硅酸盐缓冲层促进酸性膜电极体系中电催化CO2还原

doi:10.1016/S1872-2067(24)60129-4

催化学报 ›› 2024, Vol. 66: 139-145.DOI: 10.1016/S1872-2067(24)60129-4

硅酸盐缓冲层促进酸性膜电极体系中电催化CO₂还原

魏世蕾^a, 华航^a, 任清璇^a, 罗景山^a^,^b^,^c^,^*()

^a南开大学光电子薄膜器件与技术研究所, 光伏材料与电池全国重点实验室, 天津市太阳能高效利用重点实验室, 教育部薄膜光电子技术工程研究中心, 天津 300350
^b南开大学有机新物质创造前沿科学中心, 天津 300071
^c物质绿色创造与制造海河实验室, 天津 300192

收稿日期:2024-06-15 接受日期:2024-08-30 出版日期:2024-11-18 发布日期:2024-11-10
通讯作者: *电子信箱: jingshan.luo@nankai.edu.cn (罗景山).
基金资助:
国家重点研发项目(2019YFE0123400);天津杰出青年基金(20JCJQJC00260);安徽省科技重大专项基金(202203f07020007);安徽省海螺集团

Enhanced electrochemical carbon dioxide reduction in membrane electrode assemblies with acidic electrolytes through a silicate buffer layer

Shilei Wei^a, Hang Hua^a, Qingxuan Ren^a, Jingshan Luo^a^,^b^,^c^,^*()

^aInstitute of Photoelectronic Thin Film Devices and Technology, State Key Laboratory of Photovoltaic Materials and Cells, Tianjin Key Laboratory of Efficient Utilization of Solar Energy, Ministry of Education Engineering Research Center of Thin Film Photoelectronic Technology, Nankai University, Tianjin 300350, China
^bFrontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China
^cHaihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China

Received:2024-06-15 Accepted:2024-08-30 Online:2024-11-18 Published:2024-11-10
Contact: *E-mail: jingshan.luo@nankai.edu.cn (J. Luo).
Supported by:
National Key R&D Program of China(2019YFE0123400);Tianjin Distinguished Young Scholar Fund(20JCJQJC00260);Major Science and Technology Project of Anhui Province(202203f07020007);Anhui Conch Group Co., Ltd.

摘要/Abstract

摘要：

利用可再生能源驱动二氧化碳(CO₂)转化利用, 是降低大气温室气体浓度并促进高价值工业产品生产的一种极具前景的途径. 近年来, 大量科研工作致力于提高电催化CO₂还原反应(CO₂RR)的活性和选择性. 基于气体扩散电极的膜电极反应器已被用于克服CO₂在水溶液中的溶解度限制, 从而在高电流密度下实现高效的CO₂转化. 为了实现CO₂利用率最大化, 研究人员提出在酸性溶液中进行CO₂RR. 随着反应过程中的质子传输, 质子与阴极侧生成的碳酸根或碳酸氢根结合, 再生用于CO₂RR的CO₂气体, 理论上可实现高达100%的CO₂利用率, 然而酸性膜电极体系面临着严重的析氢竞争副反应.

本文发现在电极表面修饰硅酸盐层可以缓冲高浓度质子, 在电极表面营造稳定的反应微环境, 同时降低析氢竞争副反应发生, 提升酸性电解液条件下的CO₂转化效率和CO₂利用率. 而碱金属离子可以稳定CO₂RR中间体, 促进酸性体系下的CO₂转化. 因此, 利用硅酸盐缓冲层和碱金属阳离子的协同效应调节电极表面微环境, 实现酸性膜电极体系中CO₂高效转化是本文的主要研究思路. 本文设计了硅酸钠(Na₂SiO₃)修饰的银催化剂(NM-Ag), 通过改变电解液的阳离子种类、阳离子浓度和氢离子浓度, 分别对比了100 mA cm^-2电流密度下生成CO的法拉第效率, 结果表明, Ag催化剂在电解液pH = 2, Cs⁺浓度为1 mol L^-1时, 才可实现80%的CO法拉第效率, 但存在严重的析盐问题, 而NM-Ag催化剂在低pH和低Cs⁺浓度下均可实现高的CO法拉第效率, 并且在400 mA cm^-2电流密度下, 仍具有高于70%的CO法拉第效率. 测试和计算NM-Ag和Ag的电化学表观活性面积(ECSA), 结果表明, NM-Ag相比Ag具有更高的内部活性. 改变CO₂进气流速, 计算不同流速下的CO₂单程转化效率(SPCE), 结果表明, 在3 mL min^-1的CO₂进气流速下, NM-Ag可以实现高达67%的SPCE, 突破了碱性和中性环境下可以达到的50%的SPCE. 扫描电子显微镜、元素分析和X射线衍射结果表明, 长时间(12 h)反应后的NM-Ag中修饰层由Na₂SiO₃转化为H₂SiO₃, 证实了修饰层的稳定性, 且反应中关键作用成分为H₂SiO₃. 通过原位拉曼发现, 当电位逐渐负移, NM-Ag表现出更强的CO₂吸附和偏碱的反应微环境, 从而抑制了析氢副反应.

综上, 本文利用硅酸盐和碱金属阳离子协同作用, 实现了酸性体系较低阳离子浓度下的高效CO₂转化, 减小了析氢竞争副反应, 实现了较高的CO₂利用率, 强调了微环境调控对促进CO₂转化的重要性, 为实现酸性体系CO₂高效利用提供了思路.

关键词: 电催化, 二氧化碳还原, 微环境, 酸性体系, 膜电极

Abstract:

The electrochemical reduction of CO₂ holds considerable promise in combating global climate change while yielding valuable chemical commodities. Membrane electrode assemblies operating within acidic electrolyte have exhibited noteworthy advancements in CO₂ utilization efficiency, albeit encountering formidable competition from the hydrogen evolution reaction. In our investigation, we introduced a silicate buffer layer, which yielded exceptional outcomes even using strong acid electrolyte. Notably, our approach yielded a CO Faradic efficiency of 90% and reached a substantial current density of 400 mA cm^-2. Furthermore, our system displayed remarkable stability over a 12-hour duration, and achieved a high single-pass-conversion efficiency of 67%. Leveraging in-situ Raman analysis, we attributed these performance enhancements to the augmented CO₂ adsorption and localized alkaline environment facilitated by the incorporation of the silicate buffer layer. We think the addition of buffer layer to adjust the microenvironment is essential to achieve high performance and keep stable in acid condition.

Key words: Electrocatalysis, Reduction of CO₂, Microenvironment, Acidic system, Membrane electrode

魏世蕾, 华航, 任清璇, 罗景山. 硅酸盐缓冲层促进酸性膜电极体系中电催化CO₂还原[J]. 催化学报, 2024, 66: 139-145.

Shilei Wei, Hang Hua, Qingxuan Ren, Jingshan Luo. Enhanced electrochemical carbon dioxide reduction in membrane electrode assemblies with acidic electrolytes through a silicate buffer layer[J]. Chinese Journal of Catalysis, 2024, 66: 139-145.

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Fig. 1. Cation-induced CO2 reduction in acidic MEA systems. (A) FECO and FEH2 of Ag GDE during CO2RR within MEA using H2SO4 anolyte at varying pH levels, measured at a current density of 100 mA cm-2. (B) FECO and FEH2 of Ag GDE during CO2RR after introduced 1 mol L-1 Na+, K+, or Cs+ into H2SO4 anolyte, with pH adjustment to 2 using H2SO4. (C) FECO and FEH2 of Ag GDE during CO2RR employing different concentrations of Cs+ anolyte, with pH adjustment to 2 using H2SO4. (D) FECO and FEH2 of Ag GDE during CO2RR utilizing anolytes with varying pH levels, maintaining a constant Cs+ concentration of 1 mol L-1. (E) Duration performance analysis of CO2RR at 100 mA cm-2 employing the Ag GDE with anolyte containing 1 mol L-1 Cs+, pH adjusted to 2 using H2SO4. (F) XRD pattern depicting salt precipitation and the gas flow channel configuration post-experimentation (insert image). The error bars are determined from at least 3 separate experiments.

Fig. 2. Na2SiO3 modified Ag GDE for CO2 reduction. (A) FECO and FEH2 of Ag GDE and NM-Ag during CO2RR in H2SO4 anolyte containing 0.5 mol L-1 Cs+ at a current density of 100 mA cm-2. (B) FECO and FEH2 of NM-Ag during CO2RR employing varying concentrations of Cs+ anolytes, with pH adjustment to 2 using H2SO4. (C) FECO and FEH2 during CO2RR utilizing anolyte containing 1 mol L-1 Cs+ at different current densities. pH was adjusted to 2 using H2SO4. (D) FECO during CO2RR and the SPCE under varying gas flow rates at 100 mA cm-2. The anolyte contained 1 mol L-1 Cs+ and pH was adjusted to 2 using H2SO4. (E) Comparative analysis of cell voltage and FECO among Ag, SiO2-Ag, and NM-Ag for long time stability test. The error bars are determined from at least 3 separate experiments.

Fig. 3. In situ Raman spectra of (A) Ag and (B) NM-Ag samples in the range of 300-1200 cm-1 under varying applied potentials. The peak attributed to ν (Ag-O) corresponds to the vibration of metal Ag interacting with adjacent subsurface hydroxyl groups. (C) The working principal scheme and schematic illustrating of Ag GDE (left) and NM-Ag (right) for CO2RR in acidic MEA system.

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硅酸盐缓冲层促进酸性膜电极体系中电催化CO₂还原

Enhanced electrochemical carbon dioxide reduction in membrane electrode assemblies with acidic electrolytes through a silicate buffer layer

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