Cu基纳米材料电催化还原CO2的结构-性能关系

doi:10.11949/0438-1157.20201127

摘要/Abstract

摘要：

通过电催化方法，在常温、常压下将CO₂还原为高附加值化学品，是解决目前能源短缺和环境污染问题的理想选择之一。铜基材料是目前被证实的还原CO₂生成烃类、醇类等高附加值产物的最有效非均相电催化剂，因此受到国内外研究者的广泛关注。综述了纳米Cu材料在电催化还原CO₂领域的研究进展，重点阐述催化剂结构（晶界、表面结构与晶面、孔结构等）与性能关系，并讨论了测试条件如传质、局部pH对催化性能的影响，最后论述了该领域目前存在的问题和未来发展趋势。

关键词: 铜基催化剂, 构-效关系, 电化学, 催化, 二氧化碳, 还原

Abstract:

Using electrocatalytic methods to reduce CO₂ to high value-added chemicals under normal temperature and pressure is one of the ideal choices for solving the current energy shortage and environmental pollution problems. To date, copper based materials have been confirmed to be the most effective catalysts for reducing CO₂ to hydrocarbon products such as methane, ethene, and ethanol. Therefore, extensive attentions have been paid to explore Cu-based electrocatalyst for CO₂ reduction. In this paper, we reviewed the development of Cu-based catalysts for electrochemical CO₂ reduction, and mainly focused on the dependence of catalytic performance on catalyst morphology including grain boundaries, surface structures and open facets and testing conditions such as substrate transport and local pH. Finally, we offer some challenges and perspectives on the future outlook for electrochemical CO₂ reduction.

Key words: Cu-based catalyst, structure-performance relationship, electrochemistry, catalysis, carbon dioxide, reduction

中图分类号:

TQ 127.1

于丰收, 张鲁华. Cu基纳米材料电催化还原CO₂的结构-性能关系[J]. 化工学报, 2021, 72(4): 1815-1824.

YU Fengshou, ZHANG Luhua. Structure-performance relationship of Cu-based nanocatalyst for electrochemical CO₂ reduction[J]. CIESC Journal, 2021, 72(4): 1815-1824.

图/表 5

图1 电催化还原CO2金属催化剂分类

Fig.1 CO2 reduction metal classification

图2 电化学还原法和氢还原法制备Cu纳米线的晶体取向图(a)；Cu纳米线上不同种类晶界比例(b)；混乱大角度晶界和JCO关系曲线(c)；∑3晶界与JCO关系曲线(d)

Fig.2 Crystal orientation maps constructed for the various types of Cu nanowires (a); Distribution of the different types of grain boundaries (b); The correlations between JCO and the relative densities of high-angle grain (c) and coherent (Σ3) boundaries (d) for HR-150 nanowires

图3 不含晶界铜电极(ED-Cu) (a)和富含晶界铜电极(GB-Cu)(b)样品的HR-TEM图;样品的Cu 2p XPS表征(c); ED-Cu对不同产物的法拉第效率(d); GB-Cu对不同产物的法拉第效率(e)；样品对C2产物的法拉第效率(f)；GB-Cu原位ATR-SEIRAS表征(g)；GB-Cu DFT计算模型(h)和不同吸附位上的*CO吸附能(i)

Fig.3 HRTEM images of ED-Cu catalysts (a) and GB-Cu catalysts (b); Cu 2p XPS spectra of as-prepared Cu catalysts (c); Faradaic efficiencies of gas products on ED-Cu (d) and GB-Cu (e) as a function of the electrode potential; Comparison of Faradaic efficiencies of C2 products on electrodes (f); In situ ATR-SEIRAS spectras of GB-Cu (g); Different binding sites on the schemed atomic structure of GB-Cu (h); *CO energies in different sites of the schemed structure of GB-Cu (i)

图4 100-cycle Cu的制备过程(a)；polished Cu (b)和100-cycle Cu (c)的SEM图；100-cycle Cu的衍射图、高倍TEM图(d)和晶格间距图(e)；100-cycle Cu 对C2+, C1 and H2产物的法拉第效率(f)和电流密度(g)； Cu箔、10-cycle Cu、100-cycle Cu生成C2+/C1产物的最高比例(h)

Fig.4 Schematic diagram for the preparation of 100-cycle Cu(a); SEM images of the polished Cu foil(b) and 100-cycle Cu(c); SAED pattern and TEM image(d) of the Cu nanotube; The lattice spacing of Cu nanotubes(e); Faradaic efficiencies(f) and partial currents(g) of C2+, C1 and H2 on 100-cycle Cu; The highest C2+/C1 ratio of Cu foil, 10-cycle Cu, 100-cycle Cu(h)

图5 CO (左)、 C2 (中)和 C3 (右)物种在实心球(a)和空心球(b)内外浓度分布

Fig.5 CO (left), C2 (middle) and C3 (right) concentration distributions on the solid sphere (a) and cavity confinement structure (b)

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Cu基纳米材料电催化还原CO₂的结构-性能关系

Structure-performance relationship of Cu-based nanocatalyst for electrochemical CO₂ reduction

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