Synergistic Effect of Ag and Ag2O on Photocatalytic H2-evolution Performance of TiO2

doi:10.15541/jim20190460

Abstract

Abstract:

Highly efficient TiO₂ photocatalysts (TiO₂/Ag-Ag₂O) co-modified by Ag as electron cocatalysts and Ag₂O as interfacial catalytic active sites were synthesized via a two-step process including the initial photoinduced deposition of metallic Ag nanoparticles on the TiO₂ surface (TiO₂/Ag) and the following in situ oxidation of partial Ag into Ag₂O by low-temperature calcination. Ag nanoparticles function as effective electron cocatalysts for the steady capture and rapid transportation of photogenerated electrons from TiO₂ surface to Ag₂O, while the adsorbed H⁺ ions from solution to Ag₂O as the interfacial catalytic active sites are reduced into H₂. The synergistic effect of Ag and Ag₂O can accelerate the electrons transfer and promote the rapid H₂-evolution reaction for enhanced photocatalytic H₂-evolution performance of TiO₂/Ag-Ag₂O. The highest H₂-evolution rate of the resultant TiO₂/Ag-Ag₂O calcinated at 300 ℃ reached 75.20 μmol/h, which was higher than those of the TiO₂ (3.59 μmol/h) and TiO₂/Ag (41.13 μmol/h) by 21.0 and 1.8 times, respectively. This study provides a new strategy for the design and synthesis of highly efficient photocatalytic H₂-evolution materials.

Key words: TiO₂, electron cocatalyst, interfacial catalytic active site, synergistic effect, photocatalytic H₂ evolution

CLC Number:

O643

WANG Ping,LI Xinyu,SHI Zhanling,LI Haitao. Synergistic Effect of Ag and Ag₂O on Photocatalytic H₂-evolution Performance of TiO₂[J]. Journal of Inorganic Materials, 2020, 35(7): 781-788.

Figures/Tables 10

Fig. 1 (A) Schematic diagram of preparation for TiO2/Ag-Ag2O and (B) their corresponding photographs (a) TiO2-C; (b) TiO2/Ag; (c) TiO2/Ag-Ag2O(200); (d) TiO2/Ag-Ag2O (300); (e) TiO2/Ag-Ag2O(400)

Fig. 2 (A) XRD patterns, (B) diffraction peaks of metallic Ag and (C) diffraction peaks of Ag2O for TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x)

Fig. 3 (A-F) FESEM images of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x)with insets showing their corresponding EDS spectra and data, and TEM images of TiO2/Ag-Ag2O(300) at low (G) and high (H) magnifications

Fig. 4 (A) XPS survey spectra and (B) the high-resolution XPS spectra of Ag3d spectra of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x), and typical fitting curves of (C)Ag3d and (D)O1s for TiO2/Ag-Ag2O(300)

Table 1 Contents of elements in various samples according to XPS analysis

Element	TiO₂-C	TiO₂/Ag	TiO₂/Ag-Ag₂O(200)	TiO₂/Ag-Ag₂O(300)	TiO₂/Ag-Ag₂O(400)
C1s/%	38.97	25.82	46.37	37.05	28.11
Ti2p/%	19.53	25.01	15.18	19.39	22.73
O1s/%	41.50	48.82	38.05	42.43	46.46
Ag3d/%	-	0.36	0.40	1.13	2.70
Ag⁺/Ag⁰	-	1.02	2.15	4.42	3.52

Fig. 5 UV-Vis absorption spectra of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x) and their corresponding photographs (inset) (a) TiO2-C; (b) TiO2/Ag; (c) TiO2/Ag-Ag2O(200); (d) TiO2/Ag-Ag2O(300); (e) TiO2/Ag-Ag2O(400)

Fig. 6 (A) Photocatalytic H2-evolution activity of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x), and (B) cycling performance of TiO2/Ag-Ag2O(300)

Fig. 7 Schematic diagram of photocatalytic H2-evolution mechanism of TiO2/Ag-Ag2O

Fig. 8 (A) Linear sweep voltammetry (LSV) curves, (B) transient photocurrent responses, and (C) electrochemical impedance spectra (EIS) of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x)

Fig. 9 Photoluminescence (PL) spectra of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x)

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Synergistic Effect of Ag and Ag₂O on Photocatalytic H₂-evolution Performance of TiO₂

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