多孔炭基二氧化碳电催化材料研究进展

doi:10.11949/0438-1157.20200106

摘要/Abstract

摘要：

二氧化碳(CO₂)电催化转化引起广泛关注，其中非贵金属多孔炭基催化剂是研究热点。重点介绍了近年来多孔炭基CO₂电催化材料的孔结构、表面化学、形貌调控策略，归纳了增强多孔炭基CO₂电催化还原效率的方法，探讨了多孔炭基催化材料的活性中心类型与分布，分析了提高催化活性位密度的手段。在总结近年来取得研究进展的基础上，展望了多孔炭基催化剂在电催化CO₂转化方面的发展趋势和面临的挑战。

关键词: 多孔炭, 炭基催化剂, CO₂还原, 杂原子掺杂

Abstract:

Electrocatalytic conversion of carbon dioxide (CO₂) has attracted widespread attention. In this field, the development of precious metal-free, porous carbon-based electrocatalysts stands out being the research hot spot. First, the key parameters in terms of pore structure, surface chemistry as well as morphology of porous carbon-based electrocatalysts have been overviewed. Then, the methods to improve the porous carbon-based electrocatalysts activity are summarized. Subsequently, the nature and distribution of active centers of carbon-based electrocatalysts are discussed. In the following, the pathways to increase the density of active sites in porous carbon-based electrocatalysts are analyzed. Finally, based on the advances made in the research community in recent years, we made perspectives on the developing trend and challenges of porous carbon-based electrocatalysts for efficient CO₂ electroreduction.

Key words: porous carbons, carbon-based catalysts, CO₂ electroreduction, heteroatom doping

中图分类号:

TQ 127.1

董灵玉, 葛睿, 原亚飞, 唐宋元, 郝广平, 陆安慧. 多孔炭基二氧化碳电催化材料研究进展[J]. 化工学报, 2020, 71(6): 2492-2509.

Lingyu DONG, Rui GE, Yafei YUAN, Songyuan TANG, Guangping HAO, Anhui LU. Recent advances in porous carbon-based carbon dioxide electrocatalytic materials[J]. CIESC Journal, 2020, 71(6): 2492-2509.

图/表 10

图1 CO2分子杂化轨道及域电子分配(a), CO2原子电负性(b)和CO2活化方式(c)

Fig.1 Hybrid orbital of CO2and delocalized electrons (a), C and O element’s electronegativity in CO2(b) and the methods to activate CO2(c)

图2 CuSAs/TCNF结构表征

Fig.2 Structural characterization of CuSAs/TCNF

图3 整体炭宏观形态与电子显微镜照片

Fig.3 Macroscopic morphology and electron microscopy images of typical carbon monolith

图4 杂原子掺杂炭结构(a)及掺杂方法(b), 杂原子电负性(c)

Fig.4 Doping(a) and doping method(b) of graphitic carbon structure with heteroatoms, and the corresponding electronegativity of elements(c)

图5 石墨烯负载型氮掺杂石墨烯量子点形貌以及CO2还原电化学测试

Fig.5 Morphology of graphene-loaded nitrogen-doped graphene quantum dots and electrochemical measurement of CO2 reduction

图6 NS-C层的合成过程、形貌以及CO2还原电化学测试

Fig.6 Synthesis processes of NS-C layers, surface morphology and electrocatalytic test towards CO2 reduction

图7 M-Nx材料模型与局部结构示意图(a), 与Au基催化剂相比, M-N-C催化剂的质量归一化CO部分电流(质量活性) (b)和实验与模拟的相关性(c)

Fig.7 Model and a schematic local structure(a), and catalyst mass-normalized CO partial currents(mass activity) vs applied potential compared to state-of-art Au catalysts(b) and experimental correlation to simulations(c) for M–N–C catalysts

图8 分散在氮化石墨烯上的单个镍原子的结构表征

Fig.8 Structural characterization of single nickel atoms dispersed on nitrogenated graphene

图9 Cu–N4结构上*CO转化为CH3OH的自由能(橙色、灰色、红色和浅蓝色球体分别代表Cu、C、O和H原子)

Fig.9 Free energies for conversion of *CO to CH3OH on Cu-N4 structure(orange, gray, red and light blue spheres stand for Cu, C, O, and H atoms, respectively)

图10 碳纳米管负载的CoPc分子对CO2还原的催化性能和结构表征

Fig.10 Structural characterization and catalytic performance of CoPc molecules supported on CNTs for CO2 reduction

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