Low-cost and efficient Mn/CeO2 catalyst for photocatalytic VOCs degradation via scalable colloidal solution combustion synthesis method

doi:10.1016/j.jmst.2021.11.041

Abstract

Abstract:

Colloidal solution combustion synthesis (CSCS) is a simple and easy method for mass-production of crystalline nanomaterials with tunable pore structure. In this work, mesoporous Mn/CeO2 catalysts were fabricated via CSCS method coupled with a dip-coating process and used for photocatalytic oxidation (PCO) of toluene. Under vacuum ultraviolet (VUV) irradiation, a high toluene removal efficiency of about 92% was achieved with a toluene reaction rate of about 118 μmol/g/h in a continuous flow reactor. A possible degradation pathway was proposed based on the analysis of intermediates by Fourier transform infrared photoluminescence spectra (FTIR) and GC-Mass. Hydrogen temperature-programmed reduction (H2-TPR), Brunauer-Emmett-Teller (BET) surface areas, photoluminescence spectra (PL) spectra and X-ray photoelectron spectroscopy (XPS) were carried out to analyze physical and chemical properties of the catalysts. Compared with MnxCe1-xO2 catalysts synthesized by one step CSCS method, Mn/CeO2 has a higher photocatalytic activity, which is attributed to the presence of higher contents of Ce3+, Mn2+ and Mn3+ species. The presence of higher contents of these species plays a key role in the activity enhancement of toluene oxidation and ozone decomposition. This method is facile, efficient and scalable, and it may become a promising industrial application technology for catalyst synthesis in the near future.

Key words: Mesoporous CeO₂, Manganese modification, Scalable synthesis, Photocatalysis, VOCs abatement

Yingguang Zhang, Muyan Wu, Yifei Wang, Xiaolong Zhao, Dennis Y.C. Leung. Low-cost and efficient Mn/CeO₂ catalyst for photocatalytic VOCs degradation via scalable colloidal solution combustion synthesis method[J]. J. Mater. Sci. Technol., 2022, 116: 169-179.

Figures/Tables 13

Fig. 1. (a) Schematic illustration of the synthesis of Mn/CeO2, SEM images of (b) CeO2, (c) Mn/CeO2-1, (d) Mn/CeO2-2 and (e) Mn/CeO2-3 samples.

Fig. 2. Characterization of Mn/CeO2-2 sample: (a) TEM, (b) HRTEM with corresponding SAED image shown in the inset, (c-f) STEM images with corresponding distribution of (d) Ce, (e) Mn and (f) O elements.

Table. 1. Textural parameters of produced CeO2 and different Mn/CeO2 Samples.

Empty Cell	Surface area (m²/g)	Pore size (nm)	Pore volume (cc/g)	Mn (wt.%)
CeO₂	127	27	0.62	0
Mn/CeO₂-1	93.5	27	0.50	0.87
Mn/CeO₂-2	90.0	27	0.59	1.22
Mn/CeO₂-3	98.0	27	0.61	1.35

Fig. 3. (a and b) XRD patterns of CeO2, Mn/CeO2 and CexMn1-xO2 catalysts, (c) N2 sorption isotherms (vertically shifted for the sake of clarity), and (d) BJH pore size distribution plots of CeO2 and different Mn/CeO2 samples.

Fig. 4. XPS spectra of CeO2, CexMn1-xO2 and Mn/CeO2 samples: (a) Ce 3d, (b) O1s, (c) Mn 2p, and (d) Mn 3 s.

Table 2. Curve-fitting results from XPS spectra of CeO2, CexMn1-xO2 and Mn/CeO2 catalysts.

Sample	Ce³⁺/Ce⁴⁺	O_β BE (eV)	O_β (at.%)	O_α BE(eV)	O_α (at.%)	Atomic ratio
Sample	Ce³⁺/Ce⁴⁺	O_β BE (eV)	O_β (at.%)	O_α BE(eV)	O_α (at.%)	Mn²⁺	Mn³⁺	Mn⁴⁺
CeO₂	0.14	529.6	61.4	531.2	38.6	-	-
Mn/CeO₂	0.16	529.5	60.0	531.3	40.0	2.9	2.7	1
Ce_xMn_1-_xO₂	0.12	528.2	63.5	531.1	36.5	1.4	1.7	1

Fig. 5. Characterization of as-prepared samples; (a) H2-TPR profiles, (b) DRS spectra, (c) PL spectra of CeO2, Mn/CeO2 and CexMn1-xO2.

Fig. 6. Performance comparison of CeO2, CexMn1-xO2-1, CexMn1-xO2-2, and CexMn1-xO2-3 samples synthesized by CSCS method: (a) Toluene removal efficiency, (b) Ozone removal efficiency, (c) COx generation and (d) Mineralization.

Fig. 7. Performance comparison of CeO2, Mn/CeO2-1, Mn/CeO2-2, and Mn/CeO2-3 catalysts: (a) Toluene removal efficiency, (b) Ozone removal efficiency, (c) COx generation, (d) Mineralization, (e) cyclic test of toluene concentration and COx generation, and (f) ozone removal efficiency of Mn/CeO2.

Table 3. Comparison of PCO processes for VOCs degradation in the continuous-mode reactor.

Sample	Pollutant	Light source	Concentration (ppm)	Flow rate (mL/ min)	Catalyst dose (g)	Efficiency (%)	Kinetic rate (µmol/g/h)	Refs.
Mn-TiO₂	Benzene	Two 4 W VUV lamps	50	1000	1	58	77.7	[24]
Sn-TiO₂	Benzene	500 W Xenon lamp (λ>400 nm)	200	20	0.45	50	11.9	[41]
Cu-TiO₂-PU	Benzene	Two 5 W visible light bulbs (400<λ<700 nm)	100	100	NA	86	NA	[42]
TiO₂/diatomite	P-xylene	UVA lamps (8 W, 365 nm)	10	1000	1	60	17.7	[43]
Pd-Ag-AgBr/TiO₂	Propylene	300 W Xe arc lamp	300	44	0.14	70	160.7	[44]
Pd/TiO₂	Toluene	One 10 W VUV lamp	1	800	0.29	41.4	94.3	[45]
Mn/CeO₂	Toluene	Two 4 W VUV lamps	32	1500	1	92	118.3	This work

Fig. 8. FTIR spectra of CeO2, Mn/CeO2 and CexMn1-xO2 samples (a) before and (b) after PCO-VUV toluene degradation; GC-MS spectra of intermediates of toluene degradation from (c) surface of CeO2, Mn/CeO2 and CexMn1-xO2 samples, and outlet gasses of photolysis, CeO2, Mn/CeO2 and CexMn1-xO2 samples by (d) split and (e) splitless testing method.

Fig. 9. ESR spectra (a) DMPO-·O2- and (b) DMPO-·OH of different processes over Mn/CeO2 under VUV irradiation.

Fig. 10. (a) Possible degradation pathway and (b) proposed mechanism of VUV-PCO for toluene degradation on mesoporous Mn/CeO2 samples.

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Low-cost and efficient Mn/CeO₂ catalyst for photocatalytic VOCs degradation via scalable colloidal solution combustion synthesis method

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