Anchoring of 10-phenylphenothiazine to mesoporous silica materials: A water compatible organic photocatalyst for the degradation of pollutants

doi:10.1016/j.jmst.2021.07.004

Abstract

Abstract:

The application of organic photocatalysts towards the oxidation of pollutants in water is hampered by different limitations such as their insolubility in the media. Herein, we report that the grafting of a photo-organocatalyst into mesoporous silica materials is an ideal approach to obtain effective catalysts. Thereby, the photocatalyst 10-phenylphenothiazine (PTH) was easily anchored into three different mesoporous silica-based materials (MSN, MSU-2 and SBA-15) with different particle sizes and pore sizes through an amide bond formation. The materials were characterized using IR analysis, solid-state X-ray diffraction, porosity and microscopy (SEM and TEM) techniques, showing that PTH is immobilized inside the pores of the materials and its optical properties are maintained after the anchoring. Although homogeneous PTH was inactive in water media, the three photocatalytic materials were active for the degradation of pollutants. SBA-15-AP-PTH exhibited the highest catalytic performance towards the degradation of acetaminophen and diclofenac under solar irradiation, finding in this manner a new strategy for the decontamination of pollutants.

Key words: Organic semiconductors, Silica support, Solar photocatalysis, Water treatment, Pharmaceuticals

Daniel González-Muñoz, Almudena Gómez-Avilés, Carmen B. Molina, Jorge Bedia, Carolina Belver, Jose Alemán, Silvia Cabrera. Anchoring of 10-phenylphenothiazine to mesoporous silica materials: A water compatible organic photocatalyst for the degradation of pollutants[J]. J. Mater. Sci. Technol., 2022, 103: 134-143.

Figures/Tables 11

Fig. 1. (a) Previous works of PTH in photocatalysis; (b) Use of MS in photocatalysis; (c) This work: use of PTH-MS in degradation of pollutants.

Scheme 1. (A) Synthesis of the photocatalyst PTH-COOH; (B) Synthesis of MSN-AP-PTH, MSU-AP-PTH and SBA-15-AP-PTH materials.

Fig. 2. IR spectra of SBA-15, SBA-15-AP and SBA-15-AP-PTH.

Fig. 3. Powder XRD patterns of mesoporous silicas: (A) MSN and MSN-AP-PTH, (B) SBA-15 and SBA-15-AP-PTH, (C) MSU-2 and MSU-2-AP-PTH.

Table 1 Structural, textural and composition parameters of the mesoporous silica supports and the functionalized materials.

Sample	d₁₀₀ (Å)^a	a_o(Å)^b	S_BET ^c (m² g^-1)	S_MP ^d (m² g^-1)	S_EXT ^d (m² g^-1)	V_MP ^e (cm³ g^-1)	V_T ^e (cm³ g^-1)	S (wt%)	PTH content^f (mmol g^-1)
SBA-15	96.25	111.14	757	167	590	0.063	0.994	-	-
SBA-15-AP-PTH	95.82	110.64	125	12	113	0.003	0.185	1.26	0.394
MSN	36.50	42.15	771	190	581	0.127	0.662	-	-
MSN-AP-PTH	37.96	43.80	69	16	53	0.007	0.207	1.25	0.391
MSU-2	52.04	60.09	950	441	509	0.404	0.822	-	-
MSU-2-AP-PTH	51.55	59.52	411	145	266	0.057	0.213	1.71	0.534

Fig. 4. Nitrogen adsorption-desorption isotherms at -196 °C of the silica supports (black colour) and the functionalized materials (green colour).

Fig. 5. (A) SEM images of the three unfunctionalized (up, Scale: 1 µm for SBA-15 and MSN, 2 µm for MSU-2) and PTH-supported materials (bottom, Scale: 500 nm for MSN-AP-PTH, 5 µm for MSU-2-AP-PTH and 10 µm for SBA-15-AP-PTH). (B) TEM images of the three unfunctionalized (up, 200 nm for MSN-AP-PTH, 50 nm for MSU-2-AP-PTH and 100 nm for SBA-15-AP-PTH) and PTH-supported materials (bottom, 20 nm for MSN-AP-PTH, 50 nm for MSU-2-AP-PTH and 20 nm for SBA-15-AP-PTH).

Fig. 6. (A) UV-vis diffuse absorbance spectra, and (B) Tauc plots of the functionalized materials.

Fig. 7. Photoluminescence spectra (PL) of the functionalized materials.

Fig. 8. (A) Time-course of acetaminophen concentration under solar irradiation using the functionalized materials (250 mg/L of the corresponding photocatalyst; initial ACE concentration: 10 mg/L; intensity of irradiation: 600 W/m2); (B) Apparent first order rate constants (k) for ACE disappearance with functionalized materials. Error bars represent standard deviation based on triplicate measurements.

Fig. 9. (A) Time-course of ACE, DCF and Ph concentrations under solar irradiation (250 mg/L of SBA-15-AP-PTH; initial DCF/Ph concentration: 10 mg/L; intensity of irradiation: 600 W/m2); (B) Apparent first order rate constant (k) for ACE, DCF and Ph disappearance with SBA-15-AP-PTH. (C) Chemical structure of the compounds degraded in this study.

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