碱性刻蚀策略提高LDH电催化CO2还原产甲烷性能

The alkaline etching strategy enhances the methane production performance of LDH in electrocatalytic CO2 reduction

  • 摘要: 目前,电催化CO2还原产甲烷(CH4)催化剂主要以单原子铜基材料为主,但其在催化过程易团聚,稳定性差。层状双金属氢氧化物(LDH)材料具有层板元素可调、稳定性好、合成方法简便等优点,被认为是一种很有前途的电催化剂材料。然而,低导电率和有限的活性位点阻碍了其在CO2还原领域中的应用。基于此,采用水热法可控合成了铜基水滑石材料(CuMgAl-LDH),通过碱性刻蚀将部分Al位点去除,从而在LDH结构中产生空位缺陷。Al缺陷(Alv)不仅对活性位Cu的电子结构起到调控作用,还暴露出更多活性位点,强化其电催化CO2还原产CH4性能。系统研究了缺陷对CuMgAl-LDH的催化活性、选择性及稳定性的影响规律。通过一系列表征技术对LDH材料的形貌结构和电子结构进行了详细表征。结果表明,碱性刻蚀可以提高材料的导电性,刻蚀后的CuMgAlv-LDH在200 mA·cm−2电流密度的条件下,CH4的选择性最高可达57 %,可在超过8 h测试中保持性能稳定,为LDH材料在CO2还原领域中的应用提供了一定的思路。

     

    Abstract: Currently, electrocatalysts for CO2 reduction to methane (CH4) are mainly based on single-atom copper-based materials, but they tend to aggregate during the catalytic process, resulting in poor stability. Layered double hydroxide (LDH) materials are considered promising electrocatalysts due to their tunable layered elements, good stability, and simple synthesis methods. However, their low conductivity and limited active sites hinder their application in CO2 reduction. Based on this, Cu-based hydrotalcite materials (CuMgAl-LDH) were controllably synthesized using a hydrothermal method, and partial Al sites were removed through alkaline etching, generating vacancy defects in the LDH structure. These Al defects not only modulate the electronic structure of the material but also expose more active sites, enhancing its performance in electrocatalytic CO2 reduction to CH4. The effects of the defects on the catalytic activity, selectivity, and stability of CuMgAl-LDH were systematically studied. A series of characterization techniques were used to analyze the morphology and electronic structure of the LDH materials in detail. The results show that alkaline etching can improve the conductivity of the material, and the etched CuMgAl-LDH achieves a methane selectivity of up to 57 % at a current density of 200 mA·cm−2, maintaining stable performance for over 8 hours of testing. This provides insights for the application of LDH materials in the field of CO2 reduction.

     

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