Effect of Solvents on the Structure and Properties of Mesoporous SiO2 Supported Phosphotungstic Acid

doi:10.3724/SP.J.1077.2013.12413

Abstract

Abstract:

HPW/BMMs catalyst was prepared by supported phosphotungstic acid on mesoporous SiO₂ with two different mesoporous structures via impregnation method, and characterized by means of XRD, FTIR, nitrogen adsorption- desorption, TG and SEM. The effects of solvents, such as water, ethanol, acetone and acetonitrile, on the structure and properties of supported phosphotungstic acid were systematically investigated. The results showed that the mesoporous structures of BMMs were maintained in the catalysts synthesis process, however, the mesopores order degree, surface area and pore volume of the catalysts (HPW/BMMs) decreased as the increase of HPW loading. A new HPW species in HPW/BMMs appeared at lower loadings and disappeared as the increasing of HPW amount. In addition, the influence of aqueous solution on the Keggin structure of HPW in HPW/BMMs was remarkable, although the HPW crystal remained intact with the uniform dispersion. The acid density of the catalyst synthesis in water with 40% HPW loading (40HPW/BMMs-WA) was up to 1.381 μmol/m². In contrast, when acetonitrile was used as solvent, the Keggin structure of HPW was more likely to be maintained, but the HPW crystal phase was severely destroyed with a low dispersing inside the mesoporous channels. In comparison, the effects of ethanol and acetone as solvent were not obvious. Furthermore, the acid reduced performances of the HPW/BMMs catalysts in etherification reaction between waste oils and methanol were preliminarily investigated.

Key words: phosphotungstic acid, bimodal mesoporous SiO₂, waste oils, esterification

CLC Number:

O643

DAI Qun-He, SUN Ji-Hong, REN Bo, CHEN Dong, WU Xia. Effect of Solvents on the Structure and Properties of Mesoporous SiO₂ Supported Phosphotungstic Acid[J]. Journal of Inorganic Materials, 2013, 28(5): 537-544.

Figures/Tables 13

Fig. 1 XRD patterns of HPW/BMMs samples prepared in different solvents

Fig. 2 SEM images of the samples before and after loaded HPW

Fig. 3 FT-IR spectra of 40HPW/BMMs in different solvents

Table 1 FT-IR absorption peaks of 40HPW/BMMs samples in different solvents

Sample	Wavenumber/cm^-1
Sample	P-O_a	W=O_d	W-O_b-W	W-O_c-W
HPW	1079.9	983.5	891.0	796.5
40HPW-WA	1081.0	981.6	896.7	808.0
40HPW-AT	1080.0	981.6	896.7	809.9
40HPW-AC	1080.9	981.6	898.7	808.0
40HPW-ET	1079.9	983.5	896.7	810.0

Fig. 4 UV-Vis spectra of 40HPW/BMMs in different solvents

Fig. 5 Nitrogen adsorption/desorption isotherms and corresponding pore size distribution (insert) of HPW/BMMs-WA samples

Fig. 6 Nitrogen adsorption/desorption isotherms and pore size distribution (insert) of 40HPW/BMMs samples obtained in different solvents

Table 2 Textural properties of HPW/BMMs samples

Sample	S_BET /(m²·g^-1)	PV /(cm³·g^-1)	MSPS^a /nm	MLPS^b /nm
BMMs	1109	1.46	2.79	16.2
10HPW/BMMs-WA	983	1.29	2.81	16.2
20HPW/BMMs-WA	656	0.85	2.84	16.0
40HPW/BMMs-WA	480	0.64	2.82	16.2
40HPW/BMMs-AC	613	0.82	2.76	15.8
40HPW/BMMs-ET	583	0.80	2.90	16.0
40HPW/BMMs-AT	525	0.72	2.88	16.0

Fig. 7 TG curves of (a) 40HPW/BMMs-WA and (b) BMMs

Fig. 8 NH3-TPD profiles of 40HPW/BMMs in different solvents

Table 3 Acid density distribution of the 40HPW/BMMs samples obtained in different solvents on the basis of the NH3-TPD datas

Catalysts	Total acid density/ (μmol·m^-2)	Weak acid density^T1 /(μmol·m^-2)	Strong acid density^T2 /(μmol·m^-2)
40HPW/BMMs-WA	1.381	0.808	0.573
40HPW/BMMs-AC	0.687	0.087	0.600
40HPW/BMMs-ET	1.022	0.564	0.458

Fig. 9 31P MAS NMR spectra of (a) 10HPW/BMMs-WA and (b) 40HPW/BMMs-WA

Table 4 Catalytic performance of the loaded HPW/BMMs catalysts obtained in aqueous solution

Catalyst*	Calcination temperature/ ℃	Conversion / %
10HPW/BMMs-WA	200	19.4
20HPW/BMMs-WA	200	35.1
40HPW/BMMs-WA	110	17.1
	200	42.7
	300	36.8
HPW	200	43.0

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Effect of Solvents on the Structure and Properties of Mesoporous SiO₂ Supported Phosphotungstic Acid

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