具有高曲率结构的枝晶状Cu/Cu2O在H型电解池中实现二氧化碳到C2产物的快速高效还原

doi:10.1016/S1872-2067(24)60079-3

催化学报 ›› 2024, Vol. 63: 144-153.DOI: 10.1016/S1872-2067(24)60079-3

具有高曲率结构的枝晶状Cu/Cu₂O在H型电解池中实现二氧化碳到C₂产物的快速高效还原

邵磊, 胡博琛, 郝金辉, 荆俊杰, 施伟东^*(), 陈敏^*()

江苏大学化学化工学院，江苏镇江 212013

收稿日期:2024-03-20 接受日期:2024-05-31 出版日期:2024-08-18 发布日期:2024-08-19
通讯作者: *电子信箱: swd1978@ujs.edu.cn (施伟东),chenmin3226@sina.com (陈敏)
基金资助:
国家自然科学基金(22225808);国家自然科学基金(22075111);中德合作集团项目(GZ1579);江苏省国际科技创新支撑计划合作项目(BZ2022045)

A dendritic Cu/Cu₂O structure with high curvature enables rapid and efficient reduction of carbon dioxide to C₂ in an H-cell

Lei Shao, Bochen Hu, Jinhui Hao, Junjie Jin, Weidong Shi^*(), Min Chen^*()

School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China

Received:2024-03-20 Accepted:2024-05-31 Online:2024-08-18 Published:2024-08-19
Contact: *E-mail: swd1978@ujs.edu.cn (W. Shi), chenmin3226@sina.com (M. Chen).
Supported by:
National Natural Science Foundation of China(22225808);National Natural Science Foundation of China(22075111);Sino-German Cooperation Group Project(GZ1579);Jiangsu Province Innovation Support Program International Science and Technology Cooperation Project(BZ2022045)

摘要/Abstract

摘要：

将CO₂电还原(CO₂RR)转化为可再生燃料, 如CH₄, C₂H₄, C₂H₅OH, 被认为是实现碳循环和储存可再生能源的有效途径. 与其他材料相比, 铜(Cu)基催化剂对*CO中间体具有合适的吸附能, 能够将CO₂还原为多碳产物. 但是, Cu基催化剂在高电流密度(大于100 mA cm^‒2)下的催化活性较低, 选择性较差, 这是亟待解决的问题. 通过Cu⁰/Cu⁺界面策略可以提高CO₂RR为C₂产物的选择性. 然而, 在H型电解池中, 由于传质限制, 高质子浓度的溶液容易引起析氢反应(HER), 同时催化剂表面发生的HER竞争反应也导致了产物电流密度的降低. 随着反应进行, 催化剂表面活性位点上CO₂浓度逐渐降低, 而溶液中的CO₂不能及时补充到催化剂表面, 进一步加剧了这一问题.

本文在CO₂气氛下合成了具有高曲率结构的枝晶状Cu/Cu₂O. 实验结果表明, 得到的枝晶状Cu/Cu₂O不仅具有较高的C₂H₄ (51.42%)选择性, 而且C₂类产物(如C₂H₄, C₂H₅OH等)的总选择性达到69.82%, 同时在H型电解池中具有较高C₂H₄ (95.3 mA cm^‒2)和C₂产物分电流密度(129.5 mA cm^‒2). 有限元模拟计算结果表明, 具有高曲率结构的枝晶状Cu/Cu₂O表面产生了增强的局部电场, 从而提高了催化剂表面局部CO₂浓度. 结合弛豫时间分布分析结果, 发现高曲率的枝晶状结构能够主动吸附催化剂周围溶液环境中的CO₂, 提高了反应的传质速率, 实现了还原过程中产物的高电流密度. 在实验过程中, 通过改变催化剂表面Cu⁰/Cu⁺的原子比, 研究电子结构对催化剂性能的影响. 在Cu⁰/Cu⁺的最佳原子比时, 电荷转移电阻最小, 中间体的解吸速率慢, 更有利于C₂产物的生成. 密度泛函理论计算结果也表明, 在Cu⁰/Cu⁺界面处, 将CO₂还原为C₂的关键步骤(即决速步骤)所涉及反应中间体具有较低的吉布斯自由能, 从而促进了C₂H₄形成. Cu/Cu₂O催化剂还具有较低的Cu的d能带中心, 增强了*CO在催化剂表面的吸附稳定性, 促进了C₂产物的形成, 因此在快速传质条件下, Cu⁰/Cu⁺界面获得的是C₂产物. 最后, 利用净现值模型计算了H型电解池工业应用的经济可行性, 结果表明, H型电解池是否具有广阔的工业前景, 取决于催化剂是否同时具有高选择性和高电流密度的能力.

综上所述, 将特殊形貌与催化剂成分相结合的设计策略, 不仅可以将两者的优势相结合, 还实现了单一条件时难以达到的效果, 显著提升了CO₂RR催化剂的性能. 本研究将对CO₂RR催化剂的设计和实际应用提供参考.

关键词: CO₂还原反应, 高电流, 枝晶状结构;, Cu/Cu₂O, H型电解池

Abstract:

Electrocatalytic reduction of CO₂ (CO₂RR) to multicarbon products is an efficient approach for addressing the energy crisis and achieving carbon neutrality. In H-cells, achieving high-current C₂ products is challenging because of the inefficient mass transfer of the catalyst and the presence of the hydrogen evolution reaction (HER). In this study, dendritic Cu/Cu₂O with abundant Cu⁰/Cu⁺ interfaces and numerous dendritic curves was synthesized in a CO₂ atmosphere, resulting in the high selectivity and current density of the C₂ products. Dendritic Cu/Cu₂O achieved a C₂ Faradaic efficiency of 69.8% and a C₂ partial current density of 129.5 mA cm^‒2 in an H-cell. Finite element simulations showed that a dendritic structure with a high curvature generates a strong electric field, leading to a localized CO₂ concentration. Additionally, DRT analysis showed that a dendritic structure with a high curvature actively adsorbed the surrounding high concentration of CO₂, enhancing the mass transfer rate and achieving a high current density. During the experiment, the impact of the electronic structure on the performance of the catalyst was investigated by varying the atomic ratio of Cu⁰/Cu⁺ on the catalyst surface, which resulted in improved ethylene selectivity. Under the optimal atomic ratio of Cu⁰/Cu⁺, the charge transfer resistance was minimized, and the desorption rate of the intermediates was low, favoring C₂ generation. Density functional theory calculations indicated that the Cu⁰/Cu⁺ interfaces exhibited a lower Gibbs free energy for the rate-determining step, enhancing C₂H₄ formation. The Cu/Cu₂O catalyst also exhibited a low Cu d-band center, which enhanced the adsorption stability of *CO on the surface and facilitated C₂ formation. This observation explained the higher yield of C₂ products at the Cu⁰/Cu⁺ interface than that of H₂ under rapid mass transfer. The results of the net present value model showed that the H-cell holds promising industrial prospects, contingent upon it being a catalyst with both high selectivity and high current density. This approach of integrating the structure and composition provides new insights for advancing the CO₂RR towards high-current C₂ products.

Key words: Reduction of CO₂, High current, Dendritic structure, Cu/Cu₂O, H-cell

邵磊, 胡博琛, 郝金辉, 荆俊杰, 施伟东, 陈敏. 具有高曲率结构的枝晶状Cu/Cu₂O在H型电解池中实现二氧化碳到C₂产物的快速高效还原[J]. 催化学报, 2024, 63: 144-153.

Lei Shao, Bochen Hu, Jinhui Hao, Junjie Jin, Weidong Shi, Min Chen. A dendritic Cu/Cu₂O structure with high curvature enables rapid and efficient reduction of carbon dioxide to C₂ in an H-cell[J]. Chinese Journal of Catalysis, 2024, 63: 144-153.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60079-3

https://www.cjcatal.com/CN/Y2024/V63/I8/144

图/表 5

Fig. 1. Structural characterization of Cu/Cu2O. (a) Schematic of dendritic Cu synthesis. (b,c) SEM images. (d-i) HRTEM images.

Fig. 2. (a) XRD pattern of various Cu/Cu2O. (b) Cu 2p XPS spectra of Cu/Cu2O, Cu/Cu2O-1.7V, and Cu/Cu2O-1.9V. (c) Cu LMM Auger of Cu/Cu2O, Cu/Cu2O-1.7V, and Cu/Cu2O-1.9V. (d) Atomic contents of the Cu functional groups (at%) calculated from the XPS spectra of the Cu/Cu2O, Cu/Cu2O-1.7V and Cu/Cu2O-1.9V catalysts. (e) Cu 2p XPS spectra of Cu/Cu2O by Ar etching at 0, 30, 60, and 90 nm after CO2RR. (f) Cu LMM Auger of Cu/Cu2O by Ar etching at 0, 30, 60, and 90 nm after CO2RR.

Fig. 3. Electrochemical performance of CO2RR. (a) Cu/Cu2O. (b,c) FEs of C2H4 and C2 from the Cu/Cu2O, Cu/Cu2O-1.7V, Cu/Cu2O-1.9V, Cu and Cu2O catalysts. (d) Partial current densities of ethylene from the Cu/Cu2O, Cu/Cu2O-1.7V, and Cu/Cu2O-1.9V catalysts at -1.88 V (vs. RHE) in 1 mol L-1 KHCO3. (e) The relationship between the JC2 and FEC2 of each catalyst from previous studies (see Table 1) and this study. (f) Stability test of CO2RR over Cu/Cu2O (blue line, Jtotal; yellow ball, FEC2H4).

Fig. 4. (a) Computed electric field and Surface K+ density on the Cu/Cu2O. (b) Surface K+ density and current density on the Cu/Cu2O. (c) K+ density and current density as functions of the electric field intensity at the curve. (d) The in situ Raman spectra of Cu/Cu2O at potential ranges from -1.68 to -2.08 VRHE and OCP.

Fig. 5. DFT calculation. (a) Gibbs free energy of an intermediate compound between the CO2 to C2H4 conversion on Cu, Cu2O and Cu/Cu2O. (b) The partial DOS (PDOS) for the Cu, Cu2O and Cu/Cu2O catalysts. (c) The positive and negative charges are shown in yellow and cyan on Cu/Cu2O. (d) Gibbs free energy of an intermediate compound between the CO to CO2 conversion on Cu, Cu2O and Cu/Cu2O. (e) Structural diagram of the intermediate for the calculation simulation on Cu/Cu2O (Cu (blue), O (red), C (gray) and H (white)).

参考文献

[1]	S. I. Seneviratne, M. G. Donat, A. J. Pitman, R. Knutti, R. L. Wilby, Nature, 2016, 529, 477-483.
[2]	J. Yu, J. Wang, Y. Ma, J. Zhou, Y. Wang, P. Lu, J. Yin, R. Ye, Z. Zhu, Z. Fan, Adv. Funct. Mater., 2021, 31, 2102151.
[3]	M. K. Birhanu, M. C. Tsai, A. W. Kahsay, C. T. Chen, T. S. Zeleke, K. B. Ibrahim, C. J. Huang, W. N. Su, B. J. Hwang, Adv. Mater. Interfaces, 2018, 5, 1800919.
[4]	W. Ye, X. Guo, T. Ma, Chem. Eng. J., 2021, 414, 128825.
[5]	G. M. Tomboc, S. Choi, T. Kwon, Y. J. Hwang, K. Lee, Adv. Mater., 2020, 32, 1908398.
[6]	J. Fu, K. Liu, K. Jiang, H. Li, P. An, W. Li, N. Zhang, H. Li, X. Xu, H. Zhou, D. Tang, X. Wang, X. Qiu, M. Liu, Adv. Sci., 2019, 6, 1900796.
[7]	K. Jiang, Y. Huang, G. Zeng, F. M. Toma, W. A. Goddard, A. T. Bell, ACS Energy Lett., 2020, 5, 1206-1214.
[8]	C. Tang, J. Shi, X. Bai, A. Hu, N. Xuan, Y. Yue, T. Ye, B. Liu, P. Li, P. Zhuang, J. Shen, Y. Liu, Z. Sun, ACS Catal., 2020, 10, 2026-2032.
[9]	Y. Oh, J. Park, Y. Kim, M. Shim, T.-S. Kim, J. Y. Park, H. R. Byon, J. Mater. Chem. A, 2021, 9, 11210-11218.
[10]	L. Bian, Z.-Y. Zhang, H. Tian, N.-N. Tian, Z. Ma, Z.-L. Wang, Chin. J. Catal., 2023, 54, 199-211.
[11]	K. Yao, Y. Xia, J. Li, N. Wang, J. Han, C. Gao, M. Han, G. Shen, Y. Liu, A. Seifitokaldani, X. Sun, H. Liang, J. Mater. Chem. A, 2020, 8, 11117-11123.
[12]	P. De Luna, R. Quintero-Bermudez, C.-T. Dinh, M. B. Ross, O. S. Bushuyev, P. Todorović, T. Regier, S. O. Kelley, P. Yang, E. H. Sargent, Nat. Catal., 2018, 1, 103-110.
[13]	H. Li, T. Liu, P. Wei, L. Lin, D. Gao, G. Wang, X. Bao, Angew. Chem. Int. Ed., 2021, 60, 14329-14333.
[14]	J. Jiao, R. Lin, S. Liu, W.-C. Cheong, C. Zhang, Z. Chen, Y. Pan, J. Tang, K. Wu, S.-F. Hung, H. M. Chen, L. Zheng, Q. Lu, X. Yang, B. Xu, H. Xiao, J. Li, D. Wang, Q. Peng, C. Chen, Y. Li, Nat. Chem., 2019, 11, 222-228.
[15]	J. Zhang, Y. Wang, Z. Li, S. Xia, R. Cai, L. Ma, T. Zhang, J. Ackley, S. Yang, Y. Wu, J. Wu, Adv. Sci., 2022, 9, 2200454.
[16]	H. Yang, S. Li, Q. Xu, Chin. J. Catal., 2023, 48, 32-65.
[17]	M. Wang, H. Chen, M. Wang, J. Wang, Y. Tuo, W. Li, S. Zhou, L. Kong, G. Liu, L. Jiang, G. Wang, Angew. Chem. Int. Ed., 2023, 62, e202306456.
[18]	M. Liu, Y. Pang, B. Zhang, P. De Luna, O. Voznyy, J. Xu, X. Zheng, C. T. Dinh, F. Fan, C. Cao, F. P. G. de Arquer, T. S. Safaei, A. Mepham, A. Klinkova, E. Kumacheva, T. Filleter, D. Sinton, S. O. Kelley, E. H. Sargent, Nature, 2016, 537, 382-386.
[19]	H. Li, H. Zhou, Y. Zhou, J. Hu, M. Miyauchi, J. Fu, M. Liu, Chin. J. Catal., 2022, 43, 519-525.
[20]	D. Wu, C. Dong, D. Wu, J. Fu, H. Liu, S. Hu, Z. Jiang, S. Z. Qiao, X.-W. Du, J. Mater. Chem. A, 2018, 6, 9373-9377.
[21]	J. Yu, M. Yang, J. Zhang, Q. Ge, A. Zimina, T. Pruessmann, L. Zheng, J.-D. Grunwaldt, J. Sun, ACS Catal., 2020, 10, 14694-14706.
[22]	M. Ye, T. Shao, J. Liu, C. Li, B. Song, S. Liu, Appl. Surf. Sci., 2023, 622, 156981.
[23]	P. Wang, S. Meng, B. Zhang, M. He, P. Li, C. Yang, G. Li, Z. Li, J. Am. Chem. Soc., 2023, 145, 26133-26143.
[24]	J. Yuan, S. Chen, Y. Zhang, R. Li, J. Zhang, T. Peng, Adv. Mater., 2022, 34, 2203139.
[25]	Q. Wu, R. Du, P. Wang, G. I. N. Waterhouse, J. Li, Y. Qiu, K. Yan, Y. Zhao, W.-W. Zhao, H.-J. Tsai, M.-C. Chen, S.-F. Hung, X. Wang, G. Chen, ACS Nano, 2023, 17, 12884-12894.
[26]	X. Zhong, T. Yang, S. Liang, Z. Zhong, H. Deng, Small, 2023, 19, 2303185.
[27]	B. Ni, K. Wang, T. He, Y. Gong, L. Gu, J. Zhuang, X. Wang, Adv. Energy Mater., 2018, 8, 1702313.
[28]	L. Wang, K. Zhao, Z. Qi, Y. Yang, W. Luo, W. Yang, L. Li, J. Hao, W. Shi, Inorg. Chem., 2023, 62, 2470-2479.
[29]	H. Jiang, Z. Hou, Y. Luo, Angew. Chem. Int. Ed., 2017, 56, 15617-15621.
[30]	D. Liu, X. Li, S. Chen, H. Yan, C. Wang, C. Wu, Y. A. Haleem, S. Duan, J. Lu, B. Ge, P. M. Ajayan, Y. Luo, J. Jiang, L. Song, Nat. Energy, 2019, 4, 512-518.
[31]	Z.-Z. Niu, F.-Y. Gao, X.-L. Zhang, P.-P. Yang, R. Liu, L.-P. Chi, Z.-Z. Wu, S. Qin, X. Yu, M.-R. Gao, J. Am. Chem. Soc., 2021, 143, 8011-8021.
[32]	J. Chen, B. Ma, Z. Xie, W. Li, Y. Yang, M. Mu, X. Zou, B. Zhao, W. Song, Appl. Catal. B, 2023, 325, 122350.
[33]	X. Song, L. Xu, X. Sun, B. Han, Sci. China Chem., 2023, 66, 315-323.
[34]	Y. Yang, A. He, H. Li, Q. Zou, Z. Liu, C. Tao, J. Du, ACS Catal., 2022, 12, 12942-12953.
[35]	Y. Huang, A. D. Handoko, P. Hirunsit, B. S. Yeo, ACS Catal., 2017, 7, 1749-1756.
[36]	M. Jouny, W. Luc, F. Jiao, Ind. Eng. Chem. Res., 2018, 57, 2165-2177.

具有高曲率结构的枝晶状Cu/Cu₂O在H型电解池中实现二氧化碳到C₂产物的快速高效还原

A dendritic Cu/Cu₂O structure with high curvature enables rapid and efficient reduction of carbon dioxide to C₂ in an H-cell

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 5

参考文献

相关文章 5

编辑推荐

Metrics

[1]	李志鹏, 刘晓斌, 于青平, 屈欣悦, 万均, 肖振宇, 迟京起, 王磊. 用于高电流密度析氢反应电催化剂的研究进展[J]. 催化学报, 2024, 63(8): 33-60.
[2]	申珅玉, 郭庆丰, 武甜甜, 苏亚琼. 电催化CO₂还原过程中非均相界面的动态行为[J]. 催化学报, 2023, 53(10): 52-71.
[3]	孟翔宇, 李睿, 杨峻懿, 许世明, 张辰晨, 尤可嘉, 马宝春, 管红霞, 丁勇. 六核环状钴配合物用于光催化CO₂到CO转化[J]. 催化学报, 2022, 43(9): 2414-2424.
[4]	刘清港, 马俊国, 陈晨. 纳米催化剂的理性设计与精准调控[J]. 催化学报, 2022, 43(4): 898-912.
[5]	高海峡, 刘康, 罗涛, 陈羽, 胡俊华, 傅俊伟, 刘敏. 单原子Co位点的CO₂还原反应路径:局部配位环境的影响[J]. 催化学报, 2022, 43(3): 832-838.