钴酞菁/多孔碳气凝胶复合结构用于高效电催化CO2还原

doi:10.19286/j.cnki.cci.2023.11.031

摘要
图/表
参考文献(32)
相关文章 (0)

全文: PDF (0 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要利用可再生能源将CO2转化成高附加值的燃料或化学品，是一项实现“碳中和，碳达峰”的新资源化技术，但目前高性能电催化CO2转化的催化剂研发，仍然是一项热点问题。设计具有“类珊瑚状”结构的多级孔氮掺杂碳气凝胶（N-CA）作为优化气体传质的碳载体，利用非共价固定技术，将酞菁钴（CoPc）稳定于气凝胶骨架的表面，以实现活性位点和导电碳骨架稳定结合。CoPc@N-CA展现出优异的电催化CO2还原（CO2RR）活性，在较宽的电势窗口-0.5~-1.0 V vs. RHE下，对CO的选择性＞80%，最高为99.05%；在-0.85 V vs. RHE电位下，CoPc@N-CA对CO的部分电流密度达到14.40 mA·cm-2，约是以商业碳黑（CB）为基底设计的CoPc@CB（3.66·mA cm-2）催化剂的4倍。内在活性分析发现，CoPc@N-CA优异的活性可归因于N-CA独特的多孔结构，这不仅促进了CO2分子的传质，有利于CO2RR反应动力学，而且有利于暴露Co活性位点，从而促进CO2RR。

	服务

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	周暾1
	龚善和2
	吕晓萌3
	冯玉祥1
	黄春霞4
	朱桂生4

关键词 ：电催化CO2还原, 碳气凝胶, 多相分子催化剂, CO产物

Abstract：Electrocatalytic CO2 reduction into high value-added fuels or chemicals by renewable energy to achieve the “carbon neutrality and peak” is attractive, but still challenged by developing high-performance electrocatalytic catalysts for electrocatalytic CO2 reduction reaction (CO2RR). Herein, porous nitrogen-doped carbon aerogels (N-CA) with “coral-like” structure was designed as the substrate to optimize gas mass transfer, and cobalt phthalocyanine (CoPc) was stabilized on N-CA surface by non-covalent immobilization technology to obtain CoPc@N-CA, realizing the stable combination of active sites and conductive carbon skeleton. As a result, CoPc@N-CA exhibits excellent CO2RR activity, CO Faradaic efficiency (FECO) 80% at the wide potential window of -0.5 to -1.0 V vs. RHE, and the maximal FECO of 99.05%. Meanwhile, CoPc@N-CA reaches a high CO partial current density (jCO) of 14.40 mA·cm-2 at -0.85 V vs. RHE, which is close to 4 times of that of CoPc@CB (3.66 mA·cm-2), where carbon black (CB) was chosen as substrate to obtain CoPc@CB. Intrinsic activity analysis illustrates that the excellent activity of CoPc@N-CA can be attributed to the unique porous structure of N-CA, which not only promotes the mass transfer of CO2 molecules, but also facilitates the reaction kinetics of CO2RR, and exposes the active sites of Co, promoting the activity CO2RR.

Key words： electrocatalytic CO2 reduction carbon aerogel heterogeneous molecular catalyst CO product

基金资助:镇江市重点研发计划：CO2→CO高效稳定电催化转化关键技术的研发(GY2021004)

作者简介: 周暾（ 1975— ），男，江苏镇江人，工程师。

引用本文:

周暾1，龚善和2，吕晓萌3，冯玉祥1，黄春霞4，朱桂生4. 钴酞菁/多孔碳气凝胶复合结构用于高效电催化CO2还原[J]. 煤炭与化工, 2023, 46(11): 132-140，156.. Zhou Tun1, Gong Shanhe2, Lv Xiaomeng3, Feng Yuxiang1, Huang Chunxia4, Zhu Guisheng4. Cobalt phthalocyanine/porous carbon aerogel composite for efficient electrocatalytic CO2 reduction. CCI, 2023, 46(11): 132-140，156..

链接本文:

http://www.mtyhg.com.cn/CN/10.19286/j.cnki.cci.2023.11.031 或 http://www.mtyhg.com.cn/CN/Y2023/V46/I11/132

[ 1 ] Sun L, Reddu V, Fisher A C, et al. Understanding and decoupling the role of wavelength and defects in light-induced degradation of metal-halide perovskites[ J ]. Energy & Environmental Science, 2020( 13 ): 374 - 403. [ 2 ] Zhang Z, Zhu J, Chen S, et al.Transient and Persistent Room-Te- mperature Mechanoluminescence from a White-Light Emitting AIEgen with Tricolor Emission Switching Triggered by Light[ J ]. Angew.Chem. Int. Ed, 2023( 135 ): 1 513 - 2 022. [ 3 ] Gong S, Yang S, Wang W, et al.Solution structure of the RNA re- cognition domain of METTL3-METTL14 N6-methyladenosine methyltransferase. Protein Cell[ J ]. Small. 2023, ( 22 ): 78 - 88. [ 4 ] Gong S, Wang W, Zhang C, et al. Tuning the metal electronic stru- cture of anchored cobalt phthalocyanine via dual-regulator for efficient CO2 electroreduction and Zn-CO2 batteries[ J ]. Adv. Funct. Mater. 2022( 32 ): 211 - 649. [ 5 ] Gong S, Wang W, Lu R, et al. Mediating heterogenized nickel ph- thalocyanine into isolated Ni-N3 moiety for improving activity and stability of electrocatalytic CO2 reduction[ J ]. Appl. Catal. B Environ, 2022( 318 ): 121 - 813. [ 6 ] Zhu M, Chen J, Guo R, et al.Cobalt phthalocyanine coordinated to pyridine-functionalized carbon nanotubes with enhanced CO2 electroreduction[ J ]. Appl. Catal. B Environ. 2019( 251 ): 112 - 118. [ 7 ] Corbin N, Zeng J, Williams K, et al.Simultaneous Reduction of CO2 and splitting of H2O by a single immobilized cobalt phthalocyanine electrocatalyst[ J ]. ACS Catal. 2016( 6 ): 3 092 - 3 095. [ 8 ] Morlanes N, Takanabe K, Rodionov V. Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction[ J ]. Nat. Energy 2020( 5 ): 684 - 692. [ 9 ] Zhang X, Wang Y, Gu M, et al. A general synthesis of single atom catalysts with controllable atomic and mesoporous structures[ J ]. Nat. Synth. 2022( 1 ): 658 - 667. [ 10 ] Wu Z, Zhu P, Cullen D A, et al. Aerogels based on carbon nanom- aterials[ J ]. J. Mater. Sci. 2016( 51 ): 9 157 - 9 189. [ 11 ] Araby S, Qiu A, Wang R, et al.Recent advances in preparations a- nd applications of carbon aerogels: A review[ J ]. Carbon, 2020( 163 ): 1 - 18. [ 12 ] Lee J, Park S. Synthesis of biomass-based carbon aerogels in ene- rgy and sustainability[ J ]. J. Carbohyd. Res. 2020( 491 ): 107 - 986. [ 13 ] Sam D K, Sam E K, Durairaj A. Facile preparation and ultra-mic- roporous structure of melamine-resorcinol-formaldehyde polymeric microspheres[ J ]. Chem. Commun. 2013( 49 ): 37 - 63. [ 14 ] Zhou H, Xu S, Su H, et al. Ion-catalyzed synthesis of microporous hard carbon embedded with expanded nanographite for enhanced lithium/sodium storage[ J ]. J. Am. Chem. Soc. 2016( 138 ): 14 915 - 14 922. [ 15 ] Yu Z, Xin S,You Y, et al. Elucidating influence of the existence f- ormation of anchored cobalt phthalocyanine on electrocatalytic CO2-to-CO conversion[ J ]. Nano Energy, 2021( 84 ): 105 - 904. [ 16 ] Ni W, Xue Y, Zang X, et al. Fluorine doped cagelike carbon elec- trocatalyst: an insight into the structure-enhanced CO selectivity for CO2 reduction at high overpotential[ J ]. ACS Nano 2020( 14 ): 2 014 - 2 023. [ 17 ] Pan Y, Lin R, Chen Y, et al. Design of single-atom Co-N5 catalytic site: a robust electrocatalyst for CO2 reduction with nearly 100% CO selectivity and remarkable stability[ J ]. J. Am. Chem. Soc. 2018( 140 ): 4 218 - 4 221. [ 18 ] Zhang B, Gong S, Wang GCobalt-nitrogen-carbon sites on carbon aerogels for enhanced electrocatalytic CO2 activity[ J ]. Appl. Surf. Sci. 2023( 630 ): 157 - 437. [ 19 ] Han S G, Zhang M Fu Z H, Zheng L, et al. Enzyme-inspired mic- roenvironment engineering of a single-molecular heterojunction for promoting concerted electrochemical CO2 reduction[ J ].Adv. Mater. 2022( 34 ): 220 - 830. [ 20 ] Lin S, Diercks C S, Zhang Y B, Kornienko N, et al. Covalent orga- nic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water[ J ]. Science, 2015( 349 ): 1 208 - 1 213. [ 21 ] Zhu M, Chen J, Guo R, et al. Cobalt phthalocyanine coordinated to pyridine-functionalized carbon nanotubes with enhanced CO2 electroreduction[ J ]. Appl. Catal. B- Environ. 2019( 251 ): 112 - 118. [ 22 ] Kramer W W, McCrory C C L.Polymer coordination promotes sel- ective CO2 reduction by cobalt phthalocyanine[ J ]. Chem. Sci. 2016( 7 ): 2 506 - 2 515. [ 23 ] Hu X M, R-nne M H, Pedersen S U, et al.Daasbjerg, K. Enhanced Catalytic Activity of Cobalt Porphyrin in CO2 Electroreduction upon Immobilization on Carbon Materials[ J ]. Angew. Chem. Int. Ed. 2017( 56 ): 6 468 - 6 472. [ 24 ] Zhu M, Chen J, Huang L, et al. Covalently Grafting Cobalt Porph- yrin onto Carbon Nanotubes for Efficient CO2 Electroreduction[ J ]. Angew. Chem. Int. Ed. 2019( 58 ): 6 595 - 6 599. [ 25 ] Marianov A N, Jiang Y. Covalent ligation of Co molecular catalyst to carbon cloth for efficient electroreduction of CO2 in water[ J ]. Appl. Catal. B- Environ. 2019( 244 ): 881 - 888. [ 26 ] Zhu M, Ye R, Jin K. Elucidating the Reactivity and Mechanism of CO2 Electroreduction at Highly Dispersed Cobalt Phthalocyanine[ J ]. ACS Energy Lett. 2018( 3 ): 1 381 - 1 386. [ 27 ] Kornienko N, Zhao Y, Kley C S, et al. Metal-organic frameworks for electrocatalytic reduction of carbon dioxide[ J ]. J. Am. Chem. Soc. 2015( 137 ): 14 129 - 14 135. [ 28 ] Han N, Wang Y, Ma L, et al. Supported cobalt polyphthalocyanine for high-performance electrocatalytic CO2 reduction[ J ]. Chem 2017( 3 ):652 - 664. [ 29 ] Morlan'es N, Takanabe K, Rodionov V. Simultaneous reduction of CO2 and splitting of H2O by a single immobilized cobalt phthalocyanine electrocatalyst[ J ]. ACS Catal. 2016( 6 ): 3 092 - 3 095. [ 30 ] Zhang X, Wu Z, Zhang X, et al. Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures[ J ]. Nat. Commun. 2017( 8 ): 1 - 8. [ 31 ] Maurin A, Robert M J. Noncovalent immobilization of a molecular iron-based electrocatalyst on carbon electrodes for selective, efficient CO2-to-CO conversion in water[ J ]. J. Am. Chem. Soc. 2016( 138 ): 2 492-2 495. [ 32 ] Zhu H L, Zheng Y Q, Shui M. Synergistic interaction of nitrogen- doped carbon nanorod array anchored with cobalt phthalocyanine for electrochemical reduction of CO2[ J ]. ACS Appl. Energy Mater. 2020( 3 ): 3 893 - 3 901.