An oxygen-vacancy-rich polyoxometalate-aided Ag-based heterojunction electrocatalyst for nitrogen fixation

doi:10.1016/S1872-2067(24)60046-X

Abstract

Abstract:

Polyoxometalates (POMs) with well-defined molecular structures are sustainable and promising catalysts for reducing nitrogen to ammonia under ambient conditions. In this study, oxygen-vacancy-rich AgPW₁₁/Ag nanocube catalysts were synthesized via a one-pot method using POMs, reductants, and inducers. The oxygen-vacancy-rich AgPW₁₁/Ag heterojunction catalyst exhibited a significant ammonia yield as high as 46.02 ± 1.03 μg h^-1 mg^-1_cat. and faradaic efficiency of 34.07 ± 0.16% at a potential of -0.2 V (vs. RHE), maintaining stable catalysis for 32 h without decay and greatly outperforming the Ag catalyst. The excellent catalytic performance and mechanism were established using density functional theory calculations. The robust interaction between the d orbitals of the Ag atom in AgPW₁₁^12e and π* orbitals of N₂ activates the adsorbed N₂ and promotes the conversion of the first protonation process *N₂ to *N-NH (the potential determination step). This study provides a new avenue for designing stable Ag-based catalysts for nitrogen fixation.

Key words: Polyoxometalates, Metal-oxo cluster, Electrocatalysis, Nitrogen reduction, Oxygen vacancy, Density functional theory, Heterojunction

Xinyu Chen, Cong-Cong Zhao, Jing Ren, Bo Li, Qianqian Liu, Wei Li, Fan Yang, Siqi Lu, YuFei Zhao, Li-Kai Yan, Hong-Ying Zang. An oxygen-vacancy-rich polyoxometalate-aided Ag-based heterojunction electrocatalyst for nitrogen fixation[J]. Chinese Journal of Catalysis, 2024, 62: 209-218.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60046-X

https://www.cjcatal.com/EN/Y2024/V62/I7/209

Figures/Tables 5

Fig. 1. (a) One-pot-synthesis for AgPW11/Ag. Color code for atoms: red, oxygen; purple, phosphorus; baby blue, silver; and dark blue, tungsten. SEM images (b), EDX mapping (c) and HRTEM images (d) of the AgPW11/Ag nanocubes.

Fig. 2. (a) XRD patterns of the AgPW11/Ag nanocubes and Ag nanowires. (b) SAXS data of AgPW11/Ag and AgPW11. (c) FT-IR spectra of AgPW11/Ag and AgPW11. (d) Ag 3d XPS spectra of AgPW11/Ag and AgPW11. (e) O 1s XPS spectrum of AgPW11/Ag. (f) N2-TPD of AgPW11/Ag and AgPW11. (g) XANES spectra at the Ag K-edge of AgPW11/Ag, reference Ag, and Ag2O. (h) Fourier transform EXAFS spectra of AgPW11/Ag, reference Ag, and Ag2O.

Fig. 3. (a) LSV curves of AgPW11/Ag nanocubes under N2 and Ar in 0.1 mol L-1 HCl. Chronopotentiometry curves (b), UV-vis absorption spectra (c), rate of NH3 yield (d) and FE (e) of AgPW11/Ag nanocubes at -0.1 to -0.5 V vs. RHE. (f) 1H NMR spectra of 15NH3 in electrolyte after 2 h of the NRR and 15NH4Cl.

Fig. 4. (a) The NH3 yield rate and FE of the NRR for AgPW11/Ag and Ag. The NH3 yield rate of a series of AgPW11/Ag catalysts formed under different synthetic conditions (b) and other recently reported NRR catalysts (c). (d) Chronopotentiometry curves for long duration NRR. The NH3 yield rate (e) and FE (f) of the NRR for AgPW11/Ag at -0.2 V (vs. RHE) after the cycling test.

Fig. 5. (a) Spin density distributions computed for different reduced AgPW11. The red value represents the spin density distributed on Ag. Color code for atoms: dark blue, nitrogen; red, oxygen; orange, phosphorus; purple, potassium; baby blue, silver; and curious blue, tungsten. The adsorption configuration (b) and electron density difference (c) of N2 adsorbed on AgPW1112e. The charge accumulation and depletion are depicted in blue and pink grids, respectively. The isosurface value is 0.0004 e ?-3. (d) α-HOMO-8 of the AgPW1112e-N2 system. (e) Schematic diagram of distal, alternating, and mixed pathways for the NRR on AgPW1112e. Color code for atoms: blue, nitrogen; gray, hydrogen; and red, silver. (f-h) The computed free energy diagrams for the NRR on AgPW1112e along the three pathways.

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