Co-N4大环配合物分子应用于异相电催化CO2还原

doi:10.1016/S1872-2067(21)63880-9

催化学报 ›› 2022, Vol. 43 ›› Issue (1): 104-109.DOI: 10.1016/S1872-2067(21)63880-9

Co-N₄大环配合物分子应用于异相电催化CO₂还原

林智超^a,†, 江占^a,†, 袁誉博^a, 李欢^a, 王洪轩^a, 唐仡嵘^a, 刘春晨^a, 梁永晔^a^,^b^,^*()

^a南方科技大学材料科学与工程系, 广东深圳518055
^b南方科技大学电厂能源材料广东省重点实验室, 广东深圳518055

收稿日期:2021-06-06 接受日期:2021-06-25 出版日期:2022-01-18 发布日期:2021-07-07
通讯作者: 梁永晔
作者简介:第一联系人：
^†共同第一作者.
基金资助:
广东省重点实验室(2018B030322001);国家自然科学基金(22075125)

Cobalt-N₄ macrocyclic complexes for heterogeneous electrocatalysis of the CO₂ reduction reaction

Zhichao Lin^a,†, Zhan Jiang^a,†, Yubo Yuan^a, Huan Li^a, Hongxuan Wang^a, Yirong Tang^a, Chunchen Liu^a, Yongye Liang^a^,^b^,^*()

^aDepartment of Materials Science and Engineering, Southern University of Science and Technology of China, Shenzhen 518055, Guangdong, China
^bGuangdong Provincial Key Laboratory of Energy Materials for Electric Power, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China

Received:2021-06-06 Accepted:2021-06-25 Online:2022-01-18 Published:2021-07-07
Contact: Yongye Liang
About author:* Tel: +86-755-88018306; E-mail: liangyy@sustech.edu.cn
First author contact:
^† Contributed equally to this work.
Supported by:
Guangdong Provincial Key Laboratory(2018B030322001);National Natural Science Foundation of China(22075125)

摘要/Abstract

摘要：

利用可再生能源产生的电能催化二氧化碳还原(CO₂RR)是可持续制备碳基化学品的一种潜在途径. 电催化剂是实现这个转化的关键, 目前还需要深入地研究机理去优化催化剂的设计. M-N₄结构的大环配合物是一类结构明确、性能易调控的分子电催化剂, 是研究结构-性能关系的理想平台. 其中, 金属酞菁在异相电催化CO₂RR中展现出较好的催化性能, 受到广泛关注. 而其它M-N₄结构大环配合物(如金属卟啉、金属咔咯)在异相电催化CO₂RR中报道较少, 且催化性能一般. 本文对比研究了酞菁钴(CoPc)、四苯基卟啉钴(CoTPP)和三苯基咔咯钴(CoTPC)三种分子异相电催化CO₂RR的性能, 揭示制约金属卟啉和金属咔咯分子应用于异相体系的原因, 并提出改进方法.
首先采用碳纳米管(CNT)复合的方法对三种分子进行了研究. 结果表明, 只有CoPc能够与CNT形成性能优异的复合电催化剂, 而CoTPP和CoTPC复合电催化剂几乎不具备活性. 这是因为这两种分子具有扭曲的苯环导致分子与CNT作用力弱, 在复合物里面只有很少的分子锚定在CNT上.
本文采用直接滴涂法制备三种分子与CNT物理混合电极, 并研究了分子载量对催化性能的影响. 结果表明, 在1.08 × 10^-8 mol cm^-2低分子载量时, CoTPP+CNT和CoTPC+CNT样品基本无活性, 它们的电催化活性随着分子载量的提升而显著增加. 在5.4 × 10^-7 mol cm^-2的高载量时, CoTPC+CNT和CoTPP+CNT样品在-0.67 V(相对可逆氢电极, 下同)的电位下分别展现出14.0和7.61 mA cm^-2的CO分电流密度, 是1.08 × 10^-8 mol cm^-2载量样品的8.7和7.9倍. 这说明对于CoTPP和CoTPC分子, 可以通过加大载量来增加与CNT作用几率, 从而提高电极活性. 然而, 基于CoPc制备的样品活性随着CoPc分子载量的增加变化不明显. 这是由于在低载量下CoPc分子已经很好地与CNT相互作用, 并且CNT上CoPc分子负载量是有限的, 继续增大载量只会导致聚集.
本文进一步发展一种聚乙烯吡啶(PVP)桥连的办法, 提升CoTPP和CoTPC在低载量下的电极活性. 聚乙烯链能够通过疏水作用缠绕在CNT上, 同时吡啶能够与分子金属中心配位, 从而为分子与CNT结合建立桥梁. 当分子载量为1.08 × 10^-8 mol cm^-2时, CoTPP+CNT/PVP在-0.67 V电位下展现出85%以上的CO法拉第效率, 而且CO分电流密度达到7.84 mA cm^-2, 是没有添加PVP对比样CoTPP+CNT的8倍. 由此可见, 分子与基底的相互作用强度对异相电催化CO₂RR的性能有重要影响. 对于与基底相互作用弱的大环配合物分子可以通过大分子载量的滴涂法或引入桥连分子来提高电极性能. 这些方法可以拓展到其它分子体系, 有助于构建高效的异相分子电催化剂.

关键词: CO₂还原, 酞菁钴, 咔咯钴, 卟啉钴, 异相电催化

Abstract:

Metal-N₄ (M-N₄) macrocyclic complexes are interesting electrocatalysts due to their well-defined structures and rich molecular tuning. Among them, metal phthalocyanines have been widely studied for the carbon dioxide reduction reaction (CO₂RR) in heterogeneous systems and demonstrated good electrocatalytic performance. However, other complexes like metal corroles and metal porphyrins are much less explored, and often show inferior performances. In this study, three cobalt macrocyclic complexes, cobalt phthalocyanine, cobalt meso-tetraphenylporphyrin, and cobalt meso-triphenylcorrole (CoPc, CoTPP and CoTPC) are investigated in heterogeneous electrocatalysis of CO₂RR. Although CoPc/carbon nanotube (CNT) hybrid exhibits high electrocatalytic activity, CNT hybridization does not work for CoTPC and CoTPP that hold weak interactions with CNTs. By the drop-dry method with a high molecular loading of 5.4 × 10^-7 mol cm^-2, CoTPC and CoTPP could deliver appreciable electrode activities. Poly(4-vinylpyridine) (PVP) introduction is further demonstrated as a facile method to afford enhanced activities for CoTPP at low molecular loadings through enhancing molecule-substrate interactions. The partial current density of carbon monoxide for CoTPP+CNT/PVP is around 8 times higher than the sample without PVP at -0.67 V versus reversible hydrogen electrode. This work provides solutions to enhance the electrode activities of molecular electrocatalysts with weak substrate interactions in heterogeneous systems.

Key words: CO₂ reduction, Cobalt phthalocyanine, Cobalt corrole, Cobalt porphyrin, Heterogeneous electrocatalysis

林智超, 江占, 袁誉博, 李欢, 王洪轩, 唐仡嵘, 刘春晨, 梁永晔. Co-N₄大环配合物分子应用于异相电催化CO₂还原[J]. 催化学报, 2022, 43(1): 104-109.

Zhichao Lin, Zhan Jiang, Yubo Yuan, Huan Li, Hongxuan Wang, Yirong Tang, Chunchen Liu, Yongye Liang. Cobalt-N₄ macrocyclic complexes for heterogeneous electrocatalysis of the CO₂ reduction reaction[J]. Chinese Journal of Catalysis, 2022, 43(1): 104-109.

×
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(21)63880-9

https://www.cjcatal.com/CN/Y2022/V43/I1/104

图/表 4

Fig. 1. (a) Chemical structures of CoPc, CoTPC and CoTPP; (b) LSVs of CoPc/CNT, CoTPC/CNT and CoTPP/CNT in a CO2-saturated 0.5 M KHCO3 solution at v = 5 mV s-1; (c) Cyclic voltammograms of 10 mM DMF solutions of CoTPC and CoTPP containing 0.1 M Bu4NPF6, recorded on a GC electrode at v = 0.10 V s-1 under Ar (dash) or CO2 (solid).

Fig. 2. The fabrication process of drop-dry samples on CFP. Each sphere stands for one molecule: CoPc (green), CoTPC (red) and CoTPP (blue).

Fig. 3. (a) LSVs of CoPc+CNT, CoTPC+CNT and CoTPP+CNT mixtures with different molecular contents in a CO2 saturated 0.5 M KHCO3 solution at v = 5 mV s-1; Chronoamperometric curves (b) and FEs (c) of CoPc+CNT-e, chronoamperometric curves (d) and FEs (e) of CoTPC+CNT-e, and chronoamperometric curves (f) and FEs (g) of CoTPP+CNT-e at different voltages in a CO2 saturated 0.5 M KHCO3 solution; (h) Partial current densites of CO. Currents were taken average from 40 min eletrocatalysis at appoximately -0.67 V (vs. RHE); (i) AC impedance tests of CoPc+CNT-c, CoTPC+CNT-c and CoTPP+CNT-c mixtures on glassy carbon electrodes in CO2 saturated 0.5 M KHCO3 solution with a scanning frequency range from 200 kHz to 100 Hz with an a.c. amplitude of 5 mV. The solid lines are guides to the eye.

Fig. 4. (a) Schematic diagram for Cobalt-N4 macrocyclic complexes immobilized on CNT with the assistance of PVP; (b) LSVs of CoPc+CNT/PVP, CoTPC+CNT/PVP, CoTPP+CNT/PVP, CoTPP+CNT-a and CoPc/CNT MDEs in CO2 saturated 0.5 M KHCO3 solution at v = 5 mV s-1; Chronoamperometric curves (c) and FEs (d) at different voltages of CoTPP+CNT/PVP.

参考文献

[1]	Y. S. Wu, Z. Jiang, X. Lu, Y. Y. Liang, H. L. Wang, Nature, 2019, 575, 639-642.
[2]	P. De Luna, C. Hahn, D. Higgins, S. A. Jaffer, T. F. Jaramillo, E. H. Sargent, Science, 2019, 364, eaav3506.
[3]	T. Sakakura, J. C. Choi, H. Yasuda, Chem. Rev., 2007, 107, 2365-2387.
[4]	J. L. Qiao, Y. Y. Liu, F. Hong, J. J. Zhang, Chem. Soc. Rev., 2014, 43, 631-675.
[5]	A. S. Varela, W. Ju, P. Strasser, Adv. Energy Mater., 2018, 8, 1703614.
[6]	S. Meshitsuka, M. Ichikawa, K. Tamaru, J. Chem. Soc. Chem. Commun., 1974, 158-159
[7]	X. Zhang, Y. Wang, M. Gu, M. Y. Wang, Z. S. Zhang, W. Y. Pan, Z. Jiang, H. Z. Zheng, M. Lucero, H. L. Wang, G. E. Sterbinsky, Q. Ma, Y. G. Wang, Z. X. Feng, J. Li, H. J. Dai, Y. Y. Liang, Nat. Energy, 2020, 5, 684-692.
[8]	X. Zhang, Z. S. Wu, X. Zhang, L. W. Li, Y. Y. Li, H. M. Xu, X. X. Li, X. L. Yu, Z. S. Zhang, Y. Y. Liang, H. L. Wang, Nat. Commun., 2017, 8, 14675.
[9]	K. Takahashi, K. Hiratsuka, H. Sasaki, S. Toshima, Chem. Lett., 1979, 305-308.
[10]	K. Guo, H. T. Lei, X. L. Li, Z. Y. Zhang, Y. B. Wang, H. B. Guo, W. Zhang, Chin. J. Catal., 2021, 42, 1439-1444.
[11]	S. Lin, C. S. Diercks, Y. B. Zhang, N. Kornienko, E. M. Nichols, Y. B. Zhao, A. R. Paris, D. Kim, P. D. Yang, O. M. Yaghi, C. J. Chang, Science, 2015, 349, 1208-1213.
[12]	J. Grodkowski, P. Neta, E. Fujita, A. Mahammed, L. Simkhovich, Z. Gross, J. Phys. Chem. A, 2002, 106, 4772-4778.
[13]	C. M. Lieber, N. S. Lewis, J. Am. Chem. Soc., 1984, 106, 5033-5034.
[14]	W. Sinha, A. Mahammed, N. Fridman, Y. Diskin-Posner, L. J. W. Shimon, Z. Gross, Chem. Commun., 2019, 55, 11912-11915.
[15]	E. Boutin, L. Merakeb, B. Ma, B. Boudy, M. Wang, J. Bonin, E. Anxolabehere-Mallart, M. Robert, Chem. Soc. Rev., 2020, 49, 5772-809.
[16]	C. C. Yan, L. Lin, G. X. Wang, X. H. Bao, Chin. J. Catal., 2019, 40, 23-37.
[17]	X. M. Hu, M. H. Rønne, S. U. Pedersen, T. Skrydstrup, K. Daasbjerg, Angew. Chem. Int. Ed., 2017, 56, 6468-6472.
[18]	A. Maurin, M. Robert, J. Am. Chem. Soc., 2016, 138, 2492-2495.
[19]	A. J. Sathrum, C. P. Kubiak, J. Phys. Chem. Lett., 2011, 2, 2372-2379.
[20]	R. Francke, B. Schille, M. Roemelt, Chem. Rev., 2018, 118, 4631-4701.
[21]	M. H. Zhu, R. Q. Ye, K. Jin, N. Lazouski, K. Manthiram, ACS Energy Lett., 2018, 3, 1381-1386.
[22]	Z. Jiang, Y. Wang, X. Zhang, H. Z. Zheng, X. J. Wang, Y. Liang, Nano Res., 2019, 12, 2330-2334.
[23]	N. Morlanés, K. Takanabe, V. Rodionov, ACS Catal., 2016, 6, 3092-3095.
[24]	Z. Zhang, J. P. Xiao, X. J. Chen, S. Yu, L. Yu, R. Si, Y. Wang, S. H. Wang, X. G. Meng, Y. Wang, Z. Q. Tian, D. H. Deng, Angew. Chem. Int. Ed., 2018, 57, 16339-16342.
[25]	N. Furuya, S. Koide, Electrochim. Acta, 1991, 36, 1309-1313.
[26]	A. N. Marianov, Y. J. Jiang, Appl. Catal. B, 2019, 244, 881-888.
[27]	M. H. Zhu, J. C. Chen, L. B. Huang, R. Q. Ye, J. Xu, Y. F. Han, Angew. Chem. Int. Ed., 2019, 58, 6595-6599.
[28]	M. H. Zhu, J. C. Chen, R. Guo, J. Xu, X. C. Fang, Y. F. Han, Appl. Catal. B, 2019, 251, 112-118.
[29]	J. Shen, M. J. Kolb, A. J. Göttle, M. T. M. Koper, J. Phys. Chem. C, 2016, 120, 15714-15721.
[30]	P. Ballirano, R. Caminiti, C. Ercolani, A. Maras, M. A. Orrù, J. Am. Chem. Soc., 1998, 120, 12798-12807.
[31]	R. Paolesse, S. Licoccia, G. Bandoli, A. Dolmella, T. Boschi, Inorg. Chem., 1994, 33, 1171-1176.
[32]	E. D. Stevens, J. Am. Chem. Soc., 1981, 103, 5087-5095.
[33]	W. W. Kramer, C. C. L. McCrory, Chem. Sci., 2016, 7, 2506-2515.
[34]	Y. Pan, R. Lin, Y. J. Chen, S. J. Liu, W. Zhu, X. Cao, W. X. Chen, K. L. Wu, W. C. Cheong, Y. Wang, L. R. Zheng, J. Luo, Y. Lin, Y. Q. Liu, C. G. Liu, J. Li, Q. Lu, X. Chen, D. S. Wang, Q. Peng, C. Chen, Y. D. Li, J. Am. Chem. Soc., 2018, 140, 4218-4221.

Co-N₄大环配合物分子应用于异相电催化CO₂还原

Cobalt-N₄ macrocyclic complexes for heterogeneous electrocatalysis of the CO₂ reduction reaction

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 4

参考文献

相关文章 15

编辑推荐

Metrics

[1]	高晖, 张恭, 程东方, 王永涛, 赵静, 李晓芝, 杜晓伟, 赵志坚, 王拓, 张鹏, 巩金龙. 构建Cu台阶位促进电催化CO₂还原制醇类化学品的研究[J]. 催化学报, 2023, 52(9): 187-195.
[2]	张雯, 宋彩彩, 王嘉蔚, 蔡舒婷, 高梦语, 冯有祥, 鲁统部. 双向主客体作用促进水溶液中选择性光催化CO₂还原与醇氧化[J]. 催化学报, 2023, 52(9): 176-186.
[3]	宋明明, 宋相海, 刘鑫, 周伟强, 霍鹏伟. ZnIn₂S₄/MOF-808微球结构S型异质结光催化剂的制备及其光还原CO₂性能研究[J]. 催化学报, 2023, 51(8): 180-192.
[4]	邵秀丽, 李可, 李静萍, 程强, 王国宏, 王楷. 揭示NiS@Ta₂O₅纳米纤维中梯型电荷转移路径及光催化CO₂转化性能[J]. 催化学报, 2023, 51(8): 193-203.
[5]	李嘉明, 李源, 王小田, 杨直雄, 张高科. TiO₂上原子分散的Fe位点促进光催化CO₂还原: 增强的催化活性、 DFT计算和机制洞察[J]. 催化学报, 2023, 51(8): 145-156.
[6]	刘赵春, 宗雪, Dionisios G. Vlachos, Ivo A. W. Filot, Emiel J. M. Hensen. 金属掺杂SnO₂电化学还原CO₂制甲酸的计算研究[J]. 催化学报, 2023, 50(7): 249-259.
[7]	林敏, 罗美兰, 柳勇志, 沈锦妮, 龙金林, 张子重. 一维S型异质结W₁₈O₄₉-SiC海胆状复合催化剂增强光催化CO₂还原[J]. 催化学报, 2023, 50(7): 239-248.
[8]	李慧杰, 池漫洲, 辛兴, 王瑞杰, 刘天府, 吕红金, 杨国昱. 异金属取代的多金属氧酸盐@光响应型金属-有机框架用于高选择性光催化CO₂还原[J]. 催化学报, 2023, 50(7): 343-351.
[9]	Sang Eon Jun, Sungkyun Choi, Jaehyun Kim, Ki Chang Kwon, Sun Hwa Park, Ho Won Jang. 用于电化学能量转换反应的非贵金属单原子催化剂[J]. 催化学报, 2023, 50(7): 195-214.
[10]	李孜孜, 王嘉蔚, 黄衍钧, 欧阳钢锋. 钴(II)酞菁全氟化策略用于提升非贵金属体系中光催化还原CO₂性能[J]. 催化学报, 2023, 49(6): 160-167.
[11]	王娇, 朱芳芳, 陈必义, 邓爽, 胡博琛, 刘洪, 武猛, 郝金辉, 李龙华, 施伟东. B原子掺杂调控CuIn纳米合金电子结构以实现电化学CO₂还原宽电位活性[J]. 催化学报, 2023, 49(6): 132-140.
[12]	何厚伟, 王中辽, 代凯, 李素文, 张金锋. LSPR效应增强碳包覆In₂O₃/W₁₈O₄₉ S型异质结用于高效CO₂光还原[J]. 催化学报, 2023, 48(5): 267-278.
[13]	魏艳, 段睿智, 张巧兰, 曹有智, 王金圆, 王冰, 万雯瑞, 刘春燕, 陈加藏, 高红, 景欢旺. TiO₂/TiN纳米管异质结用于光电催化CO₂还原: 氮辅助活性氢机制[J]. 催化学报, 2023, 47(4): 243-253.
[14]	陈成成, 刘芳庭, 张巧钰, 张正国, 刘琼, 方晓明. 理论设计和实验研究吡啶掺杂聚合氮化碳提升光催化CO₂还原性能[J]. 催化学报, 2023, 46(3): 91-102.
[15]	张平, 陈浩, 陈林, 熊鹰, 孙子其, 杨浩宇, 付莹珂, 张亚萍, 廖婷, 李斐. 基于NiZn层状双金属氢氧化物制备高效电催化CO₂还原的原子分散Ni-N-C催化剂[J]. 催化学报, 2023, 45(2): 152-161.