Proximity electronic effect of adjacent Ni Site enhances compatibility of hydrogenation and deoxygenation over Cu Site to boost nitrate electroreduction to ammonia

doi:10.1016/S1872-2067(24)60221-4

Abstract

Abstract:

Electrocatalytic conversion of nitrate to ammonia (NITRR) can simultaneously achieve the removal of nitrate and the synthesis of value-added ammonia, a promising candidate to replace Haber-Bosch process with low carbon dioxide emissions. However, high hydrogenation energy barrier for *NO intermediates and insufficient supply of active hydrogen cause slow hydrogenation process, and further result in low efficiency of nitrate conversion and ammonia synthesis. Herein, a series of tandem catalysts, one-dimensional coordination polymers (1D CCPs) with dual sites are synthesized and obtained 190.4 mg h^-1 mg_cat^-1 ammonia production rate with Faradaic efficiency of 97.16%, outperforming to the most of recent reported catalysts. The catalytic performances are well-maintained even after a long-term stability test of 1200 h, laying the foundation for practical applications. Density functional theory results reveal that the stationary adsorbed *NO on Ni site induced proximity electronic effect could reduce the energy barrier for hydrogenation of *NO intermediates over Cu site. In addition, the Ni site in the dual sites 1D CCPs is conducive to generating active hydrogen, providing rich proton source to boost the hydrogenation of *NO, and further enhancing the compatibility of deoxygenation and hydrogenation process. Our work paves a new insight into the mechanism of NITRR process and will inspire more research interests in exploring the proximity electronic effect in catalytic process.

Key words: Electrocatalysis, Ammonia synthesis, Nitrate reduction, Proximity electronic effect, Dual sites

Xue-Feng Cheng, Qing Liu, Qi-Meng Sun, Huilong Dong, Dong-Yun Chen, Ying Zheng, Qing-Feng Xu, Jian-Mei Lu. Proximity electronic effect of adjacent Ni Site enhances compatibility of hydrogenation and deoxygenation over Cu Site to boost nitrate electroreduction to ammonia[J]. Chinese Journal of Catalysis, 2025, 70: 285-298.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60221-4

https://www.cjcatal.com/EN/Y2025/V70/I3/285

Figures/Tables 7

Fig. 1. Synthesis and characterizations of NixCuy-BTA. (a) Schematic diagram of synthetic route. FT-IR spectra of BTA (b) and NixCuy-BTA (c). (d) XRD patterns of NixCuy-BTA.

Fig. 2. SEM images of Ni-BTA (a) and Ni1Cu1-BTA (c). TEM images of Ni-BTA (b) and Ni1Cu1-BTA (d). (e) HAADF and corresponding EDS elemental mapping images of Ni1Cu1-BTA.

Fig. 3. Composition characterization of NixCuy-BTA. Ni 2p (a) and Cu 2p (b) spectra of Ni-BTA, Cu-BTA and Ni1Cu1-BTA. Ni K-edge XANES spectra for Ni1Cu1-BTA, NiO, NiPc (nickel phthalocyanine), and Ni foil (c) and corresponding k3-weight Fourier transforms (d). Cu K-edge XANES spectra for Ni1Cu1-BTA, CuO, CuPc and Cu foil (e) and corresponding k3-weight Fourier transforms (f). WT of the Ni K-edge for Ni foil (g), NiO (h), NiPc (i), Ni1Cu1-BTA (j), and Cu K-edge for Cu foil (k), CuO (l), CuPc (copper phthalocyanine) (m), and Ni1Cu1-BTA (n).

Fig. 4. Electrocatalytic NITRR performances of NixCuy-BTA. (a) LSV curves of the Ni1Cu1-BTA in 1 mol L?1 KOH with and without 0.1 mol L?1 KNO3 electrolyte. (b) NH3 yield rates and FEs for Ni-BTA, NixCuy-BTA and Cu-BTA at ?0.9 V vs. RHE and (c) Ni1Cu1-BTA at various applied potentials in 1 mol L?1 KOH with 0.1 mol L?1 KNO3. (d) Comparison of the nitrate reduction performance for Ni-BTA, Ni1Cu1-BTA and Cu-BTA. (e) Time-dependent concentrations change of N-NO3?, N-NO2? and N-NH3. (f) Nitrate reduction performance of Ni1Cu1-BTA with different conditions. (g) 1H NMR spectra of (14NH4)2SO4, (15NH4)2SO4 and the electrolyte after NITRR using 14NO3? and 15NO3? as sources. (h) 1H NMR spectra of the electrolyte after 15NO3? reduction tests at various time. (i) Long-term stability tests of Ni1Cu1-BTA at ?0.9 V vs. RHE (the reaction period for each cycle is 20 h). (j) Comparison of the NH3 yield rates and FEs of Ni1Cu1-BTA with other previously reported catalysts.

Fig. 5. Characterizations of electrocatalytic NITRR process over Ni1Cu1-BTA. In-situ DEMS (a), in-situ Raman spectra (b) and in-situ IR spectra (c) of Ni1Cu1-BTA in K14NO3 electrolyte. ESR spectra of Ni1Cu1-BTA (d) and Ni-BTA (e) in electrolyte with different concentrations of NO3?. (f) Corresponding linear fit curves of the intensities of ESR signal and the concentrations of NO3?.

Fig. 6. (a) The optimized structures and DFT-calculated total energies (Etotal) of bilayer CuNi-BTA with different stacking configurations. (b) The adsorption energies of NO on Cu site and Ni site in ML-CuNi-BTA, BL-Cu/Ni-BTA and BL-CuNi-BTA. (c) The isosurface of charge density on BL-Ni-BTA, BL-Cu-BTA, and BL-CuNi-BTA, along with the Bader charge assigned on the metal atoms. Reaction pathway of NITRR on Ni site in BL-CuNi-BTA (d), Cu site in BL-CuNi-BTA (e), Ni site in Cu pre-adsorbed BL-CuNi-BTA (f), and Cu site in Ni pre-adsorbed BL-CuNi-BTA (g). The *NOCu and *NONi denote that the Cu or Ni site is pre-adsorbed by a generated NO molecule.

Fig. 7. The performances of Zn-NO3- battery. (a) Schematic illustration for Zn-NO3- battery with Ni1Cu1-BTA cathode. The open circuit voltage (b), polarization curves and power density (c) for Ni1Cu1-BTA-based Zn-NO3- battery. Galvanostatic discharge curves at certain current densities (d) and corresponding NH3 yield and FE (e) of Zn-NO3- battery. (f) Charge-discharge cycling curves at 4 mA cm-2. (g) Comparison with other reported Zn-NO3- batteries. (h) Long-term stability tests of Zn-NO3- battery system and corresponding NH3 yield and FE.

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