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

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

Chinese Journal of Catalysis ›› 2024, Vol. 59: 195-203.DOI: 10.1016/S1872-2067(23)64634-0

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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)

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64634-0

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

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