自支撑Bi@Cu纳米树电极高效电化学还原CO2制甲酸

doi:10.15541/jim20230590

无机材料学报 ›› 2024, Vol. 39 ›› Issue (7): 810-818.DOI: 10.15541/jim20230590 CSTR: 32189.14.10.15541/jim20230590

自支撑Bi@Cu纳米树电极高效电化学还原CO₂制甲酸

施桐¹^,²(), 甘乔炜², 刘东², 张莹², 冯浩²(), 李强¹^,²()

1.西安交通大学能源与动力工程学院, 动力工程多相流国家重点实验室, 西安 710049
2.南京理工大学能源与动力工程学院, 电子设备热控制工信部重点实验室, 南京 210094

收稿日期:2023-12-21 修回日期:2024-01-30 出版日期:2024-07-20 网络出版日期:2024-02-26
通讯作者: 冯浩, 副教授. E-mail: fenghao@njust.edu.cn;
李强, 教授. E-mail: liqiang@njust.edu.cn
作者简介:施桐(1997-), 男, 博士研究生. E-mail: shitong@stu.xjtu.edu.cn
基金资助:
国家自然科学基金(52488201);江苏省前沿引领技术基础重大项目(BK20232022)

Boost Electrochemical Reduction of CO₂ to Formate Using a Self-supporting Bi@Cu Nanotree Electrode

SHI Tong¹^,²(), GAN Qiaowei², LIU Dong², ZHANG Ying², FENG Hao²(), LI Qiang¹^,²()

1. State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an 710049, China
2. MIIT Key Laboratory of Thermal Control of Electronic Equipment, School of Energy and Power Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

Received:2023-12-21 Revised:2024-01-30 Published:2024-07-20 Online:2024-02-26
Contact: FENG Hao, associate professor. E-mail: fenghao@njust.edu.cn;
LI Qiang, professor. E-mail: liqiang@njust.edu.cn
About author:SHI Tong (1997-), male, PhD candidate. E-mail: shitong@stu.xjtu.edu.cn
Supported by:
National Natural Science Foundation of China(52488201);Natural Science Foundation of Jiangsu Province(BK20232022)

摘要/Abstract

摘要：

利用电化学方法将CO₂转化为高值化学品是实现碳中和目标的一条有效途径。制备高性能电极是实现CO₂高效转化的关键一环。常规喷涂法所制电极中催化层与集流体间的不良接触会严重影响电催化活性以及稳定性。为此, 本研究结合电化学沉积和离子置换反应法, 构建了一种原位生长的Bi@Cu纳米树(Bi@Cu NTs)自支撑电极。自支撑纳米树结构在降低界面电阻、确保空间结构稳定的同时, 为反应提供了丰富的活性位点和发达的孔隙结构, 进而实现CO₂分子、电解液离子以及电子的协同传输, 并进一步促进电化学CO₂转化。实验结果表明, Bi@Cu NTs电极在电化学活性和长期运行稳定性方面表现出色。在-1.4~-0.8 V (vs. RHE)的宽工作电位窗口范围内, 甲酸选择性均超过90%; 在-1.2 V的工作电位下, 该电极同时实现了高达97.9%的甲酸选择性和170.6 mA·cm^-2的电流密度。此外, 该电极在-1.0 V下经过50 h持续电解, 获得了超过90%的平均甲酸选择性及大于110 mA·cm^-2的平均电流密度, 且性能未见明显衰减, 稳定性优异。

关键词: 电化学还原CO₂, 甲酸, 自支撑电极, 纳米树结构, Bi纳米片

Abstract:

Electrochemical reduction of CO₂ to high value-added hydrocarbon fuels and chemicals has emerged as an effective strategy to achieve carbon neutrality. In conventional electrocatalytic powder-coated electrodes fabricated by spraying method, poor contact between electrocatalyst and substrate can severely impact the electrocatalytic activity and stability. Herein, a self-supporting nanotree electrode (Bi@Cu NTs) for efficient electroreduction from CO₂ to formate was structured by combing facile electrodeposition method and galvanic replacement reaction. The advantages of self-supporting nanotree structure including: 1) minimization of the interfacial resistance and improvement of the spatial structure stability; 2) rich active sites and plentiful pore structures. The charge transfer resistant could be effectively reduced while ensuring the stability of the electrode operation. Results demonstrated that the prepared Bi@Cu NTs electrode exhibited outstanding performance for CO₂ conversion in both electrochemical activity and long-term operation stability. In a wide operating potential window from -1.4 to -0.8 V (vs. RHE), the proposed Bi@Cu NTs electrode presented excellent formate selectivity, where the Faradaic efficiency of CO₂-to-formate (FE_Formate) at each operating potential was above 90%. Typically, at -1.2 V, the proposed electrode achieved a high FE_Formate of 97.9% and a current density of 170.6 mA·cm^-2, simultaneously. Meanwhile, the self-supporting Bi@Cu NTs electrode also revealed excellent stability in a long-term operation, as evidenced by maintaining an average FE_Formate of more than 90% and an average current density higher than 110 mA·cm^-2 over 50 h of continuous electrolysis at a controlled potential of -1.0 V without any degradation in performance.

Key words: electrochemical reduction CO₂, formate, self-supporting electrode, nanotree structure, Bi nanosheet

中图分类号:

TQ151

施桐, 甘乔炜, 刘东, 张莹, 冯浩, 李强. 自支撑Bi@Cu纳米树电极高效电化学还原CO₂制甲酸[J]. 无机材料学报, 2024, 39(7): 810-818.

SHI Tong, GAN Qiaowei, LIU Dong, ZHANG Ying, FENG Hao, LI Qiang. Boost Electrochemical Reduction of CO₂ to Formate Using a Self-supporting Bi@Cu Nanotree Electrode[J]. Journal of Inorganic Materials, 2024, 39(7): 810-818.

图/表 12

图S1 (a)用于电化学CO2RR测试的流动池结构; (b)装配后的流动式反应池; (c)测试系统示意图

Fig. S1 (a) Flow-cell structure for electrochemical CO2 RR measurement; (b) Assembled flow-cell; (c) Schematic of the test system

图1 Bi@Cu NTs电极制备流程示意图

Fig. 1 Schematic diagram of Bi@Cu NTs electrode preparation

图2 形貌表征与元素分布

Fig. 2 Morphology and element distribution (a-d) SEM images of (a, b) Cu NDs electrode and (c, d) Bi@Cu NTs electrode; (e1-e4) Regional EDS mapping results of nanotree structure

图3 晶相特征与表面化学态

Fig. 3 Crystal characteristics and surface chemical states (a) XRD patterns of blank carbon paper and Bi@Cu NTs electrode; (b) HRTEM image, high-resolution (c) Bi4f and (d) O1s XPS spectra of Bi@Cu NTs electrode

图4 电化学活性面积与交流阻抗谱

Fig. 4 ECSA and AC impedance spectra (a, b) CV curves of (a) Cu NDs and (b) Bi@Cu NTs electrodes; (c) Comparison of Cdl of different electrodes; (d) Nyquist plots and corresponding fitting curves of commercial Bi nanopowder, Cu NDs and Bi@Cu NTs electrodes with inset showing equivalent circuit Colorful figures are available on website

表S1 不同制备电极的EIS拟合结果

Table S1 EIS fitting results of different prepared electrodes

Electrode	R_Ω/Ω	R_ct/Ω
Cu NDs	2.11	9.95
Bi@Cu NTs	1.83	2.28
Commercial Bi nanopowder	2.92	23.54

图5 CO2RR性能对比

Fig. 5 CO2RR performance comparison (a, c) I-t curves and (b, d) Faraday efficiency distributions with corresponding average current density of (a, b) commercial Bi nanopowder electrode and (c, d) Bi@Cu NTs electrode; (e) Comparison of distributions of FEFormate and JFormate of different electrodes; Colorful figures are available on website

图6 Cu NDs以及Bi@Cu NTs电极在不同电位下的HER(左)与CO2RR活性(右)分布

Fig. 6 Activity distributions of hydrogen evolution (left) and CO2 reduction reaction (right) of Cu NDs and Bi@Cu NTs electrodes at different potentials Colorful figures is available on website

图7 Bi@Cu NTs电极在-1.0 V恒电位下50 h的长时间稳定性测试

Fig. 7 Long-term stability test of Bi@Cu NTs electrode at the constant potential of -1.0 V for up to 50 h

表S2 Bi@Cu NTs电极与近期研究报道的在相同/相似测试条件下电化学还原CO2制甲酸性能比较

Table S2 Comparison of the electrochemical reduction of CO2 to formate performance on Bi@Cu NTs electrode with recent reports under the same/similar conditions

Catalyst	Electrolyte	Potential/ V (vs. RHE)	Current density/ (mA·cm^-2)	FE_Formate/%	Stability test	Ref.
Bi₁₉Br₃S₂₇	1 mol·L^-1 KOH	-1.0	~94	~82	20 h (~10 mA·cm^-2 with FE_Formate of 97% in H-cell)	[S1]
Bi₁₉Br₃S₂₇	1 mol·L^-1 KOH	-1.2	150	~90	20 h (~10 mA·cm^-2 with FE_Formate of 97% in H-cell)	[S1]
SOR Bi@C NPs	1 mol·L^-1 KOH	-1.12	100	90	18 h (~12 mA·cm^-2 with FE_Formate of 92% in H-cell)	[S2]
Self-supporting Bi-Sb nanoleaf	1 mol·L^-1 KOH	-1.2	160	81.3	25 h (160 mA·cm^-2 with FE_Formate of 81.3% in flow-cell)	[S3]
MIL-68(In)-NH₂	1 mol·L^-1 KOH	-1.1	114	94.4	24 h (at -1.1 V (vs. RHE), FE_Formate over 90% in flow-cell)	[S4]
MOD-BiIn	1 mol·L^-1 KOH	-1.4	~142	~96	12 h (100 mA·cm^-2 with FE_Formate of ~95% in flow-cell)	[S5]
Bi₂O₂SO₄	1 mol·L^-1 KOH	-1.2	163.5	97.2	12 h (91.5 mA·cm^-2 with FE_Formate of ~96% in flow-cell)	[S6]
BOC_R	1 mol·L^-1 KOH	-1.1	168.9	93.55	16 h (at -0.9 V (vs. RHE), FE_Formate over 90% in flow-cell)	[S7]
SnO₂/PANI	1 mol·L^-1 KHCO₃	-1.2	23.5	72	6 h (at -1.2 V (vs. RHE), FE_Formate of ~ 70% in flow-cell)	[S8]
Bi@NCFs	0.5 mol·L^-1 KHCO₃	-1.0	116	91	48 h (~12 mA·cm^-2 with FE_Formate over 81.3% in H-cell)	[S9]
Self-supporting Bi@Cu NTs	1 mol·L^-1 KOH	-1.2	170.6	97.9	50 h (~110 mA·cm^-2 with FE_Formate over 90% in flow-cell)	This work
Self-supporting Bi@Cu NTs	1 mol·L^-1 KOH	-1.4	242.2	96.7	50 h (~110 mA·cm^-2 with FE_Formate over 90% in flow-cell)	This work

图8 本研究与文献报道的CO2转化制甲酸相关工作性能对比[24⇓⇓⇓⇓⇓⇓-31]

Fig. 8 Comparison of this work with reported performances of CO2-to-formate[23⇓⇓⇓⇓⇓⇓⇓-31] (a) FEFormate; (b) Current density

图9 Bi@Cu NTs电极在恒电位-1.0 V下运行不同时间(0, 3, 45以及90 s)的原位拉曼光谱图

Fig. 9 In-situ Raman spectra of Bi@Cu NTs electrode at constant potential of -1.0 V with different run time (0, 3, 45 and 90 s) OCP: Open circuit potential

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自支撑Bi@Cu纳米树电极高效电化学还原CO₂制甲酸

Boost Electrochemical Reduction of CO₂ to Formate Using a Self-supporting Bi@Cu Nanotree Electrode

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