CuWO<sub>4</sub>/SBA-15催化剂的制备及其光催化氧化脱硫性能

李剑; 王雪莹; 黄鑫; 洪帅领; 杨丽娜

CuWO₄/SBA-15催化剂的制备及其光催化氧化脱硫性能

1.
辽宁石油化工大学化学化工与环境学部, 辽宁抚顺 113001
2.
中国石化燕山石化公司, 北京 102500

基金项目:

辽宁省高等学校杰出青年学者成长计划项目 LJQ2015062

辽宁省科学技术厅项目 20170540585

辽宁省教育厅项目 L2015296

辽宁省教育厅项目 L2016018

详细信息

通讯作者:
杨丽娜E-mail: 767527173@qq.com

中图分类号: TQ462.1
计量
- 文章访问数: 246
- HTML全文浏览量: 34
- PDF下载量: 14
- 被引次数: 0
出版历程
- 收稿日期: 2020-02-01
- 修回日期: 2020-04-14
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-05-10

Preparation of the CuWO₄/SBA-15 catalyst and its performance in the photocatalytic oxidation desulfurization

1.
College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113001, China
2.
Sinopec Yanshan Petrochemical Company, Beijing 102500, China

Funds:

Program for Liaoning Excellent Talents in University LJQ2015062

Program for Science and Technology Agency of Liaoning Province 20170540585

General Scientific Research Project of Liaoning Provincial Department of Education L2015296

General Scientific Research Project of Liaoning Provincial Department of Education L2016018

摘要

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。
- 脱硫 /
- SBA-15 /
- CuWO₄ /
- 光催化 /
- 氧化
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.
- desulfurization /
- SBA-15 /
- CuWO₄ /
- photocatalytic /
- oxidation

HTML全文

下载: 全尺寸图片幻灯片

图 1 SBA-15和CuWO₄/SBA-15的小角XRD谱图

a: CuWO₄/SBA-15(0.094); b: CuWO₄/SBA-15(0.07); c: CuWO₄/SBA-15(0.047); d: CuWO₄/SBA-15(0.023); e: SBA-15

Figure 1 Small angle XRD patterns of various SBA-15 and CuWO₄/SBA-15 samples

下载: 全尺寸图片幻灯片

图 2 CuWO₄/SBA-15的大角XRD谱图

a: CuWO₄; b: CuWO₄/SBA-15(0.094); c: CuWO₄/SBA-15(0.07); d: CuWO₄/SBA-15(0.047); e: CuWO₄/SBA-15(0.023)

Figure 2 Wide angle XRD patterns of various CuWO₄/SBA-15 samples

下载: 全尺寸图片幻灯片

图 3 SBA-15和CuWO₄/SBA-15的N₂吸附-脱附等温线(a)和孔径分布(b)

Figure 3 N₂ adsorption-desorption isotherms (a) and pore diameter distribution (b) of SBA-15 and CuWO₄/SBA-15

下载: 全尺寸图片幻灯片

图 4 CuWO₄、SBA-15和CuWO₄/SBA-15的FT-IR谱图

a: SBA-15; b: CuWO₄; c: CuWO₄/SBA-15(0.094); d: CuWO₄/SBA-15(0.07); e: CuWO₄/SBA-15 (0.047); f: CuWO₄/SBA-15(0.023)

Figure 4 FT-IR spectra of various CuWO₄, SBA-15 and CuWO₄/SBA-15 samples

下载: 全尺寸图片幻灯片

图 5 CuWO₄和CuWO₄/SBA-15的紫外-可见吸收光谱(a)和(ahv)^1/2对hv关系图(b)

Figure 5 UV-vis spectra (a) and (αhv)^1/2 vs hv curves (b) of CuWO₄ and CuWO₄/SBA-15

下载: 全尺寸图片幻灯片

图 6 CuWO₄/SBA-15(0.07)的SEM照片

Figure 6 SEM image of CuWO₄/SBA-15(0.07)

下载: 全尺寸图片幻灯片

图 7 CuWO₄/SBA-15(0.07)的EDS照片

Figure 7 EDS photographs of CuWO₄/SBA-15(0.07)

下载: 全尺寸图片幻灯片

图 8 SBA-15(a)和CuWO₄/SBA-15(0.07)(b)的TEM照片

Figure 8 TEM images of SBA-15 (a) and CuWO4/SBA-15(0.07) (b)

下载: 全尺寸图片幻灯片

图 9 CuWO₄与CuWO₄/SBA-15的催化活性

a: CuWO₄; b: CuWO₄/SBA-15(0.094); c: CuWO₄/SBA-15(0.07); d: CuWO₄/SBA-15(0.047); e: CuWO₄/SBA-15(0.023)

Figure 9 Catalytic activities of CuWO₄ and CuWO₄/SBA-15 in the photocatalytic oxidation desulfurization (PODS) of dibenzothiophene (DBT)-containing model oil

下载: 全尺寸图片幻灯片

图 10 催化剂用量对脱硫率的影响

Figure 10 Effect of catalysts dosage on desulfurization rate

下载: 全尺寸图片幻灯片

图 11 O/S物质的量比对脱硫率的影响

Figure 11 Effect of O/S molar ratio on desulfurization rate

下载: 全尺寸图片幻灯片

图 12 剂油体积比对脱硫率的影响

Figure 12 Effect of the volume ratio of the extractant to the model fuel on desulfurization rate

下载: 全尺寸图片幻灯片

图 13 CuWO₄/SBA-15催化剂重复使用性能

Figure 13 Recycling performance of CuWO₄/SBA-15

下载: 全尺寸图片幻灯片

图 14 CuWO₄/SBA-15可见光PODS过程中的活性物种捕获实验

Figure 14 Trapping experiments of active species under visible light irradiation in the presence of CuWO₄/SBA-15

下载: 全尺寸图片幻灯片

图 15 CuWO₄/SBA-15光催化氧化脱硫机理示意图

Figure 15 Proposed reaction mechanism of photocatalytic oxidation desulfurization on CuWO₄/SBA-15

下载: 全尺寸图片幻灯片

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

下载: 导出CSV

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

下载: 导出CSV

参考文献(27)

[1]	周宁, 张月月, 黄现礼, 徐泽华, 梁元伟, 施敏媛. Pt/g-C₃N₄的可见光光催化异辛烷脱硫性能及机理[J].石油化工, 2017, 46(8):1012-1016. doi: 10.3969/j.issn.1000-8144.2017.08.009 ZHOU Ning, ZHANG Yue-yue, HUANG Xian-li, XU Ze-hua, LIANG Yuan-wei, SHI Min-yuan. Photocatalytic desulfurization activity and mechanism of Pt/g-C₃N₄ in isooctane under visible light irradiation[J]. Petrochem Technol, 2017, 46(8):1012-1016. doi: 10.3969/j.issn.1000-8144.2017.08.009
[2]	ZHANG G, GAO M, TIAN M, ZHAO W F. In situ hydrothermal preparation and photocatalytic desulfurization performance of graphene wrapped TiO₂ composites[J]. J Solid State Chem, 2019, 279:120953. doi: 10.1016/j.jssc.2019.120953
[3]	MEHDI M K. Facile hydrothermal synthesis of egg-like BiVO₄ nanostructures for photocatalytic desulfurization of thiophene under visible light irradiation[J]. J Mater Sci:Mater Electron, 2019, 30(19):17735-17740. doi: 10.1007/s10854-019-02123-0
[4]	赵帅, 刘亚亚, 马博文, 沈健. TiO₂-β/SBA-15的制备及其光催化氧化脱硫性能[J].石油化工, 2018, 47(8):795-801. doi: 10.3969/j.issn.1000-8144.2018.08.004 ZHAO Shuai, LIU Ya-ya, MA Bo-wen, SHEN Jian. Preparation of TiO₂-β/SBA-15 and its performance on photocatalytic oxidation desulfurization[J]. Petrochem Technol, 2018, 47(8):795-801. doi: 10.3969/j.issn.1000-8144.2018.08.004
[5]	王喆, 纪桂杰, 沈健. TiO₂/SBA-15光催化氧化汽油脱硫的研究[J].石油炼制与化工, 2015, 46(4):51-54. doi: 10.3969/j.issn.1005-2399.2015.04.010 WANG Zhe, JI Gui-jie, SHEN Jian. Study of photocatalytic oxidation desulfurization of gasoline with TiO₂/SBA-15[J]. Pet Process Petrochem, 2015, 6(4):51-54. doi: 10.3969/j.issn.1005-2399.2015.04.010
[6]	王鑫, 张静. CdS异相结的固相法制备及其光催化性能[J].辽宁石油化工大学学报, 2019, 39(3):30-34. doi: 10.3969/j.issn.1672-6952.2019.03.006 WANG Xin, ZHANG Jing. Preparation of CdS phase junction by solid phase method and photocatalytic performance[J]. J Liaoning Shihua Univ, 2019, 39(3):30-34. doi: 10.3969/j.issn.1672-6952.2019.03.006
[7]	LU X W, LI X Z, QIAN J C, MIAO N M, YAO C, CHEN Z G. Synthesis and characterization of CeO₂/TiO₂ nanotube arrays and enhanced photocatalytic oxidative desulfurization performance[J]. J Alloys Compd, 2016, 661:363-371. doi: 10.1016/j.jallcom.2015.11.148
[8]	KHYZHUN O Y, BEKENEV V L, SOLONIN Y M. First-principles calculations and X-ray spectroscopy studies of the electronic structure of CuWO₄[J]. J Alloys Compd, 2009, 480(2):184-189. doi: 10.1016/j.jallcom.2009.01.119
[9]	何德文, 阳洋, 唐建军, 周康根, 陈伟, 陈益清. CuWO₄促进TiO₂光催化降解水中阿特拉津[J].水处理技术, 2019, 45(6):43-47. http://www.cqvip.com/QK/90921X/201906/7002218456.html HE De-wen, YANG Yang, TANG Jian-jun, ZHOU Kang-gen, CHEN Wei, CHEN Yi-qing. CuWO₄ promoting TiO₂ photocatalytic degradation of atrazine in water[J]. Technol Water Treat, 2019, 45(6):43-47. http://www.cqvip.com/QK/90921X/201906/7002218456.html
[10]	韩娜, 陈政利, 苏炜, 沈健, 任铁强. BiVO₄/SBA-15催化剂的制备及其光催化氧化脱硫性能[J].燃料化学学报, 2019, 47(2):191-198. doi: 10.3969/j.issn.0253-2409.2019.02.008 HAN Na, CHEN Zheng-li, SU Wei, SHEN Jian, REN Tie-qiang. Preparation of BiVO₄/SBA-15 catalyst and its performance in the photocatalytic oxidation desulfurization[J]. J Fuel ChemTechnol, 2019, 47(2):191-198. doi: 10.3969/j.issn.0253-2409.2019.02.008
[11]	ZHOU K D, DING Y C, ZHANG L F, WU H D, GUO J. Synthesis of mesoporous ZnO/TiO₂-SiO₂ composite material and its application in photocatalytic adsorption desulfurization without the addition of an extra oxidant[J]. Dalton trans, 2020, 49(5):1600-1612. doi: 10.1039/C9DT04454J
[12]	XU M Z, YANG L N, LI J. Photocatalytic oxidative desulfurization of dibenzothiophene on TiO₂ modified bimodal mesoporous silica[J].China Pet Process Petrochem Technol, 2017, 19(3):59-67. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgsyjgysyhgjs201703009
[13]	张璐璐, 孙悦, 王喆, 孙尧, 詹金友, 沈健, 郝慧源. TiO₂/SBA-15的制备及光催化氧化脱硫性能[J].硅酸盐学报, 2016, 44(1):56-62. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=gsyxb201601009 ZHANG Lu-lu, SUN Yue, WANG Zhe, SUN Yao, ZHAN Jin-you, SHEN Jian, HAO Hui-yuan. Preparatione of TiO₂/SBA-15 and its photocatalytic oxidation desulfurization performanc[J]. J Chin Ceram Soc, 2016, 44(1):56-62. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=gsyxb201601009
[14]	VIGNESH K, PRIYANKA R, HARIHARAN R, RAJARAJANET M, SUGANTHIA A. Fabrication of CdS and CuWO₄ modified TiO₂nanoparticles and its photocatalytic activity under visible light irradiation[J]. J Ind Eng Chem, 2014, 20(2):435-443. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=1e5b056398049e86d5a42c6aaa17baa7
[15]	ZHAO D Y, FENG J L, HUO Q S, MELOSH N, FREDRICKSON G H, CHMELKA B F, STUCKY G D. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J]. Science, 1998, 279(5350):548-552. doi: 10.1126/science.279.5350.548
[16]	PATTERSON E M, SHELDEN C E, STOCKTON B H. Kubelka-Munk optical properties of a barium sulfate white reflectance standard[J]. Appl Opt, 1977, 16(3):729-732. doi: 10.1364/AO.16.000729
[17]	GAILLARD N, CHANG Y, DEANGELIS A, HIGGINS S, BRAUN A. A nanocomposite photoelectrode made of 2.2 eV band gap copper tungstate (CuWO₄) and multi-wall carbon nanotubes for solar-assisted water splitting[J]. Int J Hydrogen Energy, 2013, 38(8):3166-3176. doi: 10.1016/j.ijhydene.2012.12.104
[18]	张源, 卢伟伟. WO₃/BiVO₄薄膜光电极构建及光电转化性能[J].河南科技大学学报(自然科学版), 2019, 40(4):94-99+10. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=lygxyxb201904017 ZHANG Yuan, LU Wei-wei. Construction and photoelectric conversion properties of WO₃/BiVO₄ composite film photoelectrode[J]. J Henan Univ Sci Technol(Nat Sci), 2019, 40(4):94-99+10. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=lygxyxb201904017
[19]	陈新富, 王振翠, 马丹妮, 王取振, 罗娅琼, 曾觉平. TiO₂/SBA-15介孔复合材料的制备及光催化性能研究[J].环境科学与技术, 2019, 42(10):57-63. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=hjkxyjs201910009 CHEN Xin-fu, WANG Zhen-cui, MA Dan-ni, WANG Qu-zhen, LUO Ya-qiong, ZENG Jue-ping. Preparation of TiO₂/SBA-15 mesoporous composite and its photocatalytic performance[J]. Environ Sci Technol, 2019, 42(10):57-63. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=hjkxyjs201910009
[20]	张凤利, 郑远辉, 詹瑛瑛, 林性贻, 张汉辉, 郑起. Ag-TiO₂/KIT-6复合纳米光催化剂的研究[J].光谱学与光谱分析, 2009, 29(8):152-156. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=gpxygpfx200908035 ZHANG Feng-li, ZHENG Yuang-hui, ZHAN Ying-ying, LIN Xing-yi, ZHANG Han-hui, ZHENG Qi. Studies on Ag-TiO₂/KIT-6 composite nanosized photocatalyst[J]. Spectrosc Spect Anal, 2009, 29(8):152-156. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=gpxygpfx200908035
[21]	李艳荣, 宋明娟, 顾海芳, 黄曜, 牛国兴, 赵东元.适合SBA-15介孔材料工业化生产的改良方法[J].催化学报, 2012, 33(8):1360-1366. http://d.old.wanfangdata.com.cn/Periodical/cuihuaxb201208017 LI Yan-rong, SONG Ming-juan, GU Hai-Fang, HUANG Yao, NIU Guo-Xing, ZHAO Dong-Yuan. Improved synthesis of SBA-15 mesoporous silica fitting for industrial production[J]. Chin J Catal, 2012, 33(8):1360-1366. http://d.old.wanfangdata.com.cn/Periodical/cuihuaxb201208017
[22]	黄健, 张思月, 郭基辉, 许先猛, 马欣. Co改性SBA-15分子筛结构稳定性研究[J].当代化工研究, 2019, (9):74-77. doi: 10.3969/j.issn.1672-8114.2019.09.034 HUANG Jian, ZHANG Si-yue, GUO Ji-hui, XU Xian-meng, MA Xin. Studise on stability of cobalt modified SBA-15 molecular sieve[J]. Mod Chem Res, 2019, (9):74-77. doi: 10.3969/j.issn.1672-8114.2019.09.034
[23]	SOHRABNEZHAD S, POURAHMAD A, SALAVATIYAN T. CuO-MMT nanocomposite:Effective photocatalyst for the discoloration of methylene blue in the absence of H₂O₂[J]. Appl Phys A, 2016, 122(2):1-12. doi: 10.1007/s00339-016-9645-2
[24]	WANG G J, ZHANG J K, LIU Y. Catalytic oxidative desulfurization of benzothiophene with hydrogen peroxide over Fe/AC in a biphasic model diesel-acetonitrile system[J]. Korean J Chem Eng, 2013, 30(8):1559-1565. doi: 10.1007/s11814-013-0052-5
[25]	WU J, LI J, LIU J, BAI J, YANG L. A novel Nb₂O₅/Bi₂WO₆ heterojunction photocatalytic oxidative desulfurization catalyst with high visible light-induced photocatalytic activity[J]. RSC Adv, 2017, 7:51046-51054. doi: 10.1039/C7RA09829D
[26]	郭梅, 任学昌, 王建钊, 康赟, 孟悦. TiO₂/pg-C₃N₄复合催化剂的制备及光催化性能[J].中国环境科学, 2019, 39(12):5119-5125. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zghjkx201912023 GUO Mei, REN Xue-chang, WANG Jian-zhao, KANG Fu, MENG Yue. Preparation and photocatalytic properties of TiO₂/pg-C₃N₄ composite photocatalyst[J]. China Environ Sci, 2019, 39(12):5119-5125. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zghjkx201912023
[27]	高玲, 王英, 史丽英, 季安.对铜离子高选择性的SBA-15介孔内自组装新型荧光化学传感器[J].传感技术学报, 2006, 19(1):70-73. http://d.old.wanfangdata.com.cn/Periodical/cgjsxb200601016 GAO Ling, WANG Ying, SHI Li-ying, JI An. Highly selective fluorescent chemosensor for Cu²⁺ insitu-assembled within mesoporous SBA-15[J]. Chin J Sens Actuators, 2006, 19(1):70-73. http://d.old.wanfangdata.com.cn/Periodical/cgjsxb200601016