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

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64578-4

https://www.cjcatal.com/EN/Y2024/V56/I1/104

Figures/Tables 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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