Constructing S-scheme 2D/0D g-C3N4/TiO2 NPs/MPs heterojunction with 2D-Ti3AlC2 MAX cocatalyst for photocatalytic CO2 reduction to CO/CH4 in fixed-bed and monolith photoreactors

doi:10.1016/j.jmst.2021.08.019

Abstract

Abstract:

Exfoliated 2D MAX Ti₃AlC₂ conductive cocatalyst anchored with g-C₃N₄/TiO₂ to construct 2D/0D/2D heterojunction has been explored for enhanced CO₂ photoreduction in a fixed-bed and monolith photoreactor. The TiO₂ particle sizes (NPs and MPs) were systematically investigated to determine effective metal-support interaction with faster charge carrier separation among the composite materials. When TiO₂ NPs were anchored with 2D Ti₃AlC₂ MAX structure, 10.44 folds higher CH₄ production was observed compared to anchoring TiO₂ MPs. Maximum CH₄ yield rate of 2103.5 µmol g^-1 h^-1 achieved at selectivity 96.59% using ternary g-C₃N₄/TiO₂/Ti₃AlC₂ 2D/0D/2D composite which is 2.73 and 7.45 folds higher than using binary g-C₃N₄/Ti₃AlC₂ MAX and TiO₂ NPs/Ti₃AlC₂ samples, respectively. A step-scheme (S-scheme) photocatalytic mechanism operates in this composite, suppressed the recombination of useful electron and holes and provides higher reduction potential for efficient CO₂ conversion to CO and CH₄. More importantly, when light intensity was increased by 5 folds, CH₄ production rate was increased by 3.59 folds under visible light. The performance of composite catalyst was further investigated in a fixed-bed and monolith photoreactor and found monolithic support increased CO production by 2.64 folds, whereas, 53.99 times lower CH₄ production was noticed. The lower photocatalytic activity in a monolith photoreactor was due to lower visible light penetration into the microchannels. Thus, 2D MAX Ti₃AlC₂ composite catalyst can be constructed for selective photocatalytic CO₂ methanation under visible light in a fixed-bed photoreactor.

Key words: Photocatalytic CO₂ methanation, Exfoliated 2D MAX Ti₃AlC₂, g-C₃N₄/TiO₂, Fixed-bed reactor, Monolith photoreactor, Solar energy

Muhammad Tahir, Beenish Tahir. Constructing S-scheme 2D/0D g-C₃N₄/TiO₂ NPs/MPs heterojunction with 2D-Ti₃AlC₂ MAX cocatalyst for photocatalytic CO₂ reduction to CO/CH₄ in fixed-bed and monolith photoreactors[J]. J. Mater. Sci. Technol., 2022, 106: 195-210.

Figures/Tables 14

Fig. 1. Schematic illustration for the synthesis of TiO2/Ti3AlC2/g-C3N4 and monolithic TiO2/Ti3AlC2/g-C3N4 composite samples.

Fig. 2. (a) XRD patterns of TiO2 NPs, TiO2 MPs, Ti3AlC2 MAX, TiO2 MPs/Ti3AlC2 TiO2 NPs/Ti3AlC2 samples; (b) XRD patterns of g-C3N4, g-C3N4/TiO2 NPs, g-C3N4/Ti3AlC2 MAX and g-C3N4/TiO2/Ti3AlC2 composite samples.

Fig. 3. (a) Raman analysis 2D Ti3AlC2 MAX, pristine TiO2 NPs, Ti3AlC2 anchored TiO2 MPs and Ti3AlC2/TiO2 NPs; (b) Raman patterns of pristine g-C3N4, pristine TiO2 NPs, 2D Ti3AlC2 MAX/TiO2 NPs and g-C3N4/TiO2 NPs/Ti3AlC2 MAX composite.

Fig. 4. FESEM analysis of (a) TiO2 MPs, (b) TiO2 NPs, (c) exfoliated Ti3AlC2, (d, e) TiO2 MPs/Ti3AlC2, (f, g) TiO2 NPs/Ti3AlC2, (h-i) TEM images of TiO2 NPs/Ti3AlC2, (k) HRTEM images of TiO2 NPs/Ti3AlC2 with d-spacing analysis.

Fig. 5. (a) FESEM images of pristine g-C3N4, (b) g-C3N4/TiO2, (c) g-C3N4/Ti3AlC2 MAX, (d, e) FESEM images of g-C3N4/TiO2 NPs/Ti3AlC2, (f) TEM images of g-C3N4/TiO2 NPs/Ti3AlC2, (g) HRTEM image of composite, (h-j) d-spacing of g-C3N4/TiO2 NPs anchored Ti3AlC2 MAX composite.

Fig. 6. XPS analysis of TiO2, g-C3N4, Ti3AlC2 and their g-C3N4/TiO2 loaded 2D Ti3AlC2 MAX composite samples: (a) Ti2p; (b) N 1s; (c); C 1s; (d) Al 2p.

Fig. 7. (a) UV-Vis analysis of TiO2, g-C3N4, Ti3AlC2, and Ti3AlC2 based composites, (b) PL spectra of TiO2, Ti3AlC2 and their composite samples, (c) PL spectra of g-C3N4, Ti3AlC2 loaded TiO2 and g-C3N4/TiO2/Ti3AlC2 MAX composite samples.

Fig. 8. Effect of different photocatalysts on photocatalytic reduction of CO2 with H2O to CO and CH4 under visible light in a fixed bed photoreactor: (a) Yield of CO production, (b) Yield of CH4 evolution.

Fig. 9. Schematic of TiO2 NPs and MPs with their interaction over Ti3AlC2 2D MAX structure: (a) Charges separation in TiO2 MPs, (b) Charges separation in TiO2 NPs, (c) Interaction of TiO2 MPs with Ti3AlC2 2D MAX, (d) Interaction of 2D Ti3AlC2 with TiO2 NPs.

Fig. 10. Effect of 2D MAX Ti3AlC2 support structure on the performance of pristine TiO2 NPs, g-C3N4 and their Ti3AlC2/TiO2 NPs and Ti3AlC2/g-C3N4/TiO2 NPs composite for CO and CH4 under visible light: (a) Yield of CO production; (b) Yield of CH4 production.

Fig. 11. Performance analysis of fixed bed and monolith photoreactor under visible light of different light intensities (20 and 100 mW cm-2) for the production CO/ CH4; (a) CH4 evolution; (b) CO evolution.

Fig. 12. Schematic illustration for photocatalytic CO2 reduction process in a fixed bed and monolith photoreactor: (a) Fixed bed photoreactor, (b) Monolith photoreactor, (c) Mass transfer process with external and internal diffusion affects.

Table 1. Evaluation of production rate, selectivity, QY and TON for CO and CH4 production over g-C3N4 and modified g-C3N4 samples.

Photocatalyst	Intensity (mW cm^-2)	Photoreactor	Production rate (µmole g^-1 h^-1)		Selectivity (%)		QY (%)
Photocatalyst	Intensity (mW cm^-2)	Photoreactor	CO	CH₄	CO	CH₄	CO	CH₄
TiO₂ MPs	20	Fixed-bed	94.61	7.78	75.25	24.75	0.401	0.132
TiO₂ NPs	20	Fixed-bed	150.71	21.53	63.64	36.36	0.638	0.365
g-C₃N₄	20	Fixed-bed	75.64	27.54	40.71	59.29	0.320	0.467
TiO₂MPs/Ti₃AlC₂	20	Fixed-bed	240.32	27.025	68.97	31.03	0.339	0.153
TiO₂ NPs/Ti₃AlC₂	20	Fixed-bed	240.09	282.39	17.53	82.47	1.695	7.975
g-C₃N₄/Ti₃AlC₂ MAX	20	Fixed-bed	255.81	770.74	7.66	92.34	1.084	13.059
g-C₃N₄/TiO₂/Ti₃AlC₂ MAX	20	Fixed-bed	297.26	2103.50	3.41	96.59	1.259	35.642
g-C₃N₄/TiO₂/Ti₃AlC₂ MAX	100	Fixed-bed	571.99	7546.83	1.86	98.14	0.485	25.575
g-C₃N₄/TiO₂/Ti₃AlC₂ MAX	100	Monolith	1510.44	139.77	72.99	27.01	2.133	0.789

Fig. 13. Schematic illustration of S-scheme heterojunction for photocatalytic CO2 reduction with H2O over 2D MAX Ti3AlC2 dispersed g-C3N4/TiO2 composite.

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Constructing S-scheme 2D/0D g-C₃N₄/TiO₂ NPs/MPs heterojunction with 2D-Ti₃AlC₂ MAX cocatalyst for photocatalytic CO₂ reduction to CO/CH₄ in fixed-bed and monolith photoreactors

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