CuPc/FeNC双组分催化剂协同催化硝酸盐转化为氨

doi:10.1016/S1872-2067(23)64578-4

催化学报 ›› 2024, Vol. 56: 104-113.DOI: 10.1016/S1872-2067(23)64578-4

CuPc/FeNC双组分催化剂协同催化硝酸盐转化为氨

王毅^a^,^b^,¹, 王硕^a^,¹, 付云凡^a^,^b, 桑佳琪^a^,^b, 臧一鹏^a, 魏鹏飞^a, 李合肥^a, 汪国雄^a^,^*(), 包信和^a

^a中国科学院大连化学物理研究所, 能源材料化学协同创新中心, 大连洁净能源国家实验室, 催化基础国家重点实验室, 辽宁大连116023
^b中国科学院大学能源学院, 北京100049

收稿日期:2023-10-30 接受日期:2023-12-05 出版日期:2024-01-18 发布日期:2024-01-10
通讯作者: *电子信箱: wanggx@dicp.ac.cn (汪国雄).
作者简介:¹共同第一作者.
基金资助:
国家重点研发项目(2022YFA1504000);国家自然科学基金(22125205);国家自然科学基金(92045302);中央高校基础研究经费(20720220008);洁净能源国家实验室基金(DNL202007);洁净能源国家实验室基金(DNL201923)

Synergistic catalytic conversion of nitrate into ammonia on copper phthalocyanine and FeNC two-component catalyst

Yi Wang^a^,^b^,¹, Shuo Wang^a^,¹, Yunfan Fu^a^,^b, Jiaqi Sang^a^,^b, Yipeng Zang^a, Pengfei Wei^a, Hefei Li^a, Guoxiong Wang^a^,^*(), Xinhe Bao^a

^aState Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bCollege of Energy, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2023-10-30 Accepted:2023-12-05 Online:2024-01-18 Published:2024-01-10
Contact: *E-mail: wanggx@dicp.ac.cn (G. Wang).
About author:¹Contributed equally to this work.
Supported by:
National Key R&D Program of China(2022YFA1504000);National Natural Science Foundation of China(22125205);National Natural Science Foundation of China(92045302);Fundamental Research Funds for the Central Universities(20720220008);Dalian National Laboratory for Clean Energy(DNL202007);Dalian National Laboratory for Clean Energy(DNL201923)

摘要/Abstract

摘要：

氨(NH₃)作为重要的化学品和能源储存介质, 需求量与日俱增. 本文旨在通过电化学硝酸根还原反应(NO₃⁻RR), 将NO₃⁻转化为NH₃, 不仅解决了NO₃⁻引起的环境污染问题, 又可以满足对NH₃的迫切需求. 然而, NO₃⁻RR涉及多个电子和质子转移过程, 其中, NO₂⁻是NO₃⁻活化转化和深度还原合成NH₃的重要中间体. 酞菁铜(CuPc)能够高效地活化转化NO₃⁻为NO₂⁻, 但在低过电位时无法有效地将NO₂⁻还原为NH₃, 难以获得较高的氨法拉第效率(FE_NH3)和分电流密度. 而氮配位的铁单原子催化剂(FeNC)则有较好的NO₂⁻吸附活化特性. 因此, 利用双组分催化剂之间的协同作用以实现高效NO₃⁻RR的活性和选择性是本文的主要研究思路.

本文设计了CuPc/FeNC串联催化剂, 利用CuPc和FeNC对NO₃⁻和NO₂⁻的吸附活化能力的差异, 实现了高效的协同催化转化. X射线衍射、高角环形暗场扫描透射电镜、X射线光电子能谱及X射线吸收谱结果表明, FeNC催化剂中Fe原子均匀分布于ZIF-8热解后的基底. 通过将FeNC和CuPc负载于气体扩散电极, 在流动电解池中完成NO₃⁻RR. CuPc/FeNC催化剂在较低电势区间中能够实现接近100%的NH₃法拉第效率, 同时在−0.57 V vs. RHE时达到273 mA cm^-2的NH₃分电流密度, 并且在整个电势范围内有效地抑制了NO₂^-聚集. 与单组分催化剂CuPc和FeNC对比结果表明, 在−0.53 V vs. RHE时, CuPc/FeNC催化剂表现出较高的FE_(NH3)/FE_(NO2−)比值, 是CuPc催化剂的50倍; 同时CuPc/FeNC催化剂上NH₃分电流密度是FeNC催化剂的1.5倍. 进一步研究了NO₃^-RR中的串联反应机制, 其中FeNC催化剂表现出较高的NO₂^-RR活性, 并且有效抑制了析氢反应. 此外, CuPc/FeNC催化剂和FeNC催化剂在NO₂⁻RR中表现出类似的NH₃分电流密度, 这表明在NO₃⁻RR中, CuPc/FeNC催化剂性能的提高来源于FeNC位点能够进一步还原CuPc位点产生的NO₂^-. 理论计算结果表明, FeNC比CuPc表现出更强的NO₂^-吸附活化能力, 说明NO₂⁻在FeNC上更容易进行加氢还原. NO₃⁻RR反应全路径分析结果表明, 对于^*NO₃还原到^*NO₂过程, CuPc相对于FeNC位点具有明显降低的反应自由能, 说明CuPc有利于NO₂⁻的生成; 而FeNC位点在后续的^*NO₂还原合成^*NH₃过程中具有更低的反应自由能, 这与实验结果一致. 一系列非原位和原位表征证明了CuPc催化剂在高电位下存在少量金属颗粒析出, 与CuPc催化剂在高电位下NH₃分电流密度快速增加结果一致.

综上, 本工作中CuPc和FeNC催化剂之间的协同作用弥补了各自的不足, 通过串联反应机制, 在低过电位下有效增加了NH₃的法拉第效率和电流密度, 实现了高效的协同催化转化, 为设计和合成高效催化剂提供了新思路.

关键词: 硝酸根电化学还原为氨, 协同催化转化, 串联催化, 双组分催化剂, 动态现场原位表征

Abstract:

Cu-based catalysts have been extensively studied to enhance the performance of the electrochemical nitrate reduction reaction (NO₃⁻RR), while it is still a challenge to balance high ammonia (NH₃) current density and Faradaic efficiency. Here, we incorporated nitrogen coordinated iron single atom catalyst (FeNC) with copper phthalocyanine (CuPc), denoted as CuPc/FeNC, for NO₃⁻RR. Compared with the two individual catalysts, this two-component catalyst increases NH₃ Faradaic efficiency and current density at low overpotentials, achieves efficient synergistic catalytic conversion. Experiments and theoretical calculations reveal that the enhanced electrochemical performance of CuPc/FeNC catalyst comes from the tandem process, in which NO₂^‒ is produced on CuPc and then transferred to FeNC and further reduced to NH₃. In this exceptional tandem catalyst system, an outstanding NH₃ Faradaic efficiency close to 100% was achieved at potentials greater than −0.35 V vs. RHE, coupled with a peak NH₃ partial current density of 273 mA cm^‒2 at −0.57 V vs. RHE, effectively suppressing NO₂^‒ production across the entire potential range. This strategy provides a design platform for the continued advancement of NO₃^‒RR catalysts.

Key words: Electrochemical reduction of nitrate, to ammonia, Synergistic catalytic conversion, Tandem catalysis, Two-component catalyst, Operando characterization

王毅, 王硕, 付云凡, 桑佳琪, 臧一鹏, 魏鹏飞, 李合肥, 汪国雄, 包信和. CuPc/FeNC双组分催化剂协同催化硝酸盐转化为氨[J]. 催化学报, 2024, 56: 104-113.

Yi Wang, Shuo Wang, Yunfan Fu, Jiaqi Sang, Yipeng Zang, Pengfei Wei, Hefei Li, Guoxiong Wang, Xinhe Bao. Synergistic catalytic conversion of nitrate into ammonia on copper phthalocyanine and FeNC two-component catalyst[J]. Chinese Journal of Catalysis, 2024, 56: 104-113.

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图/表 5

Scheme 1. Schematic of a tandem catalyst composed of CuPc and FeNC. Brown, blue, green, pink and red represent C, N, Fe, O and Cu atoms, respectively.

Fig. 1. Structure characterizations of FeNC catalyst. HRTEM (a) and HAADF-STEM (b) images of FeNC catalyst. Fe K edge XANES spectra(c) and Fourier transformed (FT) k2-weighted x(k)-function of the EXAFS spectra (d) for Fe K-edge of FeNC catalyst. (e) Wavelet transforms for the Fe K-edge k2-weighted EXAFS oscillations of Fe foil, FeNC, and FePc.

Fig. 2. Electrocatalytic nitrate reduction performance. NH3 Faradaic efficiency (a), NO2? Faradaic efficiency (b), Faradaic efficiency ratio of NH3/NO2? and NH3 partial current density at ?0.53 V (vs. RHE) (c), NH3 partial current density (d) of CuPc/FeNC, FeNC and CuPc/XC-72R electrodes.

Fig. 3. Elucidation of nitrite intermediate mechanistic investigation over CuPc/FeNC tandem system. (a) NH3 Faradaic efficiency and corresponding partial current density of NO3?RR on FeNC electrode. (b) NH3 Faradaic efficiency and corresponding partial current density of NO2?RR on FeNC electrode. (c) NH3 current density of NO2?RR over different electrodes. (d) The adsorption Gibbs free energy of *NO3 and *NO2 on FeNC.

Fig. 5. DFT calculations. (a) Free-energy profile of NO3? to NH3 on the FeNC and CuPc and the corresponding intermediate structures are shown in (b). (c) Charge density difference mappings between NO2? and FeNC, CuPc. The blue and yellow isosurfaces stand for the negative and positive charges, respectively. The isosurface of charge density is set to 0.003 ? bohr?3; The inserted numbers are the transferred electrons of Bader charge. (d) The pathways of alkaline HER on FeNC and CuPc.

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CuPc/FeNC双组分催化剂协同催化硝酸盐转化为氨

Synergistic catalytic conversion of nitrate into ammonia on copper phthalocyanine and FeNC two-component catalyst

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