Ag nanoparticles anchored organic/inorganic Z-scheme 3DOMM-TiO2‒x-based heterojunction for efficient photocatalytic and photoelectrochemical water splitting

doi:10.1016/S1872-2067(21)63978-5

Abstract

Abstract:

Narrow spectral response, low charge separation efficiency and slow water oxidation kinetics of TiO₂ limit its application in photoelectrochemical and photocatalytic water splitting. Herein, a promising organic/inorganic composite catalyst Ag/PANI/3DOMM-TiO_2-_x with a three-dimensional ordered macro-and meso-porous (3DOMM) structure, oxygen vacancy and Ti³⁺ defects, heterojunction formation and noble metal Ag was designed based on the Z-scheme mechanism and successfully prepared. The Ag/PANI/3DOMM-TiO_2-_x ternary catalyst exhibited enhanced hydrogen production activity in both photocatalytic and photoelectrochemical water splitting. The photocatalytic hydrogen production rate is 420.90 μmol g^-1 h^-1, which are 19.80 times and 2.06 times higher than the commercial P25 and 3DOMM-TiO₂, respectively. In the photoelectrochemical tests, the Ag/PANI/3DOMM-TiO_2-_x photoelectrode shows enhanced separation and transfer of carriers with a high current density of 1.55 mA cm^-2 at equilibrium potential of 1.23 V under simulated AM 1.5 G illumination, which is approximately 5 times greater than the 3DOMM-TiO₂. The present work has demonstrated the promising potential of organic/inorganic Z-scheme photocatalyst in driving water splitting for hydrogen production.

Key words: Photoelectrochemical, Photocatalysis, Organic/inorganic composite, Heterojunction, Water splitting

Zhiying Xu, Chunyu Guo, Xin Liu, Ling Li, Liang Wang, Haolan Xu, Dongke Zhang, Chunhu Li, Qin Li, Wentai Wang. Ag nanoparticles anchored organic/inorganic Z-scheme 3DOMM-TiO_2‒_x-based heterojunction for efficient photocatalytic and photoelectrochemical water splitting[J]. Chinese Journal of Catalysis, 2022, 43(5): 1360-1370.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63978-5

https://www.cjcatal.com/EN/Y2022/V43/I5/1360

Figures/Tables 11

Scheme 1. The synthesis procedure of Ag/PANI/3DOMM-TiO2-x samples.

Fig. 1. TEM images of PANI/3DOMM-TiO2-x (a) and Ag/PANI/ 3DOMM-TiO2-x (b); HRTEM images of 3DOMM-TiO2-x (c) and Ag/PANI/ 3DOMM-TiO2-x (d); (e) EDS images of Ag/PANI/3DOMM-TiO2-x.

Fig. 2. (a) XRD patterns of 3DOMM-TiO2, 3DOMM-TiO2-x, PANI/3DOMM-TiO2-x and Ag/PANI/3DOMM-TiO2-x; (b) EPR spectrum of Ag/PANI/3DOMM-TiO2-x.

Fig. 3. (a) XPS survey spectrum of Ag/PANI/3DOMM-TiO2-x; (b) High resolution C 1s spectra; (c) N 1s spectra; (d) Ti 2p spectra; (e) O 1s spectra; (f) Ag 3d spectra.

Fig. 4. UV-Vis DRS pattern (a) and the Tauc plot of the (αhν)1/2 vs. photon energy (hν) (b) of 3DOMM-TiO2-x, PANI/3DOMM-TiO2-x and Ag/PANI/3DOMM-TiO2-x; (c) The XPS valence band spectrum of Ag/PANI/3DOMM-TiO2-x.

Fig. 5. Transient photocurrent curves (a) and EIS Nyquist plots (b) of 3DOMM-TiO2, 3DOMM-TiO2-x, PANI/3DOMM-TiO2-x and Ag/PANI/3DOMM-TiO2-x (1.23V vs. RHE).

Fig. 6. (a) The hydrogen production rate of different samples; (b) The stability of Ag/PANI/3DOMM-TiO2-x for hydrogen production.

Fig. 7. LSV measurements (a) and ABPE (b) of 3DOMM-TiO2, 3DOMM-TiO2-x, PANI/3DOMM-TiO2-x and Ag/PANI/3DOMM-TiO2-x; (c) Stability at 1.23 V vs. RHE of Ag/PANI/3DOMM-TiO2-x photoanodes; (d) Linear current-voltage curves with a scan rate of 50 mV/s of 3DOMM-TiO2 and Ag/PANI/3DOMM-TiO2-x photoelectrodes without illumination.

Fig. 8. (a) J-V curves of 3DOMM-TiO2 and Ag/PANI@3DOMM-TiO2-x measured with 1 mol/L NaSO3 and without 1 mol/L NaSO3; (b) ηinjection of 3DOMM-TiO2 and Ag/PANI/3DOMM-TiO2-x.

Fig. 9. Mott-Schottky plots of 3DOMM-TiO2-x, PANI/3DOMM-TiO2-x and Ag/PANI/3DOMM-TiO2-x.

Scheme 2. Schematic of photocatalytic and PEC hydrogen evolution on Ag/PANI/3DOMM-TiO2-x.

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