Defect-rich Cu@CuTCNQ composites for enhanced electrocatalytic nitrate reduction to ammonia

doi:10.1016/S1872-2067(23)64454-7

Abstract

Abstract:

Electrochemical conversion of nitrate (NO₃^‒) pollutants into chemical feedstock and fuel ammonia (NH₃) can contribute to sustainable mitigation of the current severe energy and environmental crises. However, the electrocatalytic NO₃^‒ reduction to NH₃ (NRA) involves a sluggish multielectron and proton transfer process that competes with the hydrogen evolution reaction (HER) in aqueous media, imposing great challenges in developing highly selective catalysts for NRA. In this study, we developed a copper and copper-tetracyanoquinodimethane composite catalyst (Cu@CuTCNQ), which possesses a high density of copper vacancy defects. This catalyst has been proven to be efficient for NRA through an in situ electrochemical reconstruction method. The structural evolution of CuTCNQ during NRA was investigated by in situ Raman spectroscopy, which indicated an accelerated charge transfer from the CuTCNQ substrate to the derived Cu, which facilitated the adsorption activation of NO₃^‒. The obtained Cu@CuTCNQ exhibited an excellent catalytic performance for NRA, with a Faradaic efficiency of 96.4% and productivity of 144.8 μmol h^-1 cm^-2 at -0.6 V vs. a reversible hydrogen electrode, superior to Cu nanoparticle counterparts and most Cu-based catalysts. Cu vacancy defects and sufficient interfacial charge transfer synergistically optimize the charge distribution of Cu active sites, reduce the energy barrier for NO₃^‒ adsorption, and promote deoxidation and hydrogenation processes, thus enhancing NRA and selectivity.

Key words: Nitrate reduction, Ammonia synthesis, Copper vacancy, Electrocatalysis, Electrochemical reconstruction

Na Zhou, Jiazhi Wang, Ning Zhang, Zhi Wang, Hengguo Wang, Gang Huang, Di Bao, Haixia Zhong, Xinbo Zhang. Defect-rich Cu@CuTCNQ composites for enhanced electrocatalytic nitrate reduction to ammonia[J]. Chinese Journal of Catalysis, 2023, 50: 324-333.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64454-7

https://www.cjcatal.com/EN/Y2023/V50/I7/324

Figures/Tables 6

Fig. 1. (a) Chemical structure of CuTCNQ phase I. (b) XRD and Rietveld refinement patterns of CuTCNQ phase I sample. XANES (c) and FT-EXAFS (d) spectra of Cu K-edge for CuTCNQ and reference samples. Wavelet transform (WT) of EXAFS of Cu foil(e), CuPc (f), and CuTCNQ (g).

Fig. 2. Ex situ SEM characterization for the morphological evolution of CuTCNQ during in situ electrochemical reconstruction.

Fig. 3. (a) XRD patterns of Cu@CuTCNQ composites formed by electrochemical reconstruction of CuTCNQ. (b) TEM image of CuTCNQ. (c,d) TEM images of Cu@CuTCNQ. (e) HRTEM image of Cu@CuTCNQ. (f) Elemental mapping images of Cu@CuTCNQ.

Fig. 4. (a) LSV polarization curves of CuTCNQ and Cu@CuTCNQ in 0.1 mol L?1 KOH electrolyte with and without 0.1 mol L?1 NO3?. The scan rate is 10 mV s-1. (b) Chronoamperometry curves of Cu@CuTCNQ in 0.1 mol L?1 KOH solution with 0.1 mol L?1 NO3? at various applied potentials. FE (c) and yield rates (d) of NH3 over Cu@CuTCNQ and Cu NPs in 0.1 mol L?1 KOH electrolyte with 0.1 mol L?1 NO3?. (e) 1H NMR spectra at various electrolysis time intervals at the applied potential of -0.6 V vs. RHE, using 0.1 mol L?1 KOH containing 0.1 mol L?1 15NO3? as the electrolyte. (f) Current density at the applied potential of -0.6 V vs. RHE for 10 h.

Fig. 5. (a,b) Raman spectra of TCNQ and CuTCNQ at open-circuit voltage (OCV) and 0.25 V vs. RHE, respectively. (c,d) Potential-dependent in situ Raman spectra of CuTCNQ in 0.1 mol L?1 KOH solution containing 0.1 mol L?1 NO3?.

Fig. 6. (a) DEMS measurement of NRA over Cu@CuTCNQ. (b) Optimized charge density difference between perfectly crystallized Cu and VCu-Cu after adsorbing NO3?. Cyan and yellow regions indicate the depletion and accumulation of the electron density, respectively. (c) Gibbs free-energy diagram of NRA on Cu and VCu-Cu. U = 0.0 V vs. RHE. The inset is the optimized structure models of NRA intermediates adsorbed on VCu-Cu. (d) Schematic illustration of the NRA pathway on vacancy defect-rich Cu (111) surface. (e) Free energy of H2 formation over Cu and VCu-Cu. Blue, red, white, and pink spheres represent Cu, O, N, and H atoms, respectively.

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