Deciphering the synergy between electron localization and alloying for photoelectrochemical nitrogen reduction to ammonia

doi:10.1016/S1872-2067(22)64178-0

Abstract

Abstract:

Photoelectrochemistry that directly takes advantage of solar energy by photoelectrodes is a promising green route for the nitrogen fixation, but is currently far from practical application. It is necessary to understand the structure-reactivity interplay of the photocathodes for rendering rational improvement of the existing challenges. Here, we make efforts to reveal AuCoPd-CoO_x/SiO₂/Si photocathodes capable of selective photoelectrochemical conversion of nitrogen to ammonia at varied pressures, achieving an ammonia yield rate of 22.2 ± 0.4 μg·h^-1·cm^-2 and a faradic efficiency of 22.9% at -0.1 V vs. reversible hydrogen electrode under 3-MPa nitrogen. In particular, we focus on the remarkable, but often subtle, roles of the synergy between electron localization and alloying in determining the reactivity of the photocathodes. Specifically, operando XPS and XAS illustrate that the oxidation states of Au and Pd enable the photoinduced electron capture as the reduction sites to produce the *N₂ and *H active species, respectively, facilitating the couple of N-H for ammonia synthesis. Although this study is not sufficient to break through bottleneck, there is much insight on the design of efficient and robust photocathodes for photoelectrochemical nitrogen fixation.

Key words: Photoelectrochemical nitrogen fixation, Electron localization, Alloying, Pressurized reaction, Synergy mechanism

Jianyun Zheng, Yanhong Lyu, Aibin Huang, Bernt Johannessen, Xun Cao, San Ping Jiang, Shuangyin Wang. Deciphering the synergy between electron localization and alloying for photoelectrochemical nitrogen reduction to ammonia[J]. Chinese Journal of Catalysis, 2023, 45: 141-151.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64178-0

https://www.cjcatal.com/EN/Y2023/V45/I2/141

Figures/Tables 7

Fig. 1. Preparation and structural characterization of ACP sample. (a) Schematic diagram for the preparation of ACP sample. (b) Cross-sectional HRTEM images of ACP sample. The inset is the magnified image of the specified area. High-magnification images on the right corresponds to the marked area in the inset. (c) STEM image with the elemental distribution maps of Au, Co, Pd and O for ACP sample.

Fig. 2. AR-XPS depth of ACP sample at θTO of 45° and 90°. (a) Au 4f spectra. (b) Co 2p3/2 spectra. (c) Pd 3d spectra. (d) VB spectra. The inset of (d) is high magnification image corresponding to the designated area by green ellipse.

Fig. 3. Ex-situ XAS characterizations of the AC and ACP samples and comparison with relevant standards. (a) Au L3-edge XANES spectra. (b) FT k3-weighted EXAFS spectra obtained from Au L3-edge absorption spectra. (c) Co K-edge XANES spectra. (d) Average oxidation state of Co in the samples by Co K-edge XANES. (e) Pd K-edge XANES spectra. (f) FT k3-weighted EXAFS spectra obtained from Pd K-edge absorption spectra.

Fig. 4. Performance of pressurized PEC NRR in 0.05 mol·L-1 potassium phosphate buffer aqueous solution under 1 sun irradiation. (a) 1H NMR spectra of the electrolytes after PEC NRR by the feeding gas of 14N2 and 15N2. (b) NH3 yield rate and FE of ACP sample as a function of applied potentials under ambient conditions. (c) NH3 yield rate and FE of ACP sample with different reaction pressures. (d) The curve of time-dependent photocurrent density for the ACP sample at -0.3 V vs. RHE under ambient conditions. The inset is time-dependent NH3 yield and FE obtained from ACP sample at -0.3 V vs. RHE under ambient conditions.

Fig. 5. Analysis of active sites on the ACP sample by operando XPS. Au 4f (a), Co 2p3/2 (b), and Pd 3d (c) spectra of the ACP sample tested at θTO = 90° under illumination. The laser light with 520 nm was generated by a 1 mW laser product with ~0.1 cm2 light spot. (d) Proposed mechanism for separation and transfer of photoinduced electron-hole pairs on the ACP sample.

Fig. 6. Atomic coordination environment of ACP sample in the PEC NRR process under ambient conditions by operando XAS. (a) Au L3-edge XANES spectra of the ACP sample at different applied potentials during PEC NRR. The PEC reactions of ACP sample operated in the dark or He conditions were employed as the control experiments. (b) The difference XANES spectra of Au L3-edge for the ACP sample measured at different applied potentials. The spectrum tested in the dark as the baseline was selected to obtain the various difference spectra. (c) FT k3-weighted EXAFS spectra of the ACP sample at different applied potentials obtained from Au L3-edge absorption spectra. (d) Pd K-edge XANES spectra of the ACP sample as a function of applied potentials. The inset is the magnifying Pd K-edge XANES spectra ranged from 24365 to 24385 eV.

Fig. 7. Schematic representation of the work mechanism of the synergy between electron localization and alloying for PEC NRR on the Si-based photocathode. The proposed cooperative route for PEC NRR mainly the session of N≡N bond on *Au sites and the formation of Had on *Pd sites.

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