In2O3-x(OH)y/Bi2MoO6 S-scheme heterojunction for enhanced photocatalytic performance

doi:10.1016/j.jmst.2020.02.061

Abstract

Abstract:

Surface heterojunction engineering has been extensively studied to promote efficient charge separation in semiconductor materials. Designing an effective heterojunction system to optimize the separation and transport of photo-induced charges is an appealing strategy to enhance the photocatalytic efficiency. In this work, In₂O_3-_x(OH)_y in situ decorated Bi₂MoO₆ two-dimensional step-scheme heterojunctions were synthesized through a controlled dehydroxylation process of indium-based precursors. The charge transfer mechanism of this step-scheme heterojunctions was confirmed by the characterization of electron structures, reactive species, photoelectric properties and DFT theoretical calculation. The band bending and the internal electric field caused by the charge transfer upon hybridization can effectively promote the separation of charges and present the optimal redox capacity. In addition, surface residual hydroxyl groups can regulate the surface energy state and optimize the interfacial charge transfer kinetics of the prepared step-scheme heterojunction. Eventually, the step-scheme heterojunction exhibits superior performance in photocatalytic reduction of hexavalent chromium and degradation of organic pollutants under visible light irradiation. This work provides an innovative perspective to construct photocatalyst with superior activity.

Key words: Step-scheme, Heterojunction, Bi₂MoO₆, Photocatalyst

Zhongfu Li, Zhaohui Wu, Rongan He, Long Wan, Shiying Zhang. In₂O_3-_x(OH)_y/Bi₂MoO₆ S-scheme heterojunction for enhanced photocatalytic performance[J]. J. Mater. Sci. Technol., 2020, 56: 151-161.

Figures/Tables 16

Fig. 1. XRD patterns of prepared samples (a) and locally enlarged diffraction patterns (b).

Fig. 2. FT-IR spectra of prepared samples, fingerprint spectra (a) and hydroxyl characteristic spectra (b).

Fig. 3. FESEM images of S0 (a) and S10 (c), TEM images of S0 (b) and S10 (d) and the corresponding SEM-EDS mapping images of Bi, Mo, O and In (e), respectively.

Fig. 4. Isothermal nitrogen adsorption-desorption curves and pore structure (insert) of S0, S100 and S10.

Table 1 Specific surface area and pore structure of prepared samples.

Sample	Pore Volume (cm³/g)	Pore Diameter (nm)	Specific Surface Area (m³/g)
S0	0.03	0.74	14.45
S10	0.16	1.98	33.55
S100	0.26	3.34	43.69

Fig. 5. The survey XPS spectra (a), high resolution spectra of Bi 4f (b), Mo 3d (c) and In 3d (d), O 1s (e) and TG results of simulated precursor calcination process (f).

Fig. 6. Photocatalytic reduction of Cr(VI) over S0, S100 and In2O3-x(OH)y/Bi2MoO6 heterojunction (a), kinetic constants of photocatalytic reaction (b), the apparent rate constants (c) and recycling performance for Cr(VI) reduction of S10 (d).

Fig. 7. Visible light driven photodegradation of RhB with the synthesized samples (a), the degradation spectrum of S10 (b), kinetic constants of photocatalytic reaction (c) and (d).

Fig. 8. DRS spectra of prepared samples (a) and the band energy of S0 and S100 (inset), PL spectra of the Bi2MoO6 based samples (b), transient photocurrent responses (i-t) measured at 0 V (c) and Nyquist plots of pure Bi2MoO6 and In2O3-x(OH)y/Bi2MoO6 heterojunctions (d).

Fig. 9. Time-resolved transient photofluorescence decay spectra of prepared samples.

Table 2 The summary of the photoluminescence decay time (τ) and pre-exponential factor obtained from the time-resolved photoluminescence spectroscopy.

Samples	B₁	τ₁	B₂	τ₂	τ_(ave) (ns)
S0	52.25	10.74	903.52	1.01	4.09
S10	34.25	8.10	927.50	0.73	2.35
S100	49.36	8.50	826.65	0.92	3.02

Fig. 10. DFT calculated band structures and corresponding DOS for In2O3 (a, b) and Bi2MoO6 (c, d).

Fig. 11. EPR spectra of S0, S100 and S10 for DMPO-·O2- (a) and DMPO-·OH (b) with xenon lamp (λ> 420 nm) irradiated for 2 min.

Fig. 12. Mott-Schottky plot for Bi2MoO6 (a), In2O3-x(OH)y electrode (b), the possible S scheme charge transfer mechanism (c) and XPS valence band spectra of In2O3 and In2O3-x(OH)y (d).

Fig. 13. XRD (a) and SEM (b) of the samples after the cyclic photoreduction reaction.

Table 3 Comparison of the photocatalytic performance with various reported photocatalysts.

No.	Catalyst	Concentration (mg/mL)	Light	Pollutant	C₀ (mg/L)	Efficiency (%)	t (min)	k (min^-1)	Refs.
1	Pd NSs@Bi₂MoO₆	1	300 W Xenon lamp (λ>400 nm)	Cr(VI)	40	80	120	0.0072	[57]
2	Ag-TB_2-x/C₃N₄	1.4	300 W Xenon lamp (λ> 420 nm)	Cr(VI)	5	93	210	0.0127	[58]
3	Fe-g-C₃N₄/MoS₂	0.6	500 W Xenon lamp (λ> 420 nm)	Cr(VI)	20	91	150	0.0210	[59]
4	BiOCl/Bi₂S₃	0.5	500 W Xenon lamp (λ> 400 nm)	Cr(VI)	40	100	180	0.0164	[60]
5	In₂O_3-_x(OH)_y/Bi₂MoO₆	0.5	36W LED (λ> 420 nm)	Cr(VI)	40	96	70	0.0338	This work
6	BN-Bi₂MoO₆	1	300 W halogen tungsten lamp (λ> 420 nm)	RhB	10	99	120	-	[61]
7	Bi₂MoO₆/FePt	1	300W Xenon lamp (λ> 400 nm)	RhB	10	100	70	0.0716	[62]
8	Bi₂MoO₆/N-rGO	1	500 W tungsten lamp (λ> 420 nm)	RhB	10	100	90	0.0461	[63]
9	Ag/Bi₂MoO₆	1	Xenon lamp (λ> 420 nm)	RhB	4.79	98	150	0.0234	[64]
10	In₂O_3-_x(OH)_y/Bi₂MoO₆	0.25	36W LED (λ> 420 nm)	RhB	20	97.5	50	0.0745	This work

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In₂O_3-_x(OH)_y/Bi₂MoO₆ S-scheme heterojunction for enhanced photocatalytic performance

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