与传统的CO₂RR/WOR系统相比，在相同的电压下，CO₂RR/FOR耦合系统的CO₂RR电流密度和产物的生成速率具有更大的优势。此外，在合适的电压下，CO₂RR/FOR耦合系统可以将HCHO选择性地转化为HCOOH。具体来说，两电极CO₂RR/FOR耦合系统中，在3.5 V的槽电压下，近90%的HCHO可以被去除，且HCHO转化为HCOOH的转化率约为48%。更重要的是，在不同的工作电流下，FOR相比于WOR所需电压更小。在−10 mA∙cm⁻²电流密度下，CO₂RR/FOR耦合系统能降低约210 mV的槽电压，并且其能耗比单独的CO₂RR系统和FOR系统的能耗之和降低45.13%。此外，当使用商业多晶硅太阳能电池作为电源时，在CO₂RR/FOR耦合系统中的阴极CO₂RR电流密度、产物的生成速率和阳极HCHO转化为HCOOH的选择性都可以实现较大的提升。目前的工作将进一步研究新型的CO₂RR耦合系统，以经济有效地将CO₂和有机污染物同时转化为有价值的化学品。

关键词: 二氧化碳还原, 甲醛氧化, 电化学耦合系统, 铜, 氧化锰

Abstract:

Due to rapid industrial development and human activities, CO₂ emissions have led to serious environmental/ecological problems and climate changes such as global warming. Due to this situation, achieving carbon neutrality has become an urgent mission to improve the future of mankind. The use of the electrocatalytic CO₂ reduction reaction (CO₂RR) to produce higher-value fuels and chemicals is an effective strategy for reducing CO₂ emissions and easing the energy crisis. The water oxidation half-reaction (WOR), which occurs at the anode in a traditional CO₂RR system, typically suffers from slow kinetics, a large overpotential, and high energy consumption. The organic pollutant formaldehyde (HCHO) is oxidized into industrial materials (such as formic acid) under neutral conditions, which is of great significance for the sustainable production of energy and lessening environmental pollution. In addition, the number of electron transfers involved and the required potential for the HCHO oxidation half-reaction (FOR) are smaller than those of WOR, suggesting that FOR could potentially replace WOR as a coupling reaction with CO₂ reduction. In this study, FOR at a MnO₂/CP anode is introduced to produce a novel paired CO₂RR/FOR system. The current density and generation rate of CO₂RR products in this paired CO₂RR/FOR system are generally larger than those of conventional CO₂RR/WOR systems at the same applied potential. Moreover, in paired CO₂RR/FOR systems, HCHO can be selectively converted into HCOOH at certain applied potentials. Nearly 90% of the HCHO can be selectively converted to HCOOH with a conversion efficiency of about 48% at a cell voltage of 3.5 V in a two-electrode paired CO₂RR/FOR system. More significantly, under a different working current, the potentials required for FOR are systemically smaller than those for WOR. At −10 mA∙cm⁻², the cell voltage of the paired CO₂RR/FOR system can be reduced by 210 mV, and the required electric energy for the paired CO₂RR/FOR system can be reduced by 45.13% compared with the sum of single CO₂RR and FOR systems. Notably, when a commercial polysilicon solar cell is used as the power supply, improvements in the current density, the generation rate of CO₂RR products, and the HCHO to HCOOH selectivity can be still achieved in the paired CO₂RR/FOR system. The present work will inspire further studies for developing novel paired CO₂RR systems for the cost-effective, simultaneous conversion of CO₂ and organic pollutants into valuable chemicals.

Key words: CO₂ reduction, HCHO oxidation, Paired electrochemical system, Cu, MnO₂

吕旭东, 邵涛, 刘均炎, 叶萌, 刘升卫. CO₂还原和HCHO氧化耦合电催化反应系统高效益生产高附加值产物[J]. 物理化学学报, 2024, 40(5), 2305028. doi: 10.3866/PKU.WHXB202305028

Xudong Lv, Tao Shao, Junyan Liu, Meng Ye, Shengwei Liu. Paired Electrochemical CO₂ Reduction and HCHO Oxidation for the Cost-Effective Production of Value-Added Chemicals[J]. Acta Phys. -Chim. Sin. 2024, 40(5), 2305028. doi: 10.3866/PKU.WHXB202305028

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202305028

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I5/2305028

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E_cell /V	CO₂ RR/WOR system				Paired CO₂ RR/FOR system
E_cell /V	E_anode/V	E_cathode/V		E_IR/V	E_anode/V	E_cathode/V	E_IR/V
2.0	1.05	−0.91	0.04		0.81	−1.11	0.08
2.5	1.15	−1.16	0.19		0.91	−1.23	0.36
3.0	1.19	−1.32	0.49		0.97	−1.39	0.64
3.5	1.26	−1.47	0.77		1.05	−1.52	0.93

J/(mA∙cm⁻²)	E_cathode/V	CO₂RR/WOR			Paired CO₂RR/FOR			E_IR/V	ΔE_cell/V	ΔQ/Q₁ (%)
J/(mA∙cm⁻²)	E_cathode/V	E_cell/V	E_anode/V	Q₁/J	E_cell/V	E_anode/V	Q₂/J	E_IR/V	ΔE_cell/V	ΔQ/Q₁ (%)
−1.00	−1.09	2.28	1.12	12.32	1.99	0.81	10.75	0.08	0.29	12.74
−2.00	−1.16	2.52	1.15	27.22	2.25	0.88	24.30	0.21	0.27	10.71
−3.00	−1.23	2.75	1.18	44.55	2.48	0.91	40.18	0.34	0.27	9.82
−4.00	−1.30	2.94	1.19	63.51	2.67	0.92	57.67	0.45	0.27	9.18
−5.00	−1.36	3.11	1.21	83.97	2.86	0.96	77.22	0.54	0.25	8.04
−6.00	−1.42	3.28	1.23	106.27	3.03	0.98	98.17	0.63	0.25	7.62
−7.00	−1.46	3.44	1.25	130.03	3.21	1.02	121.34	0.73	0.23	6.69
−8.00	−1.49	3.61	1.27	155.95	3.38	1.04	146.02	0.85	0.23	6.37
−9.00	−1.56	3.77	1.28	183.22	3.54	1.05	172.04	0.93	0.23	6.10
−10.00	−1.61	3.93	1.30	212.22	3.72	1.09	200.88	1.02	0.21	5.34
−11.00	−1.65	4.11	1.32	244.13	3.92	1.13	232.85	1.14	0.19	4.62
−12.00	−1.69	4.27	1.34	276.70	4.12	1.19	266.98	1.24	0.15	3.51
−13.00	−1.72	4.43	1.35	310.99	4.33	1.25	303.97	1.36	0.10	2.26
−14.00	−1.76	4.59	1.37	347.00	4.50	1.28	340.2	1.46	0.09	1.96
−16.00	−1.83	4.91	1.40	424.22	4.85	1.34	419.04	1.68	0.06	1.22

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CO₂还原和HCHO氧化耦合电催化反应系统高效益生产高附加值产物

Paired Electrochemical CO₂ Reduction and HCHO Oxidation for the Cost-Effective Production of Value-Added Chemicals

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