Designed Synthesis of SBA-15 Supported Sulfated Zirconia Solid Acid Materials and Their Catalytic Performance for Transesterification Reaction

doi:10.6023/A24030095

Abstract

Ordered mesoporous Zr-SBA-15 material with a highly homogenous distribution of Zr within mesoporous walls was synthesized by a facile one-step high temperature hydrothermal treatment approach. In the proposed approach, the cooperative self-assembly between amphiphilic triblock copolymer P123 and silicon hydroxyl (Si-OH) species from the hydrolysis of tetraethyl orthosilicate (TEOS) was carried out to form an organic-inorganic composite with an ordered mesostructure (as-synthesized SBA-15, silica matrices with an embeddedness of P123 micelles) under a weak acidic medium originated from the hydrolysis of zirconium tetranitrate; during the followed high temperature hydrothermal treatment process, the further hydrolysis of zirconium precursor promotes more Zr⁴⁺ transferring to zirconium hydroxyl (Zr-OH) species, and the condensation between the Zr-OH species and Si-OH species, which exist in the synthesis solution and within the mesoporous walls of as-synthesized SBA-15, respectively, leads to a large amount of Zr atoms being highly homogenously grafted into the mesoporous walls of as-synthesized SBA-15 and the formation of framework Zr—O—Si bonds. After calcination to remove the organic P123 micelles, the ordered mesoporous Zr-SBA-15 material was obtained and used as a support for the immobilization of sulfuric acid by a traditional impregnation method. The characterization results confirmed that compared to supports SBA-15 and SBA-15-supported zirconia (Zr/SBA-15, prepared by the impregnation of SBA-15 with zirconium tetranitrate aqueous soliton followed drying and calcination treatments), the use of support Zr-SBA-15 can realize a stable immobilization of much more sulfuric acid groups, due to the highly homogenous dispersions of ZrO_x species on the mesoporous surface of Zr-SBA-15. In addition, the double attracting electron role from supported sulfuric acid group and Si element with higher electronegativity than that of Zr element can further induce an decrease in the electron cloud density of Zr⁴⁺ existing in the surface Zr—O—Si bonds, which plays an important role in promoting the formation of super strong Brönsted and Lewis acidic sites. More importantly, the formation of surface Zr—O—Si bonds can exert a significant influence on restraining the leaching of active sulfated ZrO_x species during the reaction. The resultant solid acid SO₄²⁻/Zr-SBA-15 exhibits an ordered two-dimensional hexagonal mesostructure, a uniform mesoporous size, a high specific surface area, a large pore volume, and a prominently improved acidity. For soybean oil transesterification with methanol, the catalyst SO₄²⁻/Zr-SBA-15 demonstrated a much higher soybean oil conversion (up to 100%) along with a fatty acid methyl ester yield of 99.8% and a desirable reusability, compared to the traditional supported sulfated zirconia catalysts. The superior catalytic performance of SO₄²⁻/Zr-SBA-15 is associated with the outstanding structural and textural properties of support Zr-SBA-15 and the for-mation of surface Zr—O—Si bonds, thus benefiting the fast mass and heat transfer and the generation of a large number of stable active sites with a highly homogenous dispersion.

Key words: mesoporous material, solid acids, sulfated zirconia, Zr-SBA-15, transesterification

Cite this article

Xiaoxuan Duan, Hengyan Wang, Dahai Pan, Shuwei Chen, Feng Yu, Xiaoliang Yan, Ruifeng Li. Designed Synthesis of SBA-15 Supported Sulfated Zirconia Solid Acid Materials and Their Catalytic Performance for Transesterification Reaction[J]. Acta Chimica Sinica, 2024, 82(7): 755-762.

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Fig. & Tab. 13

Figure 1. Si 2p (a), Zr 3d (b), and O 1s (c) XPS spectra of samples Zr-SBA-15, Zr/SBA-15, and SBA-15

Figure 2. N2 adsorption-desorption isotherms (a) and the corresponding pore size distribution curves (b) of solid acid samples S/Zr-SBA-15, SZr/SBA-15, and S/SBA-15

Sample	a₀^a/ nm	S_BET^b/ (m²•g⁻¹)	V_P^c/ (cm³•g⁻¹)	D_P^d/ nm	w(S)^e/ %
S/Zr-SBA-15	10.7	539	0.96	9.1	1.91
S/SBA-15	9.8	627	0.98	8.8	0.31
SZr/SBA-15	9.8	467	0.91	7.7	0.98

Table 1. The physicochemical properties of solid acid samples S/Zr-SBA-15, SZr/SBA-15, and S/SBA-15

Figure 3. The small-angle (a) and wide-angle (b) XRD patterns of solid acid samples S/Zr-SBA-15, SZr/SBA-15, and S/SBA-15

Figure 4. TEM images along [110] (a) and [100] (b) directions of solid acid S/Zr-SBA-15

Figure 5. A flow chart for the synthesis of soild acid S/Zr-SBA-15

Figure 6. SEM images of solid acid S/Zr-SBA-15

Figure 7. Elemental analysis mapping for three different regions of soild acid S/Zr-SBA-15

Figure 8. NH3-TPD curves of soild acid samples S/Zr-SBA-15, SZr/SBA-15, and S/SBA-15

Sample	Weak acid/ (μmol•g⁻¹)	Medium acid/ (μmol•g⁻¹)	Strong acid/ (μmol•g⁻¹)	Super acid/ (μmol•g⁻¹)	Total acid/ (μmol•g⁻¹)
S/Zr-SBA-15	40.10	67.44	188.42	22.26	318.23
SZr/SBA-15	39.98	106.76	69.34	—	216.08
S/SBA-15	17.63	43.69	27.88	—	89.20

Table 2. The acidic properties of solid acid samples S/Zr-SBA-15, SZr/SBA-15, and S/SBA-15

Figure 9. The Py-FTIR spectra of solid acid samples S/Zr-SBA-15 (a) and SZr/SBA-15 (b)

Figure 10. The initial catalytic performance (a) and reproducibility tests (b) of solid acid samples S/Zr-SBA-15, SZr/SBA-15, and S/SBA-15

Figure 11. The contents of S (a) and Zr (b) for solid acid samples SZr/SBA-15 and S/Zr-SBA-15 before and after the three time reaction

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