Preparation of the CuWO4/SBA-15 catalyst and its performance in the photocatalytic oxidation desulfurization
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摘要: 以CuWO4为活性组分、SBA-15介孔分子筛为载体,制备CuWO4/SBA-15催化剂,利用XRD、N2吸附-脱附、FT-IR、UV-vis、SEM、EDS和TEM对催化剂进行表征分析;以二苯并噻吩(DBT)的十二烷溶液为模拟油,研究了CuWO4/SBA-15的光催化氧化脱硫(PODS)性能。结果表明,CuWO4/SBA-15保持了载体高度有序的二维六方介孔结构,活性组分分布均匀,且随负载量增加,其比表面积、孔径和孔容依次减小。与CuWO4相比,CuWO4/SBA-15的UV-vis吸收边界蓝移,禁带宽度增加。以二苯并噻吩(DBT)的十二烷溶液为模拟油,评价催化剂的光催化氧化脱硫(PODS)性能。当CuWO4与SiO2质量比为0.07,催化剂用量为3%,O/S物质的量比为10:1,剂油体积比为1:1,光照反应100 min时,催化剂脱硫率最高,可达到81.5%,明显高于CuWO4,催化剂重复使用六次后,活性没有明显下降。在PODS反应过程中,·OH和h+是反应的主要活性物种。Abstract: The CuWO4/SBA-15 catalyst was prepared with CuWO4 as the active composite and mesoporous SBA-15 molecular sieve as the support and characterized by XRD, N2 adsorption and desorption, FT-IR, UV-vis, SEM, EDS and TEM; the performance of CuWO4/SBA-15 catalyst in the photocatalytic oxidation desulfurization (PODS) was investigated by using the dodecane solution of dibenzothiophene (DBT) as the model fuel. The results show that the CuWO4/SBA-15 catalyst can maintain the two-dimensional hexagonal mesoporous structure of the support and the active component is evenly distributed on the support; the surface area, pore size and pore volume of the CuWO4/SBA-15 catalyst decrease with an increase in the amount of active component. Compared with CuWO4, the CuWO4/SBA-15 catalyst displays a blue shift in absorption boundary of UV-vis spectra and an increase of the band gap. With a CuWO4/SiO2 mass ratio of 0.07, catalyst mass percentage of 3% in the model fuel, O/S molar ratio of 10:1, and extractant/oil volume ratio of 1:1, the desulfurization rate reaches 81.5% by carrying out the PODS reaction under light for 100 min, which is obviously higher than that over CuWO4; moreover, no obvious decrease of catalytic activity for CuWO4/SBA-15 was observed after 6 runs of PODS. It is proposed that ·OH and h+ are the main reactive intermediates in PODS.
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Key words:
- desulfurization /
- SBA-15 /
- CuWO4 /
- photocatalytic /
- oxidation
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表 1 样品的孔结构物理参数
Table 1 Textural properties of various SBA-15 and CuWO4/SBA-15 samples
Sample Surface areaA/(m2·g-1) Pore volumev/(cm3·g-1) Pore diameterd/nm CuWO4/SBA-15(0.094) 683.30 0.91 7.03 CuWO4/SBA-15(0.07) 708.75 0.94 7.57 CuWO4/SBA-15(0.047) 717.66 0.96 7.61 CuWO4/SBA-15(0.023) 730.71 0.97 7.71 SBA-15 740.68 0.99 7.86 表 2 催化体系对比
Table 2 Comparison of different catalytic systems
Items Conditions Desulfurization rateη/% 1 H2O2+DBT+CH3OH 41.1 2 DBT+CuWO4/SBA-15+CH3OH 41.7 3 H2O2+DBT+CuWO4/SBA-15+CH3OH 93.2 notes: the effects of the dark adsorption were not taken away from results -
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