从富含缺陷的碳载体到酞菁钴的质子供给用于增强CO2电还原

doi:10.1016/S1872-2067(24)60061-6

催化学报 ›› 2024, Vol. 62: 190-197.DOI: 10.1016/S1872-2067(24)60061-6

从富含缺陷的碳载体到酞菁钴的质子供给用于增强CO₂电还原

梅子雯, 陈克军, 谭耀, 刘秋文, 陈琴, 王其忧, 汪喜庆, 蔡超, 刘康^*(), 傅俊伟^*(), 刘敏^*()

中南大学物理学院, 湖南省二氧化碳绿色资源化利用国际联合研究中心, 湖南长沙 410083

收稿日期:2024-02-28 接受日期:2024-04-29 出版日期:2024-07-18 发布日期:2024-07-10
通讯作者: *电子邮箱: minliu@csu.edu.cn (刘敏), fujunwei@csu.edu.cn (傅俊伟), lkfillz@csu.edu.cn (刘康).
基金资助:
国家自然科学基金(22376222);国家自然科学基金(52372253);国家自然科学基金(52202125);湖南省科技厅科技创新项目(2023RC1012);中南大学前沿交叉项目(2023QYJC012);中南大学创新驱动研究项目(2023CXQD042)

Proton feeding from defect-rich carbon support to cobalt phthalocyanine for efficient CO₂ electroreduction

Ziwen Mei, Kejun Chen, Yao Tan, Qiuwen Liu, Qin Chen, Qiyou Wang, Xiqing Wang, Chao Cai, Kang Liu^*(), Junwei Fu^*(), Min Liu^*()

Hunan Joint International Research Center for Carbon Dioxide Resource Utilization, School of Physics, Central South University, Changsha 410083, Hunan, China

Received:2024-02-28 Accepted:2024-04-29 Online:2024-07-18 Published:2024-07-10
Contact: *E-mail: minliu@csu.edu.cn (M. Liu), fujunwei@csu.edu.cn (J. Fu), lkfillz@csu.edu.cn (K. Liu).
Supported by:
National Natural Science Foundation of China(22376222);National Natural Science Foundation of China(52372253);National Natural Science Foundation of China(52202125);Science and Technology Innovation Program of Hunan Province(2023RC1012);Central South University Research Pro-gramme of Advanced Interdisciplinary Studies(2023QYJC012);Central South University Innovation-Driven Research Programme(2023CXQD042)

摘要/Abstract

摘要：

利用可再生电力将二氧化碳转化为高附加值产品的电催化二氧化碳还原反应(CO₂RR)是一项具有革命性潜力的技术, 因而备受关注. 其中, 一氧化碳被视为CO₂RR中最具经济效益的产物之一, 可直接利用费托合成工艺将其用于合成醛、酮、烃类等产品. 酞菁钴(CoPc)作为单位点催化剂, 因其高原子利用率和高催化选择性能, 在二氧化碳转化为一氧化碳过程中具有很大优势. 然而, CoPc无法为CO₂RR中的质子化过程提供足够质子, 导致其在工业大电流密度下的效率较低. 因此, 探索一种能够解决CO₂RR中质子供给不足问题的高效电催化剂对于提升CO₂RR的性能至关重要.

本文设计了具有增强质子供给作用的缺陷碳纳米管(d-CNT), 将其作为导电载体分散CoPc, 用于制备CoPc/d-CNT电催化剂. 通过引入富缺陷的碳纳米管(d-CNT), 加速水解离进而增加CO₂RR的质子供给量. X射线光电子能谱、X射线吸收近边光谱和扩展X射线吸收精细结构谱结果表明, CoPc/d-CNT成功合成, 同时保留了CoPc完整的Co-N₄配位结构. 透射电镜、粉末X射线衍射谱和拉曼光谱共同表明, d-CNT表面缺陷相对于商用CNT明显增加. 动力学实验和原位衰减全反射表面增强红外吸收光谱研究表明, 含大量缺陷的d-CNT具有加速水解离的能力, 显著提高了二氧化碳还原反应过程中的质子供给, 从而促进了CoPc上CO₂活化生成*COOH. 同时, 密度泛函理论计算结果表明, d-CNT表面缺陷位点上从吸附水(*H₂O)到质子水(H₃O⁺)的吉布斯自由能为0.74 eV, 远低于CNT (超过2 eV), 表明d-CNT促进了水解过程和质子传递, 再次证实了d-CNT降低了水分子解离的势垒. 通过实验和理论的共同验证, 阐明了d-CNT中的缺陷能够促进水解离, 改善CO₂RR反应过程中质子供给, 增强CoPc高效催化CO₂RR的能力. 因此, CoPc/d-CNT混合材料表现出较好的催化性能. 在电流密度为500 mA cm^-2的流动电池中, CoPc/d-CNT的CO法拉第效率(FE_CO)高达96%. 相对而言, CoPc/CNT在200 mA cm^-2时FE_CO已经下降到90%以下. 此外, 在150 mA cm⁻²的电流密度下, CoPc/d-CNT能够在20 h内维持FE_CO超过90%.

综上, 本文通过引入具有水解离能力的缺陷碳位点, 解决了单位点催化剂CoPc在CO₂RR中质子供给不足的问题, 为设计高性能催化剂提供了新见解.

关键词: 碳缺陷, 二氧化碳还原反应, 酞菁钴, 质子供给, 电催化

Abstract:

Electrocatalytic CO₂ reduction reaction (CO₂RR) holds significant promise for sustainable energy conversion, with cobalt phthalocyanine (CoPc) emerging as a notable catalyst due to its high CO selectivity. However, CoPc's efficacy is hindered by its limited ability to provide sufficient proton for the protonation process, particularly at industrial current densities. Herein, we introduce defect-engineered carbon nanotubes (d-CNT) to augment proton feeding for CO₂RR over CoPc, achieved by expediting water dissociation. Our kinetic measurements and in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy reveal d-CNT significantly enhances proton feeding, thereby facilitating CO₂ activation to *COOH in CoPc. Density functional theory calculations corroborate these findings, illustrating that d-CNT decreases the barrier to water dissociation. Consequently, the CoPc/d-CNT mixture demonstrates robust performance, achieving 500 mA cm^-2 for CO₂RR with CO selectivity exceeding 96%. Notably, CoPc/d-CNT remains stability for a duration of 20 h under a substantial current density of 150 mA cm^-2. The study broadens the scope of practical applications for molecular catalysts in CO₂RR, marking a significant step towards sustainable energy conversion.

Key words: Carbon defectCO₂ reduction reaction, Cobalt phthalocyanine, Proton feeding, Electrocatlysis

梅子雯, 陈克军, 谭耀, 刘秋文, 陈琴, 王其忧, 汪喜庆, 蔡超, 刘康, 傅俊伟, 刘敏. 从富含缺陷的碳载体到酞菁钴的质子供给用于增强CO₂电还原[J]. 催化学报, 2024, 62: 190-197.

Ziwen Mei, Kejun Chen, Yao Tan, Qiuwen Liu, Qin Chen, Qiyou Wang, Xiqing Wang, Chao Cai, Kang Liu, Junwei Fu, Min Liu. Proton feeding from defect-rich carbon support to cobalt phthalocyanine for efficient CO₂ electroreduction[J]. Chinese Journal of Catalysis, 2024, 62: 190-197.

×
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)60061-6

https://www.cjcatal.com/CN/Y2024/V62/I7/190

图/表 5

Fig. 1. (a) Schematic diagram of the synthetic pathway about CoPc/d-CNT. (b) XPS survey of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT. The inset shows the peaks of Co 2p3/2 and Co 2p1/2 in CNT, d-CNT, CoPc/CNT and CoPc/d-CNT. (c) High-resolution Co 2p XPS spectra of CoPc/CNT and CoPc/d-CNT. XANES spectra of Co K-edge (d) and EXAFS spectra of Co K-edge (e).

Fig. 2. (a,b) TEM images of CoPc/CNT and CoPc/d-CNT. (c) HAADF-STEM image and element mapping of CoPc/d-CNT. (d) XRD patterns of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT. (e) Raman spectra of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT.

Fig. 3. (a) LSV of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT based on 0.5 mol L?1 CO2-saturated KHCO3 electrolyte in the H-cell. (b) KIE of CoPc/CNT and CoPc/d-CNT measured at -0.55 V (vs. RHE) in a 0.5 mol L?1 CO2-saturated KHCO3 electrolyte. In-situ ATR-SEIRAS of CoPc/d-CNT (c) and CoPc/CNT (d).

Fig. 4. (a,b) Theoretically computed model of d-CNT with *H2O and H3O+. (c,d) Theoretically computed model of CNT with *H2O and H3O+. (e) Reaction free energy of d-CNT (red) and CNT (green) from *H2O to H3O+.

Fig. 5. (a) LSV of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT based on CO2 saturation in H-cell. (b) I-V curve of CoPc/CNT and CoPc/d-CNT in flow cell. (c) FECO of CoPc/CNT and CoPc/d-CNT. (d) Performance comparison chart. (e) Stability of CoPc/d-CNT at 150 mA cm?2 in flow cell.

参考文献

[1]	G. Chen, H. Li, Y. Zhou, C. Cai, K. Liu, J. Hu, H. Li, J. Fu, M. Liu, Nanoscale, 2021, 13, 13604-13609.
[2]	W. Ma, S. Xie, X.-G. Zhang, F. Sun, J. Kang, Z. Jiang, Q. Zhang, D.-Y. Wu, Y. Wang, Nat. Commun., 2019, 10, 892.
[3]	X. Wang, Q. Chen, Y. Zhou, Y. Tan, Y. Wang, H. Li, Y. Chen, M. Sayed, R. A. Geioushy, N. K. Allam, J. Fu, Y. Sun, M. Liu, Nano Res., 2023, 17, 1101-1106.
[4]	X.-D. Zhang, K. Liu, J.-W. Fu, H.-M. Li, H. Pan, J.-H. Hu, M. Liu, Front. Phys., 2021, 16, 63500.
[5]	Z. Li, J.-W. Wang, Y. Huang, G. Ouyang, Chin. J. Catal., 2023, 49, 160-167.
[6]	Y. Fan, C. Wang, D. Ma, X. Bao, Chin. J. Catal., 2010, 31, 302-306.
[7]	J. Fu, S. Wang, Z. Wang, K. Liu, H. Li, H. Liu, J. Hu, X. Xu, H. Li, M. Liu, Front. Phys., 2020, 15, 33201.
[8]	H. Gu, L. Zhong, G. Shi, J. Li, K. Yu, J. Li, S. Zhang, C. Zhu, S. Chen, C. Yang, Y. Kong, C. Chen, S. Li, J. Zhang, L. Zhang, J. Am. Chem. Soc., 2021, 143, 8679-8688.
[9]	K. Liu, J. Fu, L. Zhu, X. Zhang, H. Li, H. Liu, J. Hu, M. Liu, Nanoscale, 2020, 12, 4903-4908.
[10]	W. Zheng, D. Wang, W. Cui, X. Sang, X. Qin, Z. Zhao, Z. Li, B. Yang, M. Zhong, L. Lei, Q. Zheng, S. Yao, G. Wu, Y. Hou, Energy Environ. Sci., 2023, 16, 1007-1015.
[11]	K. Chen, M. Cao, Y. Lin, J. Fu, H. Liao, Y. Zhou, H. Li, X. Qiu, J. Hu, X. Zheng, M. Shakouri, Q. Xiao, Y. Hu, J. Li, J. Liu, E. Cortes, M. Liu, Adv. Funct. Mater., 2022, 32, 2111322.
[12]	K. Chen, M. Cao, G. Ni, S. Chen, H. Liao, L. Zhu, H. Li, J. Fu, J. Hu, E. Cortes, M. Liu, Appl. Catal. B, 2022, 306, 121093.
[13]	K. Chen, K. Liu, P. An, H. Li, Y. Lin, J. Hu, C. Jia, J. Fu, H. Li, H. Liu, Z. Lin, W. Li, J. Li, Y.-R. Lu, T.-S. Chan, N. Zhang, M. Liu, Nat. Commun., 2020, 11, 4173.
[14]	S. Yang, Y. Yu, X. Gao, Z. Zhang, F. Wang, Chem. Soc. Rev., 2021, 50, 12985-13011.
[15]	S. Ren, D. Joulie, D. Salvatore, K. Torbensen, M. Wang, M. Robert, C. P. Berlinguette, Science, 2019, 365, 367-369.
[16]	J. Zhao, J. Qiu, X. Gou, C. Hua, B. Chen, Chin. J. Catal., 2016, 37, 571-578.
[17]	Y. J. Zhang, B. Liang, Y. Z. Pan, R. He, Chin. J. Catal., 2003, 24, 765-768.
[18]	J. Zhu, S. Mu, Adv. Funct. Mater., 2020, 30, 2001097.
[19]	W. Zheng, D. Wang, Y. Zhang, S. Zheng, B. Yang, Z. Li, R. D. Rodriguez, T. Zhang, L. Lei, S. Yao, Y. Hou, Nano Energy, 2023, 105, 107980.
[20]	H. Zhang, J. Gao, D. Raciti, A. S. Hall, Nat. Catal., 2023, 6, 807-817.
[21]	X. Wang, X. Sang, C.-L. Dong, S. Yao, L. Shuai, J. Lu, B. Yang, Z. Li, L. Lei, M. Qiu, L. Dai, Y. Hou, Angew. Chem. Int. Ed., 2021, 60, 11959-11965.
[22]	Y. Wang, P. Han, X. Lv, L. Zhang, G. Zheng, Joule, 2018, 2, 2551-2582.
[23]	S. Chen, X. Li, C.-W. Kao, T. Luo, K. Chen, J. Fu, C. Ma, H. Li, M. Li, T.-S. Chan, M. Liu, Angew. Chem. Int. Ed., 2022, 61, e202206233.
[24]	Y. Jia, L. Zhang, A. Du, G. Gao, J. Chen, X. Yan, C. L. Brown, X. Yao, Adv. Mater., 2016, 28, 9532-9538.
[25]	K. Wu, Y. Zhang, Z. Yong, Q. Li, Acta Phys.-Chim. Sin., 2022, 38, 2106034.
[26]	Y. Zhao, Q. Yuan, K. Sun, A. Wang, R. Xu, J. Xu, Y. Wang, M. Fan, J. Jiang, ACS Appl. Mater. Interfaces, 2023, 15, 37593-37601.
[27]	Kresse, Hafner, Phys. Rev. B, 1994, 49, 14251-14269.
[28]	Perdew, Burke, Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[29]	G. Henkelman, H. Jónsson, J. Chem. Phys., 2000, 113, 9978-9985.
[30]	G. Henkelman, B. P. Uberuaga, H. Jónsson, J. Chem. Phys., 2000, 113, 9901-9904.
[31]	X. Chen, J. Chen, H. Chen, Q. Zhang, J. Li, J. Cui, Y. Sun, D. Wang, J. Ye, L. Liu, Nat. Commun., 2023, 14, 751.
[32]	X. Ma, Y. Zhang, T. Fan, D. Wei, Z. Huang, Z. Zhang, Z. Zhang, Y. Dong, Q. Hong, Z. Chen, X. Yi, Adv. Funct. Mater., 2023, 33, 2213145.
[33]	V. Chandra, J. Park, Y. Chun, J. W. Lee, I.-C. Hwang, K. S. Kim, ACS Nano, 2010, 4, 3979-3986.
[34]	Q. Wang, K. Liu, K. Hu, C. Cai, H. Li, H. Li, M. Herran, Y.-R. Lu, T.-S. Chan, C. Ma, J. Fu, S. Zhang, Y. Liang, E. Cortes, M. Liu, Nat. Commun., 2022, 13, 6082.
[35]	X. Zhang, Y. Wang, M. Gu, M. Wang, Z. Zhang, W. Pan, Z. Jiang, H. Zheng, M. Lucero, H. Wang, G. E. Sterbinsky, Q. Ma, Y.-G. Wang, Z. Feng, J. Li, H. Dai, Y. Liang, Nat. Energy, 2020, 5, 684-692.
[36]	P. Yue, L. Zhong, Y. Deng, J. Li, L. Zhang, D. Ye, X. Zhu, Q. Fu, Q. Liao, Small, 2023, 19, 2300051.
[37]	H. Yang, Q. Lin, C. Zhang, X. Yu, Z. Cheng, G. Li, Q. Hu, X. Ren, Q. Zhang, J. Liu, C. He, Nat. Commun., 2020, 11, 593.
[38]	X. Wu, J.Y. Zhao, J. W. Sun, W.J. Li, H. Y. Yuan, P. F. Liu, S. Dai, H. G. Yang, Small, 2023, 19, 2207037.
[39]	R. Wang, X. Wang, W. Weng, Y. Yao, P. Kidkhunthod, C. Wang, Y. Hou, J. Guo, Angew. Chem. Int. Ed., 2022, 61, e202115503.
[40]	L. Sun, V. Reddu, S. Xi, C. Dai, Y. Sheng, T. Su, A. C. Fisher, X. Wang, Adv. Energy Mater., 2022, 12, 2202108.
[41]	S. Ren, E. W. Lees, C. Hunt, A. Jewlal, Y. Kim, Z. Zhang, B. A. W. Mowbray, A. G. Fink, L. Melo, E. R. Grant, C. P. Berlinguette, J. Am. Chem. Soc., 2023, 145, 4414-4420.
[42]	X. Kong, B. Liu, Z. Tong, R. Bao, J. Yi, S. Bu, Y. Liu, P. Wang, C.-S. Lee, W. Zhang, SmartMat, 2024, e1262.
[43]	Y. Jin, X. Zhan, Y. Zheng, H. Wang, X. Liu, B. Yu, X. Ding, T. Zheng, K. Wang, D. Qi, J. Jiang, Appl. Catal. B, 2023, 327, 122446.
[44]	Z. Chen, X. Zhang, W. Liu, M. Jiao, K. Mou, X. Zhang, L. Liu, Energy Environ. Sci., 2021, 14, 2349-2356.

从富含缺陷的碳载体到酞菁钴的质子供给用于增强CO₂电还原

Proton feeding from defect-rich carbon support to cobalt phthalocyanine for efficient CO₂ electroreduction

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 15

编辑推荐

Metrics

[1]	肖佳勇, 蒋超, 张辉, 邢卓, 邱明, 余颖. 具有亲水性的无定形棒状核壳结构NiMoP@CuNWs用于中性介质中高效析氢[J]. 催化学报, 2024, 63(8): 154-163.
[2]	任清汇, 徐亮, 吕梦雨, 张秩远, 栗振华, 邵明飞, 段雪. 电催化还原反应中的阳离子效应:最新进展[J]. 催化学报, 2024, 63(8): 16-32.
[3]	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.
[4]	霍韵滢, 郭聪, 张永乐, 刘婧怡, 张巧, 刘芝婷, 杨光星, 李仁贵, 彭峰. 自支撑Ni(OH)₂/NF催化剂高效电催化氧化5-羟甲基糠醛反应研究[J]. 催化学报, 2024, 63(8): 282-291.
[5]	陈昕煜, 赵聪聪, 任静, 李波, 刘倩倩, 李葳, 杨帆, 陆思琦, 赵宇飞, 颜力楷, 臧宏瑛. 富含氧空位的由多金属氧簇辅助的银基异质结用于高效电催化固氮[J]. 催化学报, 2024, 62(7): 209-218.
[6]	杨树姣, 江鹏飞, 岳楷航, 郭凯, 杨璐娜, 韩金秀, 彭欣阳, 张学鹏, 郑浩铨, 杨韬, 曹睿, 严雅, 张伟. 多配位水分子的焦磷酸锰用于电催化水氧化研究[J]. 催化学报, 2024, 62(7): 166-177.
[7]	朱鸿睿, 徐慧民, 黄陈金, 张志杰, 詹麒尼, 帅婷玉, 李高仁. 光电催化析氧和CO₂还原反应催化剂的研究进展[J]. 催化学报, 2024, 62(7): 53-107.
[8]	陈振霖, 薛静, 武磊, 党昆, 籍宏伟, 陈春城, 章宇超, 赵进才. 协同光电及热效应实现铜光阴极上等离激元催化高效硝酸根还原反应[J]. 催化学报, 2024, 62(7): 219-230.
[9]	刘青, 成雪峰, 霍锦艳, 刘小芳, 董慧龙, 曾宏波, 徐庆锋, 路建美. 调控N中间体与一维共轭配位聚合物的相互作用促进电催化硝酸盐还原产氨[J]. 催化学报, 2024, 62(7): 231-242.
[10]	侯现飚, 于辰, 倪腾嘉, 张树聪, 周健, 代水星, 初蕾, 黄明华. 构筑非晶/晶体NiFe-MOF@NiS异质结构催化剂增强大电流密度下水/海水氧化[J]. 催化学报, 2024, 61(6): 192-204.
[11]	王凯琪, 何益明. 金属钛酸盐基压电催化剂的最新进展: 改善压电性能和调节载流子输运以提高催化性能[J]. 催化学报, 2024, 61(6): 111-134.
[12]	苟王燕, 王译晨, 张铭凯, 谈晓荷, 马媛媛, 瞿永泉. 设计稳定的钌基析氢和析氧反应催化剂的基本原理[J]. 催化学报, 2024, 60(5): 68-106.
[13]	海广通, 富忠恒, 刘欣, 黄秀兵. 电催化还原氮制氨的最新进展[J]. 催化学报, 2024, 60(5): 107-127.
[14]	孙泽晖, 来壮壮, 赵影影, 陈建富, 马巍. 解析单颗粒电化学分步电子转移步骤用于识别电催化剂本征活性[J]. 催化学报, 2024, 60(5): 262-271.
[15]	吴维凡, 范晋歌, 赵振宏, 潘建敏, 杨静, 阎兴斌, 詹怡. 馄饨结构的KB@Co-C₃N₄在中性电解质中作为锌空气电池的高活性和稳定性氧催化剂[J]. 催化学报, 2024, 60(5): 178-189.