Schottky junction coupling with metal size effect for the enhancement of photocatalytic nitrate reduction

doi:10.1016/S1872-2067(24)60280-9

Abstract

Abstract:

Nitrate pollution poses a significant environmental challenge, and photocatalytic nitrate reduction has garnered considerable attention due to its efficiency and environmental advantages. Among these, the development of Schottky junctions shows considerable potential for practical applications. However, the impact of metal nanoparticle size within Schottky junctions on photocatalytic nitrate reduction remains largely unexplored. In this study, we propose a novel method to modulate metal nanoparticle size within Schottky junctions by controlling light intensity during the photodeposition process. Smaller Au nanoparticles were found to enhance electron accumulation at active sites by promoting charge transfer from COF to Au, thereby improving internal electron transport. Additionally, the Schottky barrier effectively suppressed reverse electron transfer while enhancing NO₃^- adsorption and activation. The Au₂-COF exhibited remarkable nitrate reduction performance, achieving an ammonia yield of 382.48 μmol g^-1 h^-1, 5.7 times higher than that of pure COF. This work provides novel theoretical and practical insights into using controlled light intensity to regulate metal nanoparticle size within Schottky junctions, thereby enhancing photocatalytic nitrate reduction.

Key words: Schottky junction, Nitrate reduction, Photocatalysis, Covalent organic frameworks

Xuemeng Sun, Jianan Liu, Qi Li, Cheng Wang, Baojiang Jiang. Schottky junction coupling with metal size effect for the enhancement of photocatalytic nitrate reduction[J]. Chinese Journal of Catalysis, 2025, 73: 358-367.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60280-9

https://www.cjcatal.com/EN/Y2025/V73/I6/358

Figures/Tables 7

Scheme 1. Synthesis process of Au2-COF composites.

Fig. 1. (a) FT-IR spectra of COF. (b) The solid-state 13C NMR spectra of COF. (c) Experimental and simulated PXRD patterns of COF. (d) XRD images of COF, Au25-COF and Au2-COF.

Fig. 2. (a, b) SEM and TEM images of COF. (c, d) TEM and HRTEM images of Au2-COF. (e) Element mapping images of C, N and Au.

Fig. 3. (a-c) In-situ XPS spectra of C 1s (a), N 1s (b), and Au 4f (c) of samples. (d,e) Work functions of COF and Au. (f) Electron density difference of Au2-COF. (g-i) The charge transfer mechanism at the Au2-COF Schottky junction interface (Evac: Vacuum level, Ef, m: Metal Fermi level, Ef, s: Semiconductor Fermi level, EC: Conduction band level, EV: Valence band level, φ: Work function.).

Fig. 4. Transient photocurrent responses (a) and EIS Nyquist plots (b) of COF, Au25-COF and Au2-COF. Steady-state PL (c) and TRPL (d) spectra of COF, Au25-COF and Au2-COF.

Fig. 5. NH4+ yield (a) and NH4+ formation rate (b) of COF, Au25-COF and Au2-COF. (c) Comparison of photocatalytic nitrate reduction rates of Au2-COF and other catalyst. (d) NH4+ field of Au2-COF at different NO3- concentrations. (e) 1H NMR spectra of time-dependent concentration change of NH4+ using 15NO3- and 14NO3- as the NO3- source. (f) AQE of Au2-COF.

Fig. 6. (a) In-situ DRIFTS spectra from the as-prepared Au2-COF during the photocatalytic nitrate reduction. (b) Possible mechanism of photocatalytic nitrate reduction process in Au2-COF.

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