Ternary red phosphorus/CoP2/SiO2 microsphere boosts visible-light-driven photocatalytic hydrogen evolution from pure water splitting

doi:10.1016/j.jmst.2022.02.034

Abstract

Abstract:

Red phosphorus (RP) is a promising visible-light-driven semiconductor for photocatalytic hydrogen evolution, but the activity is restricted due to the rapid charge carrier recombination and sluggish surface reaction kinetics. Herein, cobalt phosphide (CoP₂) modified RP heterostructure was developed by in situ phosphorization of cobalt oxide from phosphorus vapor. By tuning the amounts of CoP₂ in the heterostructure, the optimized hybrid exhibited a HER rate reaching 11.79 μmol h^-1 under visible light illumination, which is 3.5 times higher than that of the RP with Pt as cocatalyst. It was experimentally indicated that the intimate interaction between CoP₂ and RP gave rise to improved visible light absorption and accelerated photogenerated electron-holes separation. Moreover, the CoP₂ as a noble-metal-free cocatalyst could promote the surface hydrogen evolution reaction, which synergetic benefited the photocatalytic hydrogen production activity.

Key words: Red phosphorus, Cobalt phosphide, Heterostructure, Photocatalytic hydrogen evolution

Chen Yang, Yukun Zhu, Yiming Liu, Hongwei Wang, Dongjiang Yang. Ternary red phosphorus/CoP₂/SiO₂ microsphere boosts visible-light-driven photocatalytic hydrogen evolution from pure water splitting[J]. J. Mater. Sci. Technol., 2022, 125: 59-66.

Figures/Tables 8

Fig. 1. (a) Schematic illustration of synthetic procedure of RP/CoP2/SiO2. SEM images of (b) SiO2, (c) SiO2/Co3O4 and (d) RP/CoP2(6)/SiO2. (e) HRTEM image of SiO2/Co3O4. (f) TEM of (g) HRTEM images of RP/CoP2(6)/SiO2. (h) STEM image and corresponding EDS mapping of RP/CoP2(6)/SiO2.

Fig. 2. (a) XRD patterns and (b) Raman spectra of RP/CoP2(x)/SiO2.

Fig. 3. High resolution XPS spectra of (a) P 2p for RP/SiO2, RP/Pt/SiO2 and RP/CoP2(6)/SiO2, and (b) Co 2p for RP/CoP2(6)/SiO2.

Fig. 4. (a) UV-vis diffuse reflection spectroscopy and (b) Tauc plots of as-prepared samples.

Fig. 5. Photocatalytic HER activities from pure water splitting. Comparison with (a) different co-catalyst loaded RP/SiO2 and (b) RP/CoP2(x)/SiO2 under visible light (λ ≥ 420 nm) irradiation. (c) Wavelength-dependent HER over RP/CoP2(6)/SiO2 under Xe lamp equipped with different band-pass filters (centered at 400, 420, 450, 500, 550, 600, 650, 700 and 740 nm, respectively).

Fig. 6. (a) Linear sweep voltammetry curves and (b) open circuit potential curves of different cocatalyst loaded RP/SiO2. (c) Photocurrent-time curves and (d) Nyquist plots of RP/SiO2, RP/Pt/SiO2 and RP/CoP2(x)/SiO2.

Fig. 7. (a) photoluminescence spectra and fluorescence lifetime of (b) RP/SiO2, (c) RP/Pt/SiO2 and (d) RP/CoP2(6)/SiO2 samples.

Fig. 8. (a) Mott-Schottky plot and (b) proposed mechanism for the photocatalytic hydrogen production by RP/CoP2(x)/SiO2.

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Ternary red phosphorus/CoP₂/SiO₂ microsphere boosts visible-light-driven photocatalytic hydrogen evolution from pure water splitting

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