SBA-15负载硫酸化氧化锆固体酸材料的设计合成及其酯交换反应催化性能研究

doi:10.6023/A24030095

摘要/Abstract

借助硝酸锆水解所产生的弱酸性环境, 结合高温水热处理, 一步合成了具有规整有序孔道结构且孔壁表面富含锆氧物种的Zr-SBA-15介孔材料, 并将其用于硫酸基团的高效稳定负载. 介孔骨架中大量锆原子的高度均匀掺杂及孔壁表面Zr—O—Si键的形成不仅有利于负载更多量的硫酸基团, 且能在诱使超强酸性中心产生的同时, 有效抑制硫酸化锆氧活性组分在反应过程中流失, 致使固体酸材料SO₄²⁻/Zr-SBA-15显示出较传统负载型硫酸化氧化锆固体酸更高的酸量和酸强度, 继而在大豆油合成生物柴油酯交换反应中显示出明显提升的催化活性和稳定性, 其在经三次重复使用过程中, 均可实现将91%以上的大豆油近完全转化为生物柴油.

关键词: 介孔材料, 固体酸, 硫酸化氧化锆, Zr-SBA-15, 酯交换反应

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

引用此文

段晓宣, 王恒燕, 潘大海, 陈树伟, 于峰, 闫晓亮, 李瑞丰. SBA-15负载硫酸化氧化锆固体酸材料的设计合成及其酯交换反应催化性能研究[J]. 化学学报, 2024, 82(7): 755-762.

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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图/表 13

图1. 样品Zr-SBA-15、Zr/SBA-15及SBA-15的Si 2p (a), Zr 3d (b)以及O 1s (c) XPS光谱

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

图2. 固体酸S/Zr-SBA-15、SZr/SBA-15及S/SBA-15的氮气吸附-脱附等温线(a)及相应的孔径分布曲线(b)

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

表1. 固体酸S/Zr-SBA-15、SZr/SBA-15和S/SBA-15的物化性质

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

图3. 固体酸S/Zr-SBA-15、SZr/SBA-15及S/SBA-15的小角(a)和广角(b) XRD谱图

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

图4. 固体酸S/Zr-SBA-15沿[110] (a)和[100] (b)方向的TEM照片

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

图5. 固体酸S/Zr-SBA-15的合成机理示意图

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

图6. 固体酸S/Zr-SBA-15的SEM照片

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

图7. 固体酸S/Zr-SBA-15三个不同区域的元素分析映射图

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

图8. 固体酸S/Zr-SBA-15、SZr/SBA-15及S/SBA-15的NH3-TPD曲线

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

表2. 固体酸S/Zr-SBA-15、SZr/SBA-15及S/SBA-15的酸性质

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

图9. 固体酸S/Zr-SBA-15 (a)及SZr/SBA-15 (b)的吡啶-红外谱图

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

图10. 固体酸S/Zr-SBA-15、SZr/SBA-15及S/SBA-15的初始催化性能(a)和重复性测试(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

图11. 三次反应前后固体酸SZr/SBA-15和S/Zr-SBA-15中S (a)及Zr (b)的含量

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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