Manipulating the interactions between N-intermediates and one-dimensional conjugated coordination polymers to boost electroreduction of nitrate to ammonia

doi:10.1016/S1872-2067(24)60059-8

Abstract

Abstract:

Electrocatalytic reduction of nitrate to ammonia (NITRR) is a promising strategy to remove nitrate pollutants and generate ammonia under mild conditions. However, the low conversion rate of nitrate and insufficient ammonia production rate severely limits the development of NITRR. Manipulating the adsorption of N-intermediates on the surface of catalyst greatly affects the activity and the selectivity of catalytic reaction. Herein, four one-dimensional π-d conjugated coordination polymers (1D CCPs) are synthesized and applied to NITRR. The selectivity and activity of NITRR are well improved by metal ion substitutions, which regulate the adsorption towards generated intermediates. The ammonia production rate reaches 2.28 mg h^-1 cm^-2 over Cu-BTA in 2 h, comparable to recent works at low nitrate concentrations, and the conversion rate of nitrate up to 96.74% in four hours with 79.46% ammonia selectivity. Density functional theory calculations reveal that Cu-BTA had electron-richer Cu center, causing the enhanced free energy of *NO and the attenuation of N=O bond. Therefore, the ΔG required for converting *NO to *NHO is reduced and the further hydrogenation is promoted. Additionally, the adsorption energies toward NH₃ are also effectively reduced by metal ions substitution, accelerating the desorption of generated and adsorbed NH₃, making the turnover of catalysts more frequent.

Key words: Nitrate reductionAmmonia synthesis, Electrocatalysis, One-dimensional conjugated, coordination polymers, Adsorption manipulation

Qing Liu, Xue-Feng Cheng, Jin-Yan Huo, Xiao-Fang Liu, Huilong Dong, Hongbo Zeng, Qing-Feng Xu, Jian-Mei Lu. Manipulating the interactions between N-intermediates and one-dimensional conjugated coordination polymers to boost electroreduction of nitrate to ammonia[J]. Chinese Journal of Catalysis, 2024, 62: 231-242.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60059-8

https://www.cjcatal.com/EN/Y2024/V62/I7/231

Figures/Tables 5

Fig. 1. (a) Schematic diagram of the synthesis of M-BTA. SEM image (b) and TEM image (c) of Cu-BTA electrocatalyst. (d) HAADF-STEM image of Cu-BTA and corresponding EDX element mapping images of Cu, C and N elements. XPS survey spectrum (e), FT-IR spectra (f) and XRD patterns (g) of Fe-BTA, Co-BTA, Ni-BTA and Cu-BTA.

Fig. 2. NITRR activity of the Cu-BTA electrocatalyst. (a) LSV curves of the Cu-BTA tested in 0.5 mol L-1 Na2SO4 with and without 100 mg?L?1 NO3--N. Compare faradaic efficiency for ammonia (FENH3), selectivity for ammonia (SNH3), selectivity of nitrite (SNO2-) and NH3 yield rate at different applied potentials (b) and different electrocatalysts (c). (d) Comparison of conversion for nitrate and NH3 yield rate of Cu-BTA with the previously reported catalysts (Table S3). (e) Time-dependent concentration change of NO3--N, NO2--N and NH3-N tested at ?1.2 V (vs. RHE) with 100 mg L-1 initial nitrate. (f) Consecutive 25 times cycles reduction tests at ?1.2 V vs. RHE on Cu-BTA. Potential-dependent in-situ IR (g) and in situ Raman (h) spectra of Cu-BTA.

Fig. 3. Conversion of N-NO3-, NH3 yield rate, selectivity of ammonia and nitrite. Comparison of Cu-BTA electrocatalyst with different initial N-NO3- concentrations (a), at different temperatures (b) and in different pH electrolytes (c). The effect of electrocatalytic reduction of nitrate with different concentrations of Cl-. The plots of concentration of N-NO3- (d), N-NO2- (e) and N-NH3 (f) with time. (g) TN removal rate with different concentrations of Cl-. The XRD patterns of the recovered NH4Cl(s) product (h) and synthesized MgNH4PO4·6H2O (i).

Fig. 4. (a) LSV curves of different catalysts in 0.5 mol L?1 Na2SO4 with 100 mg mL-1 NO3?-N. (b) EIS Nyquist plots of different catalysts. (c) Plots of the current density differences (Δj/2) versus a function of the scan rates at various scan rates (5-100 mV s?1) for different catalysts. (d) Tafel plots of different catalysts in 0.5 mol L?1 Na2SO4.

Fig. 5. Reaction pathway for nitrate on the surface of Cu-BTA (a), Ni-BTA, Co-BTA and Fe-BTA (b). Adsorption energies diagram of NITRR involved species (c) and free energy evolution for H2 formation on the surface of M-BTA (M: Fe, Co, Ni, Cu) (d).

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