SBA-15-Supported Molybdovanadophosphoric Acid Photothermal Catalysts for Efficient Oxidation Desulfurization at Room Temperature

doi:10.19894/j.issn.1000-0518.240111

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (10): 1469-1480.DOI: 10.19894/j.issn.1000-0518.240111

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SBA-15-Supported Molybdovanadophosphoric Acid Photothermal Catalysts for Efficient Oxidation Desulfurization at Room Temperature

Meng-Chun ZHU, Qi-Qi LI, Hong-Rui TIAN, Yan-Feng BI()

School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun 113001，China

Received:2024-04-02 Accepted:2024-08-22 Published:2024-10-01 Online:2024-10-29
Contact: Yan-Feng BI
About author:biyanfeng@lnpu.edu.cn
Supported by:
the National Natural Science Foundation of China(91961110)

Abstract

Abstract:

A series of catalysts， X%PMoV （X=10， 20， 30， 40， 50）， were prepared through loading X%（mass fraction of SBA-15） Keggin-type H₄PMo₁₁VO₄₀ （PMoV） on mesoporous SBA-15 by incipient-wetness impregnation method， which were utilized as visible-light catalysts for photothermal oxidation desulfurization at room temperature. The catalysts were characterized by brunauer Emmett Trller （BET）， fourier transform infrared spectroscopy （FT-IR）， powder X-ray diffration （PXRD）， transmission electron microscope （TEM）， X-ray photoelectron spectroscopy （XPS）， and UV-Vis. X%PMoV catalysts showed photothermal conversion ability in acetonitrile solvent， and the photothermal conversion efficiency increased with the increase of PMoV. The oxidation desulfurization experiment of dibenzothiophene （DBT， as an example） was carried out in model oil with oxidant H₂O₂. The results show that the catalyst has the synergistic oxidative desulfurization ability of photocatalysis and photo-driven thermal catalysis on DBT. Due to the effective load of the active PMoV in the SBA-15 channels， the catalyst has good cyclic stability and substrate oxidation product selectivity when the load is 30%. The photothermal catalytic desulfurization strategy is also applicable for other thiophene derivatives and thioether compounds. This paper provides a new idea for using visible-light absorption active components loaded on zeolite for photocatalytic and thermocatalytic desulfurization applications.

Key words: Molybdovanadophosphoric acid, SBA-15, Photothermal, Oxidative desulfurization

CLC Number:

O643.3

Meng-Chun ZHU, Qi-Qi LI, Hong-Rui TIAN, Yan-Feng BI. SBA-15-Supported Molybdovanadophosphoric Acid Photothermal Catalysts for Efficient Oxidation Desulfurization at Room Temperature[J]. Chinese Journal of Applied Chemistry, 2024, 41(10): 1469-1480.

Figures/Tables 12

Table 1 BET surface area， pore volume， and pore diameter of X%PMoV catalysts

Catalysts	BET surface area/（m²·g^-1）	Pore volume/（cm³·g^-1）	Pore size/nm
SBA-15	719	1.09	5.78
10%PMoV	593	0.87	5.39
20%PMoV	535	0.89	5.91
30%PMoV	488	0.85	6.02
40%PMoV	426	0.74	5.96
50%PMoV	400	0.75	6.35

Fig.1 Nitrogen adsorption-desorption isotherms （A） and pore size distributions （B） of catalysts

Fig.2 The FT-IR patterns of samples （A） and small-angle XRD diagram of SBA-15 with PMoV （B）

Fig.3 TEM images of samples

Fig.4 EDX mapping images of 10%PMoV （A） and 30%PMoV （B）

Fig.5 XPS patterns of samples （A） and high-solution XPS for Mo3d （B），V2p （C），O1s （D）

Fig.6 UV-Vis diffuse reflectance spectra of X%PMoV and H4PMo11VO40

Fig.7 Photothermal experiment for samples time-temperature curves in CH3CN solvent （A）； photothermal images of 30%PMoV （B）

Fig.8 The oxidation removal of DBT performances for X%PMoV catalysts under （A） dark and （B） irradiation

Fig.9 The oxidation removal of DBT performances for 30%PMoV at different conditions （A）； FT-IR spectrum of oxidative product DBTO2 （B）

Fig.10 Four reaction cycles （A） and FT-IR spectra for 30%PMoV sample before and after the reaction （B）

Table 2 Desulfurization efficiency of various sulfides with catalyst and oxidant H2O2a

Num	Time/h	Desulfurization rate/%
1	0.5	＞99
2	0.5	＞99
3	0.5	＞99
4	1	91
4	2	＞99
5	1	87
5	2	＞99
6	1	78
6	3	＞99
7	6	＜67

References 47

1	ALMETWALLY A A， BIN-JUMAH M， ALLAM A A. Ambient air pollution and its influence on human health and welfare： an overview［J］. Environ Sci Pollut Res Int， 2020， 27（20）： 24815-24830.
2	SALEH T A. Characterization， determination and elimination technologies for sulfur from petroleum： toward cleaner fuel and a safe environment［J］. Trends Environ Anal Chem， 2020， 25： e00080.
3	SAHA B， VEDACHALAM S， DALAI A K. Review on recent advances in adsorptive desulfurization‍［J］. Fuel Process Technol， 2021， 214： 106685.
4	REZAEE M， FEYZI F， DEHGHANI M R. Extractive desulfurization of dibenzothiophene from normal octane using deep eutectic solvents as extracting agent［J］. J Mol Liq， 2021， 333： 115991.
5	CHEN S Q， ZANG M， LI L， et al. Efficient biodesulfurization of diesel oil by Gordonia sp SC-10 with highly hydrophobic cell surfaces［J］. Chem Eng J， 2021， 174： 108094.
6	CHOI A E S， ROCES S A， DUGOS N P， et al. A comprehensive process optimization study of the mixing assisted oxidative desulfurization of diesel oil［J］. Environ Technol Innovation， 2023， 31： 103144.
7	SHAFIQ I， HUSSAIN M， SHAFIQUE S， et al. Oxidative desulfurization of refinery diesel pool fractions using LaVO₄ photocatalyst［J］. J Ind Eng Chem， 2021， 98： 283-288.
8	商宇桐，杨丽娜，管景国，等. 光催化氧化脱硫催化剂研究进展［J］. 石油化工高等学校学报， 2020， 33（2）： 17-22.
	SHANG Y T， YANG L N， GUAN J G， et al. Progress in photocatalytic oxidation desulfurization catalysts［J］. J Petrochem Univ， 2020， 33（2）： 17-22.
9	陈立东，佟欢，王旭阳，等. Keggin结构多阴阳离子构筑高活性多酸基氧化脱硫催化剂［J］. 应用化学， 2017， 34（11）： 1301-1306.
	CHEN L D， TONG H， WANG X Y， et al. Preparation of high activity oxidative desulfurization catalyst with polycation and heteropolyanion keggin structure［J］. Chin J Appl Chem， 2017， 34（11）： 1301-1306.
10	WANG C W， LIU Z， GAO R， et al. Deep oxidative desulfurization of model fuels catalyzed by polyoxometalates anchored on amine-functionalized ceria doped MCM-41 with molecular oxygen［J］. New J Chem， 2020， 44（16）： 6251-6260.
11	YASEEN M， KHATTAK S， ULLAH S， et al. Oxidative desulfurization of model and real petroleum distillates using Cu or Ni impregnated banana peels derived activated carbon-NaClO catalyst-oxidant system‍［J］. Chem Eng Res Des， 2022， 179： 107-118.
12	DOU S Y， WANG R. High-efficient utilization of gaseous oxidants in oxidative desulfurization based on sulfonated carbon materials［J］. Fuel Process Technol， 2022， 235： 107372.
13	LIN S C， NG S F， ONG W J. Life cycle assessment of environmental impacts associated with oxidative desulfurization of diesel fuels catalyzed by metal-free reduced graphene oxide［J］. Environ Pollut， 2021， 288： 117677.
14	REZVANI M A， AGHBOLAGH Z S， MONFARED H H. Green and efficient organic-inorganic hybrid nanocatalyst for oxidative desulfurization of gasoline［J］. Appl Organomet Chem， 2018， 32（12）： e4592.
15	FANG Z， ZHAO Z G， LI N， et al. Low-temperature catalytic oxidative desulfurization by two-phase system with O-bridged diiron perfluorophthalocyanine［J］. Fuel， 2021， 306： 121649.
16	GAO S R， CHEN X C， XI X T， et al. Coupled oxidation-extraction desulfurization： a novel evaluation for diesel fuel［J］. ACS Sustainable Chem Eng， 2019， 7（6）： 5660-5668.
17	ZUO M G， HUANG X Q， LI J X， et al. Oxidative desulfurization in diesel via a titanium dioxide triggered thermocatalytic mechanism［J］. Catal Sci Technol， 2019， 9（11）： 2923-2930.
18	ZHOU X Y， WANG T Y， LIU H， et al. Desulfurization through photocatalytic oxidation： a critical review［J］. ChemSusChem， 2021， 14（2）： 492-511.
19	SHAFI R F， AMMAR S H， RASHED M K. Catalytic/photocatalytic oxidative desulfurization activities of heteropolyacid immobilized on magnetic polythiophene nanocatalyst［J］. J Sulfur Chem， 2021， 42（4）： 443-463.
20	ORTIZ-BUSTOS J， PEREZ DEL PULGAR H， PEREZ Y， et al. Enhanced adsorption-catalysis combination for the removal of sulphur from fuels using polyoxometalates supported on amphipathic hybrid mesoporous silica nanoparticles‍［J］. Dalton Trans， 2023， 52（30）： 10423-10436.
21	YUZBASHI S， MOUSAZADEH M H， RAMEZANI N， et al. Mesoporous zirconium-silica nanocomposite modified with heteropoly tungstophosphoric acid catalyst for ultra-deep oxidative desulfurization［J］. Appl Organomet Chem， 2019， 34（2）： e5326.
22	LI J R， YANG Z， LI S W， et al. Review on oxidative desulfurization of fuel by supported heteropolyacid catalysts‍［J］. J Ind Eng Chem， 2020， 82： 1-16.
23	CHEN X F， ZHANG G H， LI B， et al. An integrated giant polyoxometalate complex for photothermally enhanced catalytic oxidation［J］. Sci Adv， 2021， 7（30）： eabf8413.
24	韩旭，白雪，张仲，等. PW₁₁M@Cu₃（BTC）₂杂化物的合成及燃料油深度脱硫活性［J］. 高等学校化学学报， 2023， 44（4）： 9-17.
	HAN X， BAI X， ZHANG Z， et al. Synthesis and deep desulfurization activity of fuel oil of PW₁₁M@Cu₃（BTC）₂ hybrid［J］. Chem J Chin Univ， 2023， 44（4）： 9-17.
25	ZHAO D Y， FENG J L， HUO Q S， et al. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores［J］. Science， 1998， 279（5350）： 548-552.
26	CRUCIANELLI M， BIZZARRI B M， SALADINO R. SBA-15 Anchored metal containing catalysts in the oxidative desulfurization process［J］. Catalysts， 2019， 9（12）： 984.
27	TSIGDINOS G， HALLADA C. Molybdovanadophosphoric and their salts. I. investigation of methods of preparation and characterization［J］. Inorg Chem， 1968， 7（3）： 437-441
28	HE K， LIU S J， ZHAO G Y， et al. Ni-W catalysts supported on mesoporous SBA-15： trace W steering CO₂ methanation［J］. Chem Res Chin Univ， 2022， 38（6）： 1504-1511.
29	GAO Y， CHEN Y， WANG C Y， et al. Polyoxometalates encapsulated into hollow periodic mesoporous organosilica as nanoreactors for extraction oxidation desulfurization［J］. Catalysts， 2023， 13（4）： 747.
30	LIU Y， LIAO J J， CHANG L P， et al. Ag modification of SBA-15 and MCM-41 mesoporous materials as sorbents of thiophene［J］. Fuel， 2022， 311： 122537.
31	刘宗章，张彤，徐彧超，等. 乙醇制1，3-丁二烯MgO/SBA-15催化剂的制备及其催化性能［J］. 应用化学， 2019， 36（2）： 176-181.
	LIU Z Z， ZHANG T， XU Y C， et al. Preparation of MgO/SBA-15 catalyst and its catalytic performance for the synthesis of 1，3-butadiene from ethanol［J］. Chin J Appl Chem， 2019， 36（2）： 176-181.
32	AHMADIAN M， ANBIA M. Keggin-type heteropolyanions immobilized on phosphorus slag derived SiO₂： synthesis， characterization， and their catalytic oxidative desulfurization activity［J］. Energy Fuels， 2023， 37（21）： 16790-16804.
33	JING F， KATRYNIOK B， DUMEIGNIL F， et al. Catalytic selective oxidation of isobutane to methacrylic acid on supported （NH₄）₃HPMo₁₁VO₄₀ catalysts［J］. J Catal， 2014， 309： 121-135.
34	YU S P， ZHAO X H， SU G Y， et al. Synthesis and electrocatalytic performance of a P-Mo-V Keggin heteropolyacid modified Ag @Pt/MWCNTs catalyst for oxygen reduction in proton exchange membrane fuel cell［J］. Ionics， 2019， 25（11）： 5141-5152.
35	SUBHAN F， ASLAM S， YAN Z F， et al. Highly dispersive lanthanum oxide fabricated in confined space of SBA-15 for adsorptive desulfurization［J］. Chem Eng J， 2020， 384： 123271.
36	刘宁，王丹凤，伍素云，等. 短孔道介孔分子筛Zr-Ce-SBA-15固载酸性离子液体催化合成双酚F［J］. 应用化学， 2020， 37（9）： 1038-1047.
	LIU N， WANG D F， WU S Y， et al. Catalytic synthesis of bisphenol F over short-channeled mesoporous molecular sieve Zr-Ce-SBA-15 supported acidic ionic liquids［J］. Chin J Appl Chem， 2020， 37（9）： 1038-1047.
37	POPA A， SASCA V， VERDES O， et al. Heteropolyacids anchored on amino-functionalized MCM-41 and SBA-15 and its application to the ethanol conversion reaction［J］. J Therm Anal Calorim， 2016， 127（1）： 319-334.
38	ZHANG Y， YANG W， YANG X， et al. Rational design of efficient polar heterogeneous catalysts for catalytic oxidative-adsorptive desulfurization in fuel oil［J］. Appl Catal A， 2022， 632： 118498.
39	MA S， BAO W， LIU B， et al. PMo₁₁V polyoxometalate encapsulated into hollow mesoporous carbon spheres： a highly efficient and ultra-stable catalyst for oxidative desulfurization［J］. Appl Surf Sci， 2022， 606： 119014.
40	JIANG W， XIAO J， GAO X， et al. In situ fabrication of hollow silica confined defective molybdenum oxide for enhanced catalytic oxidative desulfurization of diesel fuels［J］. Fuel， 2021， 305： 121470.
41	JI D D， XUE R， ZHOU M J， et al. Preparation and photocatalytic performance of tungstovanadophosphoric heteropoly acid salts［J］. RSC Adv， 2019， 9（32）： 18320-18325.
42	SONG C Q， WANG Z H， YIN Z， et al. Principles and applications of photothermal catalysis［J］. Chem Catal， 2022， 2（1）： 52-83.
43	ZHANG Z W， WEI K H， LI C， et al. Oxidation adsorptive desulfurization of jet fuel using mesoporous sieve loaded with TiO₂［J］. Chem Select， 2021， 6（12）： 2913-2918.
44	MATEO D， CERRILLO J L， DURINI S， et al. Fundamentals and applications of photo-thermal catalysis［J］. Chem Soc Rev， 2021， 50（3）： 2173-2210.
45	HUO H Y， LIU Y W， YUAN M， et al. Synthesis and characterization of H₅PV₂Mo₁₀O₄₀@Cu₃（BTC）₂ and its use as a heterogeneous catalyst for oxidative desulfurization： a comprehensive chemistry laboratory experiment［J］. J Chem Educ， 2021， 98（11）： 3580-3586.
46	MA L， GUO F F， MA J F. Two Cu（Ⅰ）-based inorganic-organic complexes assembled with polyoxometalate and thiacalix［4］arene for efficient catalytic reactions［J］. New J Chem， 2022， 46（15）： 6995-7002.
47	YANG H W， JIANG B， SUN Y L， et al. Polymeric cation and isopolyanion ionic self-assembly： novel thin-layer mesoporous catalyst for oxidative desulfurization［J］. Chem Eng J， 2017， 317： 32-41.

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SBA-15-Supported Molybdovanadophosphoric Acid Photothermal Catalysts for Efficient Oxidation Desulfurization at Room Temperature

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