揭示明确定义的金属-N4位点在电催化硝酸盐还原中的活性趋势

doi:10.1016/S1872-2067(23)64634-0

催化学报 ›› 2024, Vol. 59: 195-203.DOI: 10.1016/S1872-2067(23)64634-0

揭示明确定义的金属-N₄位点在电催化硝酸盐还原中的活性趋势

蒋远^a^,¹, 杨级^a^,¹, 李沐霖^a, 王雪佳^a, 杨娜^c^,^*(), 陈伟平^a^,^b, 董金超^a^,^b^,^*(), 李剑锋^a^,^b^,^*()

^a厦门大学能源学院, 固体表面物理化学国家重点实验室, 化学化工学院, 厦门大学物理科学与技术学院, 能源材料化学协同创新中心, 福建厦门 361005
^b福建能源材料科学与技术创新实验室(嘉庚创新实验室), 福建厦门 361005
^c电子科技大学材料与能源学院, 四川成都 611731

收稿日期:2023-12-09 接受日期:2024-02-24 出版日期:2024-04-18 发布日期:2024-04-15
通讯作者: *电子信箱: li@xmu.edu.cn (李剑锋), jcdong@xmu.edu.cn (董金超), yna@uestc.edu.cn (杨娜).
作者简介:
¹共同第一作者.
基金资助:
国家重点研发计划(2023YFA1508004);国家自然科学基金(21925404);国家自然科学基金(22222903);国家自然科学基金(52271229);国家自然科学基金(22021001);国家自然科学基金(22005130);国家自然科学基金(22272069);国家自然科学基金(21991151);国家自然科学基金(21902136);中央高校基本科研业务费专项资金(20720210069);中央高校基本科研业务费专项资金(20720210043);中国博士后科学基金(2023M742909);国家基础科学人才培养基金(NFFTBS);国家基础科学人才培养基金(J1310024)

Unveiling the activity tendency of well-defined metal-N₄ sites for electrocatalytic nitrate reduction

Yuan Jiang^a^,¹, Ji Yang^a^,¹, Mu-Lin Li^a, Xue-Jia Wang^a, Na Yang^c^,^*(), Wei-Ping Chen^a^,^b, Jin-Chao Dong^a^,^b^,^*(), Jian-Feng Li^a^,^b^,^*()

^aCollege of Energy, State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, College of Physical Science and Technology, Xiamen University, Xiamen 361005, Fujian, China
^bInnovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen 361005, Fujian, China
^cSchool of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China

Received:2023-12-09 Accepted:2024-02-24 Online:2024-04-18 Published:2024-04-15
Contact: *E-mail: li@xmu.edu.cn (J.-F. Li), jcdong@xmu.edu.cn (J.-C. Dong), yna@uestc.edu.cn (N. Yang).
About author:
¹Contributed equally to this work.
Supported by:
The National Key Research and Development Program of China(2023YFA1508004);The National Natural and Science Foundation of China(21925404);The National Natural and Science Foundation of China(22222903);The National Natural and Science Foundation of China(52271229);The National Natural and Science Foundation of China(22021001);The National Natural and Science Foundation of China(22005130);The National Natural and Science Foundation of China(22272069);The National Natural and Science Foundation of China(21991151);The National Natural and Science Foundation of China(21902136);The Fundamental Research Funds for the Central Universities(20720210069);The Fundamental Research Funds for the Central Universities(20720210043);The China Postdoctoral Science Foundation(2023M742909);The National Science Fund for Fostering Talents in Basic Science(NFFTBS);The National Science Fund for Fostering Talents in Basic Science(J1310024)

摘要/Abstract

摘要：

氨是一种重要的化工原材料, 广泛用于肥料、药物、塑料以及其它化工产品的生产. 特别是, 氨作为一种绿色、新型的替代燃料, 正逐渐被视为未来可持续能源体系的重要组成部分之一. 近期, 研究者们提出了一种新的等离子体电催化合成氨的方法, 为氨的生产开辟了新的途径. 该方法首先在等离子处理条件下将空气中的氮气和氧气氧化成为氮氧化物; 然后, 通过电催化还原NO_x^- (主要为NO₂^-/NO₃^-等)合成氨. 在该过程中, 金属-氮-碳单原子 (M-N-C SACs)催化剂因其金属原子利用率高、活性和选择性好等优点而受到广泛关注. 然而, 由于当前催化剂合成路线的可控性不足, 导致金属中心的配位环境复杂, MN_x配位数(x = 2-5)不明确, 阻碍了对催化剂本征活性趋势的深入揭示. 为了解决上述问题, 研究者们开始关注具有均匀且明确MN₄结构的金属酞菁(MPc), 并将其作为模型催化剂, 用于深入研究电催化硝酸盐还原反应的活性位点和反应机理.

本文将六种具有明确MN₄结构的金属酞菁催化剂(M = Mn, Fe, Co, Ni, Cu和Zn)负载在卡博特碳黑XC-72R载体上, 并探究了不同金属中心的MN₄位点对硝酸盐还原合成氨的活性影响. 扫描电子显微镜、X射线光电子能谱以及氮气吸脱附等温曲线结果表明, 六种不同金属中心的MPc/XC-72R催化剂间的差异仅在于金属中心, 从而排除了载体等其他因素的干扰. 实验结果显示, 金属中心对硝酸盐还原合成氨的活性顺序为: FeN₄ > CuN₄ > NiN₄ > MnN₄ > CoN₄ > ZnN₄. 其中, FeN₄位点表现出最好的催化活性, 在-1.0 V vs. RHE时, 氨的法拉第效率达到83.3%, 产率为2.94 mg_NH3 h^-1 cm^-2, 转化频率(TOF)为4395.2 h^-1. 相比之下, 在相同条件下, ZnN₄位点上亚硝酸盐的选择性和产率最高, 亚硝酸盐的法拉第效率为49.1%, 产率达到16.8 mg_NO2 h^-1 cm^-2. 此外, FeN₄位点的单原子催化剂表现出较好的循环稳定性, 在-0.8 V vs. RHE的电位下, 经过20次循环测试, 氨的法拉第效率仍能维持在80%左右. 密度泛函理论计算结果表明, FeN₄位点对NO₂中间体和氢原子具有适宜的吸附能, 有利于硝酸盐加氢进一步生成氨. 相比之下, NO₂在ZnN₄位点上吸附很弱, 导致NO₂容易从催化剂表面脱附至溶液中, 形成亚硝酸盐副产物. 此外, 计算结果还显示, FeN₄位点上硝酸还原反应的决速步骤NO*→HNO*的自由能差仅为0.07 eV, 进一步证实了FeN₄位点在硝酸盐还原合成氨反应中的优异活性.

综上, 本文系统研究了六种具有明确MN₄结构的金属酞菁催化剂在硝酸盐还原合成氨反应中的活性趋势, 并探究了不同MN₄位点对硝酸盐还原的活性影响. 结合密度泛函理论计算, 揭示了不同MN₄位点对硝酸盐还原反应的机理. 为深刻理解硝酸盐还原反应机制, 指导设计高效活性位提供了参考.

关键词: 电催化, 金属酞菁, 金属-N₄, 硝酸根还原成氨, 活性趋势

Abstract:

Metal-nitrogen-carbon single-atom catalysts (M-N-C SACs) have emerged as a highly promising material for ammonia synthesis from electrocatalytic nitrate reduction due to their isolated metal site and capacity to prevent the N-N coupling. However, understanding the structure-activity relationship at molecular level remains challenging because of the inhomogeneous MN_x structure presented in current synthesized M-N-C catalysts. In this study, we utilized metal phthalocyanine (MPc) as a model platform catalyst containing a uniform and well-defined MN₄ center to unravel their intrinsic activity tendency toward ammonia synthesis from nitrate reduction, both experimentally and theoretically. Our experimental results exhibit a significant activity difference for ammonia production in the order of FeN₄ > CuN₄> NiN₄> MnN₄ > CoN₄ > ZnN₄, and among which the FeN₄ site delivers much higher faradic efficiency and the highest turnover frequency of 83.3% and 4395.2 h^-1 at -1.0 V vs. RHE, respectively. Density-functional theory calculations indicates that, compared to CoN₄ and MnN₄, the FeN₄ site not only has appropriate adsorption strength for NO_x intermediate species, but also has certain inhibitory effects on hydrogen evolution reaction process. These findings provide systematic and reliable guidance for catalyst synthesis toward nitrate reduction to NH₃ from both the experimental and computational perspectives.

Key words: Electrocatalysis, Metal phthalocyanine, Metal-N₄, Nitrate reduction, Activity tendency

蒋远, 杨级, 李沐霖, 王雪佳, 杨娜, 陈伟平, 董金超, 李剑锋. 揭示明确定义的金属-N₄位点在电催化硝酸盐还原中的活性趋势[J]. 催化学报, 2024, 59: 195-203.

Yuan Jiang, Ji Yang, Mu-Lin Li, Xue-Jia Wang, Na Yang, Wei-Ping Chen, Jin-Chao Dong, Jian-Feng Li. Unveiling the activity tendency of well-defined metal-N₄ sites for electrocatalytic nitrate reduction[J]. Chinese Journal of Catalysis, 2024, 59: 195-203.

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图/表 5

Fig. 1. Synthesis and electron microscope characterizations of MPc/XC-72R catalysts. (a) Schematic illustration of synthetic procedure. (b) TEM image of FePc/XC-72R catalyst. (c) Corresponding EDX-elemental mapping of C (red), N (green) and Fe (yellow). (d) Atomic-resolution HADDF-STEM image of FeN4 catalyst.

Fig. 2. Coordination structure analysis. (a) Fe K-edge XANES spectra of FePc/XC-72R and the other references including FePc, Fe foil, FeO and Fe2O3. (b) k2-weighted Fourier transform spectra of FePc/XC-72R and the other references including FePc, Fe foil, FeO and Fe2O3. (c) The WT plots of Fe K-edge EXAFS for Fe foil (top) and FePc/XC-72R (bottom). (d) EXAFS fitting curve for FePc/XC-72R in the range of 1.0-3.0 ?. (e) Corresponding r space fitting curve.

Fig. 3. Electrocatalytic performance of nitrate reduction. (a) LSV polarization curves of different MN4 sites and Pc (N4) as the reference. (b) The production rate of ammonia at -1.0--0.4 V vs. RHE. (c) Faradaic efficiency of NH3 at -0.4--1.0 V vs. RHE. (d) TOF values of different MN4 toward nitrate reduction to ammonia at -1.0 V vs. RHE.

Fig. 4. Durability measurements of FePc/XC-72R at -0.8 V vs. RHE. (a) Faradaic efficiency of NH3 and NO2- during 20 catalytic cycles. (b,c) HAADF-STEM image after durability tests.

Fig. 5. (a) The adsorption energy of *NO2 with different MN4 centers. (b) The line plot between G and ENO2. (c) PDOS for the MN4 center, and E - EFermi is marked in each graph with the black dashed line. (d) Free energy profiles for nitrate reduction on FeN4 site.

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揭示明确定义的金属-N₄位点在电催化硝酸盐还原中的活性趋势

Unveiling the activity tendency of well-defined metal-N₄ sites for electrocatalytic nitrate reduction

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