氮掺杂碳催化剂在高效电化学CO2还原中的协同效应

doi:10.1016/S1872-2067(21)64006-8

催化学报 ›› 2022, Vol. 43 ›› Issue (7): 1697-1702.DOI: 10.1016/S1872-2067(21)64006-8

• 二氧化碳催化转化专栏 • 上一篇下一篇

氮掺杂碳催化剂在高效电化学CO₂还原中的协同效应

刘储浩^a^,^†, 吴悦^a^,^†, 方锦杰^c, 余坷^a, 李慧^a, 贺文君^b, 张永臻^d, 柳守杰^a, 陈郑^e, 董京^b^,^*(), 陈晨^a^,^#()

^a清华大学化学系, 北京100084
^b南京工业大学科研部, 江苏南京211816
^c北京化工大学软物质科学与工程高精尖创新中心, 北京100029
^d澳门大学科技学院物理及化学系, 澳门999078
^e安徽师范大学功能性分子固体教育部重点实验室, 安徽芜湖241000

收稿日期:2021-09-21 接受日期:2021-11-12 出版日期:2022-07-18 发布日期:2022-05-20
通讯作者: 董京,陈晨
作者简介:第一联系人：
^†共同第一作者
基金资助:
国家重点研发计划(2016YFA0202801);国家自然科学基金(21925202);国家自然科学基金(21872076);北京市自然科学基金(JQ18007);清华大学自主科研计划.

Synergetic effect of nitrogen-doped carbon catalysts for high-efficiency electrochemical CO₂ reduction

Chuhao Liu^a^,^†, Yue Wu^a^,^†, Jinjie Fang^c, Ke Yu^a, Hui Li^a, Wenjun He^b, Weng-Chon Cheong^d, Shoujie Liu^a, Zheng Chen^e, Jing Dong^b^,^*(), Chen Chen^a^,^#()

^aDepartment of Chemistry, Tsinghua University, Beijing 100084, China
^bScientific Research Department, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^cBeijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
^dDepartment of Physics and Chemistry, Faculty of Science and Technology, University of Macau, Macau, China
^eKey Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Normal University, Wuhu 241000, Anhui, China

Received:2021-09-21 Accepted:2021-11-12 Online:2022-07-18 Published:2022-05-20
Contact: Jing Dong, Chen Chen
About author:First author contact:
^†Contributed equally to this work.
Supported by:
National Key R&D Program of China(2016YFA0202801);National Natural Science Foundation of China(21925202);National Natural Science Foundation of China(21872076);Beijing Natural Science Foundation(JQ18007);Tsinghua University Initiative Scientific Research Program

摘要/Abstract

摘要：

利用电化学方法将温室气体CO₂还原(CO₂RR)为高附加值化学品是解决环境和能源问题的一种很有前景的办法. 目前, 大量具有催化活性的材料已被广泛应用于CO₂RR中, 主要包括金属、合金、金属氧化物和金属-碳氮复合材料等. 然而大部分金属也是很好的析氢反应(HER)活性位点, 容易在CO₂RR催化过程产生大量氢气, 同时部分金属位点容易被CO毒化导致活性与选择性下降, 而且金属成本较高也会阻碍催化剂的工业化应用. 因此, 开发低成本、高性能的无金属的氮掺碳材料(mf-NCs)作为高效CO₂RR催化剂, 以及研究相关的催化机理对于解决温室效应和能源短缺问题都至关重要. 但N活性位点不清晰以及本征活性较低等劣势阻碍了mf-NCs成为一种高性能催化剂. 精准控制合成具有明确N活性位点的mf-NCs催化剂仍然十分具有挑战性. 目前, 文献报道了一些mf-NCs(如氮杂石墨烯、氮杂纳米管)在CO₂RR中的应用. 但是, 在合成石墨烯或者碳纳米管的过程中需要使用到金属元素, 完全去除它们非常困难. 比如在合成碳纳米管时用的金属纳米颗粒往往被包覆在碳管中, 即使酸洗也无法将其完全去除, 所以很难确定其活性位点到底是金属还是非金属. 另外, 在研究mf-NCs的CO₂RR活性位点时, 虽然催化剂中存在多种N元素, 但是人们大多将活性归因于单一的N位点. 在水相的CO₂RR中, 除了CO₂外, H₂O分子也在CO₂的活化与还原过程中扮演着重要的角色. 这表明单一位点很难同时满足两种不同物质的吸附与活化. 因此, 针对mf-NCs催化剂中不同N位点需要进行更深入的研究.

本文报道了一种聚合-热解-蚀刻工艺, 构建了系列含有不同氮成分的mf-NCs-x催化剂(x表示热解温度), 并研究其在CO₂RR中的活性位点. 所制催化剂mf-NC-1000在-0.55 V(相对于可逆氢电极)时具有90%左右的CO法拉第效率(FE_CO), 并具有良好的稳定性. 通过X射线粉末衍、拉曼光谱、透射电子显微镜、扫描隧道电子显微镜、高分辨透射电子显微镜和X射线光电子能谱等表征手段, 系统考察了含有不同种类N位点的mf-NC-800, mf-NC-1000和mf-NC-1200催化剂的结构与电催化性能, 结合原位衰减全反射表面增强红外吸收光谱(in-situ ATR-SEIRAS)结果表明, 石墨N和吡啶N可以参与协同吸附CO₂和H₂O, 且更有利于CO₂的活化和还原. 综上, 本文不仅为CO₂RR电催化剂的合成提供了一种高效、经济的方法, 且通过合理的实验设计突破了对mf-NCs催化剂在CO₂RR中关于活性位点的认知.

关键词: CO₂电还原, 氮掺杂碳材料, 吡啶氮, 石墨氮, 协同作用

Abstract:

The use of carbon-based materials is an appealing strategy to solve the issue of excessive CO₂ emissions. In particular, metal-free nitrogen-doped carbon materials (mf-NCs) have the advantages of convenient synthesis, cost-effectiveness, and high conductivity and are ideal electrocatalysts for the CO₂ reduction reaction (CO₂RR). However, the unclear identification of the active N sites and the low intrinsic activity of mf-NCs hinder the further development of high-performance CO₂RR electrocatalysts. Achieving precise control over the synthesis of mf-NC catalysts with well-defined active N-species sites is still challenging. To this end, we adopted a facile synthesis method to construct a set of mf-NCs as robust catalysts for CO₂RR. The resulting best-performing catalyst obtained a Faradaic efficiency of CO of approximately 90% at -0.55 V (vs. reversible hydrogen electrode) and good stability. The electrocatalytic performance and in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements collectively revealed that graphitic and pyridinic N can synergistically adsorb CO₂ and H₂O and thus promote CO₂ activation and protonation.

Key words: CO₂ reduction reaction, Nitrogen-doped carbon material, Pyridinic N, Graphitic N, Synergetic effect

刘储浩, 吴悦, 方锦杰, 余坷, 李慧, 贺文君, 张永臻, 柳守杰, 陈郑, 董京, 陈晨. 氮掺杂碳催化剂在高效电化学CO₂还原中的协同效应[J]. 催化学报, 2022, 43(7): 1697-1702.

Chuhao Liu, Yue Wu, Jinjie Fang, Ke Yu, Hui Li, Wenjun He, Weng-Chon Cheong, Shoujie Liu, Zheng Chen, Jing Dong, Chen Chen. Synergetic effect of nitrogen-doped carbon catalysts for high-efficiency electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, 2022, 43(7): 1697-1702.

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图/表 5

Fig. 1. Schematic representation of the mf-NCs synthesis process.

Fig. 2. (a) Thermogravimetric analysis in Ar atmosphere. (b) XRD patterns. (c) Raman spectra of mf-NCs. SEM (d), TEM (e), HRTEM (f), and HAADF-STEM images (g) and corresponding elemental mapping of C (h), N (i), and overlapped (j) images of mf-NC-1000.

Fig. 3. C K-edge XANES of mf-NC-800 (a), mf-NC-1000 (b), and mf-NC-1200 (c). High-resolution N 1s XPS profiles of mf-NC-800 (d), mf-NC-1000 (e), and mf-NC-1200 (f).

Fig. 4. LSV curves (a), FECO (b), and JCO (c) of the catalysts. (d) Stability of mf-NC-1000 at -0.55 V.

Fig. 5. (a) Proposed reaction pathway of CO2RR. In situ ATR-SEIRAS spectra of mf-NC-1000 (b,c) and mf-NC-1200 (d,e).

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氮掺杂碳催化剂在高效电化学CO₂还原中的协同效应

Synergetic effect of nitrogen-doped carbon catalysts for high-efficiency electrochemical CO₂ reduction

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