溶剂效应对介孔SiO2负载磷钨酸催化剂的影响

doi:10.3724/SP.J.1077.2013.12413

摘要/Abstract

摘要：

以具有两种不同介孔结构的多孔SiO₂(BMMs)为载体, 采用浸渍法负载磷钨酸(HPW)得到负载型磷钨酸催化剂(HPW/BMMs), 通过XRD、FTIR、N₂吸附-脱附, TG和SEM等表征手段, 重点考察了水、乙醇以及丙酮和乙腈等溶剂对HPW/BMMs催化剂结构和性能的影响。结果表明: 在不同溶剂中所制备的负载型HPW/BMMs催化剂样品均保持了BMMs介孔结构, 但随着HPW负载量的增大, 样品的介孔有序度逐渐降低, 比表面积和孔体积逐渐减小; 低负载量时, 样品表面出现新的HPW物种, 通过提高HPW的负载量, 可抑制该物种的产生。水溶剂对HPW的Keggin结构影响较大, 但HPW的晶型保持完好, 分散性能较好, 负载量为40%的样品(40HPW/BMMs-WA)总酸密度最高, 达到1.381 μmol/m²; 乙腈溶剂虽更有利于保持HPW的Keggin结构, 但晶型破坏较严重, 且分散性较差; 相比较而言, 乙醇和丙酮溶剂的影响则不明显。此外, 初步考察了HPW/BMMs样品对废油脂与甲醇催化酯化的降酸效果。

关键词: 磷钨酸, 双模型介孔SiO₂, 废油脂, 酯化

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

中图分类号:

O643

戴群和, 孙继红, 任博, 陈东, 武霞. 溶剂效应对介孔SiO₂负载磷钨酸催化剂的影响[J]. 无机材料学报, 2013, 28(5): 537-544.

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.

图/表 13

图1 不同溶液(A)水、(B)乙醇、(C)丙酮及(D)乙腈中制备的HPW/BMMs样品的XRD图谱

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

图2 BMMs负载HPW前后样品的SEM照片

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

图3 不同溶剂中制备的40HPW/BMMs样品的FT-IR图谱

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

图4 不同溶剂中制备的40HPW/BMMs样品的UV-Vis图谱

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

图5 HPW/BMMs-WA样品的N2吸附-脱附曲线及孔分布图

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

图6 不同溶剂中制备的40HPW/BMMs样品N2吸附-脱附曲线及孔分布图表2 有关HPW/BMMs样品的织构数据

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

图7 (a) 40HPW/BMMs-WA样品和 (b) BMMs的TG曲线

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

图8 不同溶剂中制备的40HPW/BMMs样品的NH3-TPD曲线表3 在不同溶剂中制备的40HPW/BMMs样品的酸密度分布

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

图9 样品的31P MAS NMR图谱

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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溶剂效应对介孔SiO₂负载磷钨酸催化剂的影响

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

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