Adsorptive desulfurization of commercial diesel S500 using TiNi/AlMCM-41 and TiMo/AlMCM-41 nanoporous materials

Adsorptive desulfurization of commercial diesel S500 using TiNi/AlMCM-41 and TiMo/AlMCM-41 nanoporous materials | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Adsorptive desulfurization of commercial diesel S500 using TiNi/AlMCM-41 and TiMo/AlMCM-41 nanoporous materials Marcio D. S. Araujo, Adonias O. Teixeira, Sulene A. Araujo, Valter J. Fernandes, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8048202/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 10 Jan, 2026 Read the published version in Journal of Porous Materials → Version 1 posted 13 You are reading this latest preprint version Abstract Mesoporous adsorbents of the AlMCM-41 type impregnated with Ti-Ni and Ti-Mo bimetallic compounds were prepared, characterized and evaluated for the adsorptive desulfurization process of diesel. The AlMCM-41 materials were synthesized using the hydrothermal process, varying the times of 24, 48, and 72 hours, using cetyltrimethylammonium as a template. The calcined materials were impregnated with titanium, nickel, and molybdenum metals, with combinations of 15% by weight of active phase: 5.0% Ti and 10% Mo (TiMo) and 5.0% Ti and 10% Ni (TiNi). The materials were designated as TiMo/AlMCM-41 and TiNi/AlMCM-41. The obtained materials were tested as adsorbents for sulfur removal from a commercial S500 diesel sample, using a fixed-bed reactor containing a feeding system, a column packed with the adsorbent material and sample collectors, at room temperature under atmospheric pressure. It was verified that the sample containing TiNi/AlMCM-41 was the most efficient adsorbent, with capacity for removal of sulfur of 90%, for the sample containing the support synthesized at 48 hours. The high activity of TiNi/AlMCM-41 material was attributed to the π-complexation of the thiophene aromatic compounds and the synergism effect of the Ti-Ni bimetallic impregnated on the inner surface of the AlMCM-41 pores, allowing selective adsorption. Adsorption AlMCM-41 Desulfurization Titanium Molybdenum Nickel Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 1 Introduction Currently, due to regulations to limit pollutant emissions from petroleum-derived feedstocks, sulfur removal has become one of the most significant aspects of the refining industry. The main process for this is hydrodesulfurization (HDS), which requires high temperature and pressure, and hydrogen, requiring high energy demands. New technologies are needed to produce clean fuels to meet environmental requirements and regulations. The presence of thiophenic compounds in liquid fuels, specifically diesel, can lead to poisoning and deactivation of industrial catalysts, in addition to being harmful to the environment and human health [1] Considering this, many countries have applied stringent rules and regulations to limit emissions of sulfur compounds, and sulfur concentration in commercial gasoline and diesel fuel has been limited to 10 ppm [2,3]. Therefore, it is necessary to desulfurize these fuels before using them as secondary raw materials or making them available for transportation. The hydrodesulfurization (HDS) process has been the most widely used for removing sulfur from non-aromatic compounds. However, for thiophenic compounds, HDS technology does not work efficiently due to the stability of aromatic heterocyclic compounds and the steric hindrance of bulky sulfur-containing molecules [4–6]. Furthermore, the HDS process requires intense energy expenditure due to severe operating conditions, such as high temperatures and pressures, as well as presence of hydrogen[7–10]. Thus, adsorptive desulfurization emerges as an alternative process for removing sulfur from fuel streams under mild conditions, without hydrogen, making the process more economic [11–14]. For this process, various porous materials with active sites in specific adsorbents can be used for the adsorptive desulfurization of sulfur compounds in fuels, such as aluminosilicate based adsorbents [15,16], carbon [17–20], MOF [21–22], silica [23,24] and zeolites [25–28]. However, a limitation observed when applying microporous zeolites is related to their reduced pore diameter, which hinders the diffusion of larger molecules, common in diesel, to the internal active sites. Supported Ni and Mo catalysts are known for their activity in HDS processes for fuel production. However, catalysts are typically obtained with low-surface-area simple oxide supports, such as alumina, which can lead to poor dispersion and relatively low HDS activity [29]. Therefore, dispersing Ni and Mo on a high-surface-area mesoporous support becomes necessary, thereby improving the activity and selectivity for the removal of sulfur compounds present in gasoline and diesel fuels. Mesoporous materials have been recognized as the best supports for active phases due to their high specific area and pore volume, as well as uniform pore size distribution. MCM-41 mesoporous molecular sieves with a hexagonal arrangement of one-dimensional pores have received much attention [30]. However, the application of molecular sieves with siliceous structures is limited due to the lack of active sites. The incorporation of Al and transition metals, such as Ti emerges as a solution to this problem and has been extensively used in catalysis [31]. AlMCM-41 mesoporous materials demonstrate greater process efficiency due to their high specific area and pore volume, as well as the uniform distribution of Bronsted and Lewis acid sites within the pores [32–34]. The objective of this work is to develop nanostructured AlMCM-41 materials synthesized with different synthesis time and modified them with TiNi or TiMo metals for use as adsorbents for the removal of sulfur compounds present in diesel fuel, from the adsorptive desulfurization process of S500 commercial diesel. The use of mesoporous materials, which have significantly larger pore diameters, was investigated containing transition metal Ti, Mo and Ni, to promote π-complexation, favoring the selective adsorption process of sulfur compounds. 2 Experimental 2.1 Synthesis of TiNi and TiMo/AlMCM-41 materials The AlMCM-41 support was synthesized by the hydrothermal method described in the literature [35], using the cationic surfactant cetyltrimethylammonium bromide (CTMABr) as an organic structural template, from the following gel molar composition: 4.58SiO 2 : 0.485Na 2 O : 1CTMABr : 0.057 Al 2 O 3 : 200 H 2 O. Crystallization was then performed by transferring the final gel to an autoclave in a Teflon container and heating at 100°C for varying times of 24, 48, or 72 hours. This procedure was performed to optimize the influence of time on the structural organization process of the mesoporous materials. The gel was then filtered, washed with distilled water in a Büchner funnel, dried at 100°C, and calcined in air at 500°C for 6 h with a heating rate of 10 K/min. The deposition of Ti, Ni, and Mo metals on the calcined AlMCM-41 support was performed by co-impregnation with excess solvent using nickel nitrate hexahydrate: Ni(NO 3 ) 2 .6H 2 O (Riedel der Haen) as the nickel source, ammonium heptamolybdate: (NH 4 ) 6 Mo 7 O 24 .4H 2 O (Sigma-Aldrich) as the molybdenum source, and an acidic solution of 15% titanium chloride in HCl. Co-impregnation was performed using a porcelain crucible containing the necessary quantities to obtain mass percentages of 5% Ti and 10% Mo for TiMo/AlMCM-41 and 5% Ti and 10% Ni for TiNi/AlMCM-41. The materials were oven-dried and calcined according to the AlMCM-41 support procedure. 2.2 Physicochemical characterization of the materials All synthesized and calcined materials were characterized by the following physical and chemical methods: thermogravimetric analysis (TG/DTG), in the temperature range from room temperature to 1000°C, using nitrogen as the carrier gas, at 50 mL/min. X-ray diffraction (XRD) was performed using the powder method, in the diffraction angle range of 1 to 10 degrees. Fourier transform infrared (FTIR) absorption spectroscopy was performed to determine the structural properties of the Si-O and Al-O bond tetrahedra of the mesoporous support, in the region of 1200 to 400 cm -1 . A characteristic peak in the region of 960 cm -1 evidences the presence of the metals supported on AlMCM-41. 2.3 Fixed-bed adsorptive desulfurization The TiMo/AlMCM-41 and TiNi/MCM-41 materials, prepared using AlMCM-41 for 24, 48, and 72 hours, were tested as adsorbents for the removal of sulfur compounds present in a sample of commercial S500 diesel fuel (500 ppm of S, free of biodiesel), using the adsorptive desulfurization process, at room temperature, under atmospheric pressure. The adsorption tests were performed in a reactor containing a feed system with a peristaltic pump connected to a borosilicate glass column of 50 cm length, and 1 cm diameter containing a fixed bed of 1.0 g of adsorbent. The adsorbent was packed to prevent the movement of solid particles within the column when the fuel was introduced. This must be effective to ensure that the fuel remains in contact with the adsorbent for longer, making the removal of sulfur compounds more effective. The schematic of a fixed bed reactor containing the column packed with the mesoporous adsorbent is shown in Fig. 1 . The tests were carried out at room temperature, using a flow rate of 10 mL/h. After three hours, the diesel samples were collected and analyzed. The determination of the sulfur content present in both the original diesel sample and the diesel samples after passing through the adsorbents was performed on a Thermo Scientific TS3000 Ultraviolet Fluorescence (UVF) total sulfur analyzer. The combustion tube of the equipment was heated to 1075 ± 25°C, under an atmosphere of oxygen (420 mL/min) and helium (130 mL/min). Two calibration curves were constructed from standards with known sulfur concentrations, one with a low concentration (0 to 10 mg/kg) and the other with a medium concentration (100 to 500 mg/kg). The calibration curve was prepared with 99% dibenzothiophene standards (Sigma-Aldrich) using Xylene P.A. (Vetec) as the solvent. A 20 µL volume of the standard samples was injected directly into the combustion tube, where sulfur was oxidized to sulfur dioxide. The water produced during sample combustion was removed, and the combustion gases were exposed to ultraviolet radiation. The SO 2 absorbed energy from the radiation and was converted to excited sulfur dioxide (SO2*), and upon returning to the ground state, was detected by a photomultiplier, and the resulting signal was measured as sulfur concentration. Analyses were performed in triplicate, and the result was expressed as the average of the obtained values. 3 Results and discussion 3.1 Crystallographic properties from XRD Crystallographic properties of the materials were evaluated by X ray diffraction. From XRD data, it was verified that all synthesized materials presented ordered hexagonal structures characteristic of AlMCM-41, even after modifications induced by the impregnation of Ti, Ni and Mo metals, as illustrated in Fig. 2 . Analyzing Fig. 2 , it was found that all samples exhibited a reflection peak corresponding to the (100) plane of the typical long hexagonal structure of AlMCM-41, in the range of 2θ = 1.5–2.5 degrees. The samples containing Ti, Ni, and Mo maintained the hexagonal symmetry and exhibited a small peak shift to higher 2θ values relative to metal-free AlMCM-41. Furthermore, with increasing synthesis time of the TiMo and TiNi/AlMCM-41 samples, the (100) plane peaks became broader and lower than the pure AlMCM-41 peak. This is due to the incorporation of Ti atoms into the structure (Ti-O bond length: 0.179 nm) and the replacement of Si atoms (Si-O bond length: 0.161 nm), which causes some deformation or distortion of the tetrahedral coordination structure. In addition to the strong peak in the (100) plane, two peaks attributed to reflections from the (110) and (200) planes were observed for samples impregnated with the Ti, Ni and Mo metals. However, the peak in the (210) plane is very weak, which may also be due to distortion and shrinkage of the structure. The XRD data are given in Table 1 . Table 1 X-ray data obtained for samples AlMCM-41, TiMo/AlMCM-41 and TiNi/AlMCM-41. Sample (Synthesis time) 2θ ( o ) Index ( hkl ) d( hkl ) (nm) a 0 (nm) AlMCM-41 (24h) 2.71 (100) 3.26 3.76 AlMCM-41 (48h) 2.70 (100) 3.27 3.78 AlMCM-41 (72h) 2.63 (100) 3.36 3.88 TiMo/AlMCM-41 (24h) 2.75 (100) 3.21 3.71 TiNi/AlMCM-41 (24h) 2.76 (100) 3.20 3.70 TiMo/AlMCM-41 (48h) 2.74 (100) 3.22 3.72 TiNi/AlMCM-41 (48h) 2.67 (100) 3.31 3.82 TiMo/AlMCM-41 (72h) 2.65 (100) 3.33 3.85 TiNi/AlMCM-41 (72h) 2.67 (100) 3.31 3.82 The process of obtaining AlMCM-41 materials as ordered hexagonal mesopores was well observed at treatment times of 24 and 48 hours. For the hydrothermal synthesis time of 72 h, a lower structural disorder was observed, likely due to the increased alkaline environment generated by the release of the basic groups of the structural template (CTMA + ) to the external pore surface of AlMCM-41. The synthesis process typically involves hydrothermal treatment in alkaline media. Excessive alkalinity leads to a less ordered structure for the AlMCM-41 material, disturbing the hydrothermal equilibrium, leading to structural disorder [36]. 3.2 Structural properties from FTIR Based on the infrared spectroscopy analysis of the molecular sieve, it was possible to identify the vibrational frequencies and their respective assignments related to the organic functional groups present in the template structure (CTMA + ) and inorganic functional groups related to the support structure (3000–2850 cm -1 , 1490–1480 cm -1 , 1250–950 cm -1 , 1200–1000 cm -1 , 950 − 700 cm -1 , 650–520 cm -1 ). After the calcination step, the absorption bands related to the stretching and deformation of the bonds of the TO 4 tetrahedra (T = Si, Al) as well as the influence of the metals Ti, Ni and Mo in the structure of AlMCM-41 were observed in the spectral region of 1400 − 400 cm -1 , as can be visualized in Fig. 3 . The FTIR spectra in the structural region of the porous aluminosilicate samples (1400 − 400 cm -1 ) show characteristic bands attributed to stretching and deformation of the Si–O–Si and Si–O–M (M = Al, Ti, Ni or Mo) bonds of the TO 4 tetrahedra of the materials. The bands in the ranges of 1238–1236cm -1 and 1069–1066cm -1 are due to asymmetric and symmetric stretching of the bond in the silicates, respectively. The bands between 974–957 cm -1 are attributed to Si–O–M bonds. For the AlMCM-41 and TiNi/AlMCM-41 samples, only one band is observed in this spectral region, evidencing incorporation of Al and Ti, and high dispersion of Ni in the material. However, for the TiMo/AlMCM-41 sample, two bands were observed, at 957 cm -1 and 915 cm -1 , demonstrating low Mo dispersion and possible formation of the Mo = O bond of molybdenum oxide on the external surface of AlMCM-41. The band in the 801–803 cm-1 range is due to Si-O-Si stretching, and the band observed in the 459–455cm -1 range is due to bending of the T-O bond, opening the hexagonal pores of the materials. 3.4 Adsorptive desulfurization Adsorptive desulfurization tests were performed to evaluate the removal efficiency of sulfur compounds present in the Diesel S500 sample using the AlMCM-41, TiMo/AlMCM-41, and TiNi/AlMCM-41 materials, as well as the effect of molecular sieving on adsorbing sulfur compounds. The percentage of sulfur removed equivalent to adsorption process was determined from the equation below. $$\:Removal\:of\:Sulfur\:\left(\%\right)=\:\frac{\left({C}_{0}-{C}_{e}\right)\:}{{C}_{0}}\text{x}\:100\:\:\:$$ Where the C o and C e represent the initial concentration of sulfur compounds ( mg/L ) and residual concentration (mg /L ) at equilibrium, respectively. The results obtained for percentage of sulfur removal are shown in Fig. 4 . Sulfur compounds such as thiophene, benzothiophene, and dibenzothiophene are frequently found in commercial diesel [37–39], whose molecular dimensions are compatible with the typical pore diameters of mesoporous materials used as adsorbents. The introduction of aluminum into the MCM-41 structure promotes the formation of Lewis acid sites, which intensify electronic interactions with the sulfur atom, favoring its adsorption. The presence of titanium contributes to oxidizing properties, which aid in the activation of sulfur compounds, facilitating their retention. Furthermore, the bimetallic phases TiMo and TiNi demonstrate a synergistic effect, increasing the affinity of the materials for sulfur compounds and promoting their immobilization within the pores, resulting in greater efficiency in the adsorptive desulfurization process. Thus, the sample TiNi and TiMo supported on AlMCM-41 presented desired properties for adsorptive desulfurization of thiophenic compounds in diesel and gasoline fuels. The results obtained demonstrate the potential of TiNi/AlMCM-41 for adsorptive desulfurization as a viable and efficient alternative for the removal of sulfur compounds present in diesel fuel, operating under environmental conditions such as room temperature and atmospheric pressure. The high removal rate observed can be attributed to the high dispersion of Ni and nature of the interactions between the sulfur compounds and the surface of the adsorbents used. For adsorptive processes, three distinct mechanisms were considered: physisorption, chemisorption, and adsorption by π-complexation, with specific characteristics of selectivity, adsorption capacity, and material regenerability. A proposed scheme for π-complexation of thiophene, benzothiophene and dibenzothiophene is illustrated in Fig. 5 . In thiophene compounds, the interaction between d orbitals of Ni and π-orbitals of sulfur can occur through σ and π bonds. The σ interaction involves front-on overlap of the orbitals, while the π-interaction involves side-on overlap. The strength of this interaction depends on the compound geometry. Sulfur can also act as an electron donor, using its π orbitals to interact with vacant d orbitals of Ni. This π interaction is strongest when the sulfur and nickel orbitals are well aligned spatially, which can occur in compounds with specific geometries. In other cases, sulfur can act accepting electrons from Ni d orbitals. This π-complexation is strongest when sulfur has π orbitals with energies compatible with d orbitals of nickel. In the case of physisorption, the interactions occur predominantly through van der Waals forces, resulting in reversible and easily regenerated processes. However, the results show that this mechanism presents low selectivity and adsorptive capacity, specially against larger and more structurally complex molecules, such as those present in diesel fuel, as verified to TiMo/AlMCM-41. Chemisorption, while presenting higher adsorption capacity and selectivity values, proved to be unfavorable for adsorbent regeneration due to the formation of stronger chemical bonds between sulfur and the active sites on the surface, requiring severe conditions for desorption. Therefore, adsorption by π-complexation seemed to be the most promising among the mechanisms evaluated. Experimental data indicate that this type of interaction, based on the formation of complexes between the π-orbitals of sulfur compounds and transition metals present in the adsorbent material, results in an efficient combination of high selectivity, good adsorption capacity, and regenerability. The intermediate interaction strength allows molecules to be efficiently adsorbed without significantly compromising the reversibility of the process, which is a desirable aspect in practical applications. The literature corroborates these results [40], showing the modification of Y-type zeolites with transition metal ions to improve adsorptive performance through π-complexation. Indeed, modifying the zeolite structure led to increased selectivity, especially for compounds with sulfur-containing aromatic rings, such as dibenzothiophene and its derivatives [40]. The results showed that these materials are more effective in adsorbing sulfur compounds present in diesel, such as DBT, because they allow better diffusion of larger molecules. TiNi/AlMCM-41 functionalized with transition metal ions, demonstrated good performance, confirming the formation of stable π-complexes with aromatic sulfur compounds, which favors selective sulfur removal. Conclusion The characterizations performed to evaluate titanium, nickel, and molybdenum catalysts supported on mesoporous AlMCM-41 materials, along with adsorptive desulfurization tests, demonstrate that the hydrothermal synthesis route successfully produced AlMCM-41, TiMo/AlMCM-41, and TiNi/AlMCM-41 mesoporous materials. X-ray diffraction (XRD) analysis of the calcined samples revealed three main diffraction peaks corresponding to the (100), (110), and (200) planes, confirming the formation of hexagonal ordering in the AlMCM-41 structure. After metal impregnation, XRD patterns recorded in the 1° to 10° angular range showed minor changes in the (100) peak for TiNi-impregnated samples, without significant loss of hexagonal order, whereas TiMo- exhibited more pronounced alterations in this peak. Evaluation of sulfur compound removal rates indicated that some synthesized materials are promising for desulfurization, achieving over 20% removal and up to 90% adsorption capacity with TiNi/AlMCM-41 synthesized at 48 hours. This suggests that synthesis time can be optimized to enhance hexagonal structural organization and improve metal dispersion on the adsorbent. The observed catalytic activity is attributed to higher metal dispersion of Ni and incorporation of tetrahedrally coordinated Ti 4+ sites into the aluminosilicate framework, which activate hydroxyl groups and generate Brønsted and Lewis acid sites. Based on the analysis of the π-complexation applied to the removal of sulfur compounds, it is concluded that this process represents a highly selective and efficient strategy for the adsorptive desulfurization of liquid fuels. The interaction between the π orbitals of sulfur-containing aromatic compounds and transition bimetallic, such as Ti-Ni, enables the formation of stable and reversible complexes, which favors the regeneration of adsorbent materials under mild conditions. This characteristic gives the process a significant advantage over chemisorption, which, although selective, hinders the reuse of the adsorbent. The efficiency of π-complexation depends on both the nature of the metal and the structure of the support, with mesoporous materials such as AlMCM-41, demonstrating superior performance by facilitating the diffusion of larger molecules, typical of sulfured diesel. Despite potential limitations imposed by interference from sulfurized contaminants, π-complexation stands out as a promising alternative for the development of sustainable sulfur removal technologies, contributing to the production of cleaner fuels that are compatible with current environmental regulations. Declarations CRediT authorship contribution statement Marcio D. S. Araujo: Investigation, Data curation, Writing – original draft. Adonias A. Teixeira: Writing – review & editing. Sulene A. Araujo: Methodology, Conceptualization. Valter J. Fernandes Jr.: Data curation. Antonio S. Araujo: Supervision, Methodology. Acknowledgements The authors thank the Brazilian Agency of Petroleum, Natural Gas and Biofuel (ANP), and National Council for Scientific and Technological Development (CNPq Brazil, Grant number 312461/2022-4), for support this research. Declaration of Competing Interest The authors declare no conflict of interest. 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Cite Share Download PDF Status: Published Journal Publication published 10 Jan, 2026 Read the published version in Journal of Porous Materials → Version 1 posted Editorial decision: Revision requested 01 Dec, 2025 Reviews received at journal 27 Nov, 2025 Reviews received at journal 19 Nov, 2025 Reviews received at journal 13 Nov, 2025 Reviewers agreed at journal 10 Nov, 2025 Reviewers agreed at journal 10 Nov, 2025 Reviewers agreed at journal 10 Nov, 2025 Reviewers agreed at journal 09 Nov, 2025 Reviewers agreed at journal 09 Nov, 2025 Reviewers invited by journal 09 Nov, 2025 Editor assigned by journal 06 Nov, 2025 Submission checks completed at journal 06 Nov, 2025 First submitted to journal 06 Nov, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8048202","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":544558549,"identity":"f11a1409-8927-45fb-9e6a-e2db4e5e8abf","order_by":0,"name":"Marcio D. 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1","display":"","copyAsset":false,"role":"figure","size":146663,"visible":true,"origin":"","legend":"\u003cp\u003eScheme of the experimental setup for a fixed-bed reactor for adsorptive desulfurization of S500 Diesel, and a detail of the structure of the mesoporous adsorbent, containing transition metals (TiNi or TiMo impregnated in AlMCM-41)\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-8048202/v1/95e8407b75e81556ed9f2532.png"},{"id":96219746,"identity":"ce48c17b-0d65-44bf-b002-f929bec16e43","added_by":"auto","created_at":"2025-11-18 22:51:46","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":107359,"visible":true,"origin":"","legend":"\u003cp\u003eX-ray diffractograms for samples synthesized at 48 h and calcined: (a) AlMCM-41 support, (b) TiNi/AlMCM-41 and (c) TiMo/AlMCM-41.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-8048202/v1/d42508207f2d1f274e06b760.png"},{"id":96252744,"identity":"b31f4086-78df-43f1-902f-d7a06662712b","added_by":"auto","created_at":"2025-11-19 07:41:25","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":156922,"visible":true,"origin":"","legend":"\u003cp\u003eAbsorption spectra in the infrared region for samples synthesized at 48 h and calcined: (a) AlMCM-41 support, (b) TiNi/AlMCM-41 and (c) TiMo/AlMCM-41.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-8048202/v1/2c9a651f859997bc06eb46b7.png"},{"id":96219751,"identity":"591cd731-6f64-457c-b733-7bbc30f14702","added_by":"auto","created_at":"2025-11-18 22:51:46","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":224271,"visible":true,"origin":"","legend":"\u003cp\u003ePercentage removal of sulfur from diesel through adsorptive desulfurization using materials prepared under different conditions.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-8048202/v1/1de39dcc0e57e6334e313b72.png"},{"id":96219755,"identity":"db1202f8-9289-44fe-931b-2bd1204a2b12","added_by":"auto","created_at":"2025-11-18 22:51:46","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":179832,"visible":true,"origin":"","legend":"\u003cp\u003eProposed scheme for adsorptive desulfurization showing the π-complexation adsorption of some thiophenic compounds (thiophene, benzothiophene and dibenzothiophene) present in fuels inside the mesopore of the AlMCM-41, and some of these molecules outside the pore of the adsorbent.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-8048202/v1/0430f1e6a22d467b3f129d52.png"},{"id":100070552,"identity":"b3dea3a0-e814-4a71-8b73-68fcbdc6f117","added_by":"auto","created_at":"2026-01-12 16:18:08","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1444052,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8048202/v1/41b50bbd-4747-4844-bfe4-4d6c65a508ff.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Adsorptive desulfurization of commercial diesel S500 using TiNi/AlMCM-41 and TiMo/AlMCM-41 nanoporous materials","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eCurrently, due to regulations to limit pollutant emissions from petroleum-derived feedstocks, sulfur removal has become one of the most significant aspects of the refining industry. The main process for this is hydrodesulfurization (HDS), which requires high temperature and pressure, and hydrogen, requiring high energy demands. New technologies are needed to produce clean fuels to meet environmental requirements and regulations. The presence of thiophenic compounds in liquid fuels, specifically diesel, can lead to poisoning and deactivation of industrial catalysts, in addition to being harmful to the environment and human health [1] Considering this, many countries have applied stringent rules and regulations to limit emissions of sulfur compounds, and sulfur concentration in commercial gasoline and diesel fuel has been limited to 10 ppm [2,3]. Therefore, it is necessary to desulfurize these fuels before using them as secondary raw materials or making them available for transportation. The hydrodesulfurization (HDS) process has been the most widely used for removing sulfur from non-aromatic compounds. However, for thiophenic compounds, HDS technology does not work efficiently due to the stability of aromatic heterocyclic compounds and the steric hindrance of bulky sulfur-containing molecules [4\u0026ndash;6]. Furthermore, the HDS process requires intense energy expenditure due to severe operating conditions, such as high temperatures and pressures, as well as presence of hydrogen[7\u0026ndash;10]. Thus, adsorptive desulfurization emerges as an alternative process for removing sulfur from fuel streams under mild conditions, without hydrogen, making the process more economic [11\u0026ndash;14]. For this process, various porous materials with active sites in specific adsorbents can be used for the adsorptive desulfurization of sulfur compounds in fuels, such as aluminosilicate based adsorbents [15,16], carbon [17\u0026ndash;20], MOF [21\u0026ndash;22], silica [23,24] and zeolites [25\u0026ndash;28]. However, a limitation observed when applying microporous zeolites is related to their reduced pore diameter, which hinders the diffusion of larger molecules, common in diesel, to the internal active sites.\u003c/p\u003e\u003cp\u003eSupported Ni and Mo catalysts are known for their activity in HDS processes for fuel production. However, catalysts are typically obtained with low-surface-area simple oxide supports, such as alumina, which can lead to poor dispersion and relatively low HDS activity [29]. Therefore, dispersing Ni and Mo on a high-surface-area mesoporous support becomes necessary, thereby improving the activity and selectivity for the removal of sulfur compounds present in gasoline and diesel fuels. Mesoporous materials have been recognized as the best supports for active phases due to their high specific area and pore volume, as well as uniform pore size distribution. MCM-41 mesoporous molecular sieves with a hexagonal arrangement of one-dimensional pores have received much attention [30]. However, the application of molecular sieves with siliceous structures is limited due to the lack of active sites. The incorporation of Al and transition metals, such as Ti emerges as a solution to this problem and has been extensively used in catalysis [31]. AlMCM-41 mesoporous materials demonstrate greater process efficiency due to their high specific area and pore volume, as well as the uniform distribution of Bronsted and Lewis acid sites within the pores [32\u0026ndash;34].\u003c/p\u003e\u003cp\u003eThe objective of this work is to develop nanostructured AlMCM-41 materials synthesized with different synthesis time and modified them with TiNi or TiMo metals for use as adsorbents for the removal of sulfur compounds present in diesel fuel, from the adsorptive desulfurization process of S500 commercial diesel. The use of mesoporous materials, which have significantly larger pore diameters, was investigated containing transition metal Ti, Mo and Ni, to promote π-complexation, favoring the selective adsorption process of sulfur compounds.\u003c/p\u003e"},{"header":"2 Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003ch2\u003e2.1 Synthesis of TiNi and TiMo/AlMCM-41 materials\u003c/h2\u003e\u003cp\u003eThe AlMCM-41 support was synthesized by the hydrothermal method described in the literature [35], using the cationic surfactant cetyltrimethylammonium bromide (CTMABr) as an organic structural template, from the following gel molar composition: 4.58SiO\u003csub\u003e2\u003c/sub\u003e : 0.485Na\u003csub\u003e2\u003c/sub\u003eO : 1CTMABr : 0.057 Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e : 200 H\u003csub\u003e2\u003c/sub\u003eO. Crystallization was then performed by transferring the final gel to an autoclave in a Teflon container and heating at 100\u0026deg;C for varying times of 24, 48, or 72 hours. This procedure was performed to optimize the influence of time on the structural organization process of the mesoporous materials. The gel was then filtered, washed with distilled water in a B\u0026uuml;chner funnel, dried at 100\u0026deg;C, and calcined in air at 500\u0026deg;C for 6 h with a heating rate of 10 K/min.\u003c/p\u003e\u003cp\u003eThe deposition of Ti, Ni, and Mo metals on the calcined AlMCM-41 support was performed by co-impregnation with excess solvent using nickel nitrate hexahydrate: Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e.6H\u003csub\u003e2\u003c/sub\u003eO (Riedel der Haen) as the nickel source, ammonium heptamolybdate: (NH\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e6\u003c/sub\u003eMo\u003csub\u003e7\u003c/sub\u003eO\u003csub\u003e24\u003c/sub\u003e.4H\u003csub\u003e2\u003c/sub\u003eO (Sigma-Aldrich) as the molybdenum source, and an acidic solution of 15% titanium chloride in HCl. Co-impregnation was performed using a porcelain crucible containing the necessary quantities to obtain mass percentages of 5% Ti and 10% Mo for TiMo/AlMCM-41 and 5% Ti and 10% Ni for TiNi/AlMCM-41. The materials were oven-dried and calcined according to the AlMCM-41 support procedure.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\u003ch2\u003e2.2 Physicochemical characterization of the materials\u003c/h2\u003e\u003cp\u003eAll synthesized and calcined materials were characterized by the following physical and chemical methods: thermogravimetric analysis (TG/DTG), in the temperature range from room temperature to 1000\u0026deg;C, using nitrogen as the carrier gas, at 50 mL/min. X-ray diffraction (XRD) was performed using the powder method, in the diffraction angle range of 1 to 10 degrees. Fourier transform infrared (FTIR) absorption spectroscopy was performed to determine the structural properties of the Si-O and Al-O bond tetrahedra of the mesoporous support, in the region of 1200 to 400 cm\u003csup\u003e-1\u003c/sup\u003e. A characteristic peak in the region of 960 cm\u003csup\u003e-1\u003c/sup\u003e evidences the presence of the metals supported on AlMCM-41.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\u003ch2\u003e2.3 Fixed-bed adsorptive desulfurization\u003c/h2\u003e\u003cp\u003eThe TiMo/AlMCM-41 and TiNi/MCM-41 materials, prepared using AlMCM-41 for 24, 48, and 72 hours, were tested as adsorbents for the removal of sulfur compounds present in a sample of commercial S500 diesel fuel (500 ppm of S, free of biodiesel), using the adsorptive desulfurization process, at room temperature, under atmospheric pressure.\u003c/p\u003e\u003cp\u003eThe adsorption tests were performed in a reactor containing a feed system with a peristaltic pump connected to a borosilicate glass column of 50 cm length, and 1 cm diameter containing a fixed bed of 1.0 g of adsorbent. The adsorbent was packed to prevent the movement of solid particles within the column when the fuel was introduced. This must be effective to ensure that the fuel remains in contact with the adsorbent for longer, making the removal of sulfur compounds more effective. The schematic of a fixed bed reactor containing the column packed with the mesoporous adsorbent is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe tests were carried out at room temperature, using a flow rate of 10 mL/h. After three hours, the diesel samples were collected and analyzed. The determination of the sulfur content present in both the original diesel sample and the diesel samples after passing through the adsorbents was performed on a Thermo Scientific TS3000 Ultraviolet Fluorescence (UVF) total sulfur analyzer. The combustion tube of the equipment was heated to 1075\u0026thinsp;\u0026plusmn;\u0026thinsp;25\u0026deg;C, under an atmosphere of oxygen (420 mL/min) and helium (130 mL/min). Two calibration curves were constructed from standards with known sulfur concentrations, one with a low concentration (0 to 10 mg/kg) and the other with a medium concentration (100 to 500 mg/kg). The calibration curve was prepared with 99% dibenzothiophene standards (Sigma-Aldrich) using Xylene P.A. (Vetec) as the solvent. A 20 \u0026micro;L volume of the standard samples was injected directly into the combustion tube, where sulfur was oxidized to sulfur dioxide. The water produced during sample combustion was removed, and the combustion gases were exposed to ultraviolet radiation. The SO\u003csub\u003e2\u003c/sub\u003e absorbed energy from the radiation and was converted to excited sulfur dioxide (SO2*), and upon returning to the ground state, was detected by a photomultiplier, and the resulting signal was measured as sulfur concentration. Analyses were performed in triplicate, and the result was expressed as the average of the obtained values.\u003c/p\u003e\u003c/div\u003e"},{"header":"3 Results and discussion","content":"\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\u003ch2\u003e3.1 Crystallographic properties from XRD\u003c/h2\u003e\u003cp\u003eCrystallographic properties of the materials were evaluated by X ray diffraction. From XRD data, it was verified that all synthesized materials presented ordered hexagonal structures characteristic of AlMCM-41, even after modifications induced by the impregnation of Ti, Ni and Mo metals, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eAnalyzing Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, it was found that all samples exhibited a reflection peak corresponding to the (100) plane of the typical long hexagonal structure of AlMCM-41, in the range of 2θ\u0026thinsp;=\u0026thinsp;1.5\u0026ndash;2.5 degrees. The samples containing Ti, Ni, and Mo maintained the hexagonal symmetry and exhibited a small peak shift to higher 2θ values relative to metal-free AlMCM-41. Furthermore, with increasing synthesis time of the TiMo and TiNi/AlMCM-41 samples, the (100) plane peaks became broader and lower than the pure AlMCM-41 peak. This is due to the incorporation of Ti atoms into the structure (Ti-O bond length: 0.179 nm) and the replacement of Si atoms (Si-O bond length: 0.161 nm), which causes some deformation or distortion of the tetrahedral coordination structure.\u003c/p\u003e\u003cp\u003eIn addition to the strong peak in the (100) plane, two peaks attributed to reflections from the (110) and (200) planes were observed for samples impregnated with the Ti, Ni and Mo metals. However, the peak in the (210) plane is very weak, which may also be due to distortion and shrinkage of the structure. The XRD data are given in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eX-ray data obtained for samples AlMCM-41, TiMo/AlMCM-41 and TiNi/AlMCM-41.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"6\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eSample\u003c/p\u003e\u003cp\u003e(Synthesis time)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2θ (\u003csup\u003eo\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eIndex (\u003cem\u003ehkl\u003c/em\u003e)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e\u003cp\u003ed(\u003csub\u003ehkl\u003c/sub\u003e) (nm)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e\u003cp\u003ea\u003csub\u003e0\u003c/sub\u003e\u003c/p\u003e\u003cp\u003e(nm)\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAlMCM-41 (24h)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.71\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e(100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3.26\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003e3.76\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAlMCM-41 (48h)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.70\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e(100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3.27\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003e3.78\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAlMCM-41 (72h)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.63\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e(100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3.36\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003e3.88\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTiMo/AlMCM-41 (24h)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.75\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e(100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3.21\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003e3.71\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTiNi/AlMCM-41 (24h)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.76\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e(100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3.20\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003e3.70\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTiMo/AlMCM-41 (48h)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.74\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e(100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3.22\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003e3.72\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTiNi/AlMCM-41 (48h)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.67\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e(100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3.31\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003e3.82\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTiMo/AlMCM-41 (72h)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.65\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e(100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3.33\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003e3.85\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTiNi/AlMCM-41 (72h)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.67\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e(100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3.31\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003e3.82\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eThe process of obtaining AlMCM-41 materials as ordered hexagonal mesopores was well observed at treatment times of 24 and 48 hours. For the hydrothermal synthesis time of 72 h, a lower structural disorder was observed, likely due to the increased alkaline environment generated by the release of the basic groups of the structural template (CTMA\u003csup\u003e+\u003c/sup\u003e) to the external pore surface of AlMCM-41. The synthesis process typically involves hydrothermal treatment in alkaline media. Excessive alkalinity leads to a less ordered structure for the AlMCM-41 material, disturbing the hydrothermal equilibrium, leading to structural disorder [36].\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\u003ch2\u003e3.2 Structural properties from FTIR\u003c/h2\u003e\u003cp\u003eBased on the infrared spectroscopy analysis of the molecular sieve, it was possible to identify the vibrational frequencies and their respective assignments related to the organic functional groups present in the template structure (CTMA\u003csup\u003e+\u003c/sup\u003e) and inorganic functional groups related to the support structure (3000\u0026ndash;2850 cm\u003csup\u003e-1\u003c/sup\u003e, 1490\u0026ndash;1480 cm\u003csup\u003e-1\u003c/sup\u003e, 1250\u0026ndash;950 cm\u003csup\u003e-1\u003c/sup\u003e, 1200\u0026ndash;1000 cm\u003csup\u003e-1\u003c/sup\u003e, 950\u0026thinsp;\u0026minus;\u0026thinsp;700 cm\u003csup\u003e-1\u003c/sup\u003e, 650\u0026ndash;520 cm\u003csup\u003e-1\u003c/sup\u003e). After the calcination step, the absorption bands related to the stretching and deformation of the bonds of the TO\u003csub\u003e4\u003c/sub\u003e tetrahedra (T\u0026thinsp;=\u0026thinsp;Si, Al) as well as the influence of the metals Ti, Ni and Mo in the structure of AlMCM-41 were observed in the spectral region of 1400\u0026thinsp;\u0026minus;\u0026thinsp;400 cm\u003csup\u003e-1\u003c/sup\u003e, as can be visualized in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe FTIR spectra in the structural region of the porous aluminosilicate samples (1400\u0026thinsp;\u0026minus;\u0026thinsp;400 cm\u003csup\u003e-1\u003c/sup\u003e) show characteristic bands attributed to stretching and deformation of the Si\u0026ndash;O\u0026ndash;Si and Si\u0026ndash;O\u0026ndash;M (M\u0026thinsp;=\u0026thinsp;Al, Ti, Ni or Mo) bonds of the TO\u003csub\u003e4\u003c/sub\u003e tetrahedra of the materials. The bands in the ranges of 1238\u0026ndash;1236cm\u003csup\u003e-1\u003c/sup\u003e and 1069\u0026ndash;1066cm\u003csup\u003e-1\u003c/sup\u003e are due to asymmetric and symmetric stretching of the bond in the silicates, respectively. The bands between 974\u0026ndash;957 cm\u003csup\u003e-1\u003c/sup\u003e are attributed to Si\u0026ndash;O\u0026ndash;M bonds. For the AlMCM-41 and TiNi/AlMCM-41 samples, only one band is observed in this spectral region, evidencing incorporation of Al and Ti, and high dispersion of Ni in the material. However, for the TiMo/AlMCM-41 sample, two bands were observed, at 957 cm\u003csup\u003e-1\u003c/sup\u003e and 915 cm\u003csup\u003e-1\u003c/sup\u003e, demonstrating low Mo dispersion and possible formation of the Mo\u0026thinsp;=\u0026thinsp;O bond of molybdenum oxide on the external surface of AlMCM-41. The band in the 801\u0026ndash;803 cm-1 range is due to Si-O-Si stretching, and the band observed in the 459\u0026ndash;455cm\u003csup\u003e-1\u003c/sup\u003e range is due to bending of the T-O bond, opening the hexagonal pores of the materials.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e\u003ch2\u003e3.4 Adsorptive desulfurization\u003c/h2\u003e\u003cp\u003eAdsorptive desulfurization tests were performed to evaluate the removal efficiency of sulfur compounds present in the Diesel S500 sample using the AlMCM-41, TiMo/AlMCM-41, and TiNi/AlMCM-41 materials, as well as the effect of molecular sieving on adsorbing sulfur compounds. The percentage of sulfur removed equivalent to adsorption process was determined from the equation below.\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:Removal\\:of\\:Sulfur\\:\\left(\\%\\right)=\\:\\frac{\\left({C}_{0}-{C}_{e}\\right)\\:}{{C}_{0}}\\text{x}\\:100\\:\\:\\:$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eWhere the \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003eo\u003c/b\u003e\u003c/sub\u003e and \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003ee\u003c/b\u003e\u003c/sub\u003e represent the initial concentration of sulfur compounds (\u003cem\u003emg/L\u003c/em\u003e) and residual concentration (mg\u003cem\u003e/L\u003c/em\u003e) at equilibrium, respectively. The results obtained for percentage of sulfur removal are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eSulfur compounds such as thiophene, benzothiophene, and dibenzothiophene are frequently found in commercial diesel [37\u0026ndash;39], whose molecular dimensions are compatible with the typical pore diameters of mesoporous materials used as adsorbents. The introduction of aluminum into the MCM-41 structure promotes the formation of Lewis acid sites, which intensify electronic interactions with the sulfur atom, favoring its adsorption. The presence of titanium contributes to oxidizing properties, which aid in the activation of sulfur compounds, facilitating their retention. Furthermore, the bimetallic phases TiMo and TiNi demonstrate a synergistic effect, increasing the affinity of the materials for sulfur compounds and promoting their immobilization within the pores, resulting in greater efficiency in the adsorptive desulfurization process. Thus, the sample TiNi and TiMo supported on AlMCM-41 presented desired properties for adsorptive desulfurization of thiophenic compounds in diesel and gasoline fuels.\u003c/p\u003e\u003cp\u003eThe results obtained demonstrate the potential of TiNi/AlMCM-41 for adsorptive desulfurization as a viable and efficient alternative for the removal of sulfur compounds present in diesel fuel, operating under environmental conditions such as room temperature and atmospheric pressure. The high removal rate observed can be attributed to the high dispersion of Ni and nature of the interactions between the sulfur compounds and the surface of the adsorbents used.\u003c/p\u003e\u003cp\u003eFor adsorptive processes, three distinct mechanisms were considered: physisorption, chemisorption, and adsorption by π-complexation, with specific characteristics of selectivity, adsorption capacity, and material regenerability. A proposed scheme for π-complexation of thiophene, benzothiophene and dibenzothiophene is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eIn thiophene compounds, the interaction between \u003cb\u003ed\u003c/b\u003e orbitals of Ni and π-orbitals of sulfur can occur through σ and π bonds. The σ interaction involves front-on overlap of the orbitals, while the π-interaction involves side-on overlap. The strength of this interaction depends on the compound geometry. Sulfur can also act as an electron donor, using its π orbitals to interact with vacant \u003cb\u003ed\u003c/b\u003e orbitals of Ni. This π interaction is strongest when the sulfur and nickel orbitals are well aligned spatially, which can occur in compounds with specific geometries. In other cases, sulfur can act accepting electrons from Ni \u003cb\u003ed\u003c/b\u003e orbitals. This π-complexation is strongest when sulfur has π orbitals with energies compatible with \u003cb\u003ed\u003c/b\u003e orbitals of nickel.\u003c/p\u003e\u003cp\u003eIn the case of physisorption, the interactions occur predominantly through van der Waals forces, resulting in reversible and easily regenerated processes. However, the results show that this mechanism presents low selectivity and adsorptive capacity, specially against larger and more structurally complex molecules, such as those present in diesel fuel, as verified to TiMo/AlMCM-41. Chemisorption, while presenting higher adsorption capacity and selectivity values, proved to be unfavorable for adsorbent regeneration due to the formation of stronger chemical bonds between sulfur and the active sites on the surface, requiring severe conditions for desorption.\u003c/p\u003e\u003cp\u003eTherefore, adsorption by π-complexation seemed to be the most promising among the mechanisms evaluated. Experimental data indicate that this type of interaction, based on the formation of complexes between the π-orbitals of sulfur compounds and transition metals present in the adsorbent material, results in an efficient combination of high selectivity, good adsorption capacity, and regenerability. The intermediate interaction strength allows molecules to be efficiently adsorbed without significantly compromising the reversibility of the process, which is a desirable aspect in practical applications. The literature corroborates these results [40], showing the modification of Y-type zeolites with transition metal ions to improve adsorptive performance through π-complexation. Indeed, modifying the zeolite structure led to increased selectivity, especially for compounds with sulfur-containing aromatic rings, such as dibenzothiophene and its derivatives [40].\u003c/p\u003e\u003cp\u003eThe results showed that these materials are more effective in adsorbing sulfur compounds present in diesel, such as DBT, because they allow better diffusion of larger molecules. TiNi/AlMCM-41 functionalized with transition metal ions, demonstrated good performance, confirming the formation of stable π-complexes with aromatic sulfur compounds, which favors selective sulfur removal.\u003c/p\u003e\u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe characterizations performed to evaluate titanium, nickel, and molybdenum catalysts supported on mesoporous AlMCM-41 materials, along with adsorptive desulfurization tests, demonstrate that the hydrothermal synthesis route successfully produced AlMCM-41, TiMo/AlMCM-41, and TiNi/AlMCM-41 mesoporous materials. X-ray diffraction (XRD) analysis of the calcined samples revealed three main diffraction peaks corresponding to the (100), (110), and (200) planes, confirming the formation of hexagonal ordering in the AlMCM-41 structure. After metal impregnation, XRD patterns recorded in the 1\u0026deg; to 10\u0026deg; angular range showed minor changes in the (100) peak for TiNi-impregnated samples, without significant loss of hexagonal order, whereas TiMo- exhibited more pronounced alterations in this peak. Evaluation of sulfur compound removal rates indicated that some synthesized materials are promising for desulfurization, achieving over 20% removal and up to 90% adsorption capacity with TiNi/AlMCM-41 synthesized at 48 hours. This suggests that synthesis time can be optimized to enhance hexagonal structural organization and improve metal dispersion on the adsorbent. The observed catalytic activity is attributed to higher metal dispersion of Ni and incorporation of tetrahedrally coordinated Ti\u003csup\u003e4+\u003c/sup\u003e sites into the aluminosilicate framework, which activate hydroxyl groups and generate Br\u0026oslash;nsted and Lewis acid sites.\u003c/p\u003e\u003cp\u003eBased on the analysis of the π-complexation applied to the removal of sulfur compounds, it is concluded that this process represents a highly selective and efficient strategy for the adsorptive desulfurization of liquid fuels. The interaction between the π orbitals of sulfur-containing aromatic compounds and transition bimetallic, such as Ti-Ni, enables the formation of stable and reversible complexes, which favors the regeneration of adsorbent materials under mild conditions. This characteristic gives the process a significant advantage over chemisorption, which, although selective, hinders the reuse of the adsorbent. The efficiency of π-complexation depends on both the nature of the metal and the structure of the support, with mesoporous materials such as AlMCM-41, demonstrating superior performance by facilitating the diffusion of larger molecules, typical of sulfured diesel. Despite potential limitations imposed by interference from sulfurized contaminants, π-complexation stands out as a promising alternative for the development of sustainable sulfur removal technologies, contributing to the production of cleaner fuels that are compatible with current environmental regulations.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eCRediT authorship contribution statement\u003c/strong\u003e\u003c/p\u003e\n\n\u003cp\u003eMarcio D. S. Araujo: Investigation, Data curation, Writing \u0026ndash; original draft. Adonias A. Teixeira: Writing \u0026ndash; review \u0026amp; editing. Sulene A. Araujo: Methodology, Conceptualization. Valter J. Fernandes Jr.: Data curation. Antonio S. Araujo: Supervision, Methodology. \u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\n\u003cp\u003eThe authors thank the Brazilian Agency of Petroleum, Natural Gas and Biofuel (ANP), and National Council for Scientific and Technological Development (CNPq Brazil, Grant number 312461/2022-4), for support this research.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eDeclaration of Competing Interest \u003c/strong\u003e\u003c/p\u003e\n\n\u003cp\u003eThe authors declare no conflict of interest. The consent to participation and publication of this study was provided by the authors. All procedures performed in this study were conducted according to the ethical standards of the institutions involved.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eX.J. Zhou, J. Weber, J.Y. Yuan, Poly(ionic liquid)s: platform for CO2 capture and catalysis. Curr. Opin. Green. 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Catal. 311, 257\u0026ndash;265 (2014). \u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"journal-of-porous-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jopo","sideBox":"Learn more about [Journal of Porous Materials](http://link.springer.com/journal/10934)","snPcode":"10934","submissionUrl":"https://submission.nature.com/new-submission/10934/3","title":"Journal of Porous Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Adsorption, AlMCM-41, Desulfurization, Titanium, Molybdenum, Nickel","lastPublishedDoi":"10.21203/rs.3.rs-8048202/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8048202/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eMesoporous adsorbents of the AlMCM-41 type impregnated with Ti-Ni and Ti-Mo bimetallic compounds were prepared, characterized and evaluated for the adsorptive desulfurization process of diesel. The AlMCM-41 materials were synthesized using the hydrothermal process, varying the times of 24, 48, and 72 hours, using cetyltrimethylammonium as a template. The calcined materials were impregnated with titanium, nickel, and molybdenum metals, with combinations of 15% by weight of active phase: 5.0% Ti and 10% Mo (TiMo) and 5.0% Ti and 10% Ni (TiNi). The materials were designated as TiMo/AlMCM-41 and TiNi/AlMCM-41. The obtained materials were tested as adsorbents for sulfur removal from a commercial S500 diesel sample, using a fixed-bed reactor containing a feeding system, a column packed with the adsorbent material and sample collectors, at room temperature under atmospheric pressure. It was verified that the sample containing TiNi/AlMCM-41 was the most efficient adsorbent, with capacity for removal of sulfur of 90%, for the sample containing the support synthesized at 48 hours. The high activity of TiNi/AlMCM-41 material was attributed to the π-complexation of the thiophene aromatic compounds and the synergism effect of the Ti-Ni bimetallic impregnated on the inner surface of the AlMCM-41 pores, allowing selective adsorption.\u003c/p\u003e","manuscriptTitle":"Adsorptive desulfurization of commercial diesel S500 using TiNi/AlMCM-41 and TiMo/AlMCM-41 nanoporous materials","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-11-18 22:51:41","doi":"10.21203/rs.3.rs-8048202/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-12-01T12:37:40+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-27T15:21:14+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-19T06:58:57+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-13T13:12:25+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"256784741762501045082877550135078815712","date":"2025-11-10T16:52:22+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"273694372302725021609000579143446751356","date":"2025-11-10T09:53:05+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"187455664913656211624943324696707244903","date":"2025-11-10T08:31:40+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"45119755493157256524451752125195372899","date":"2025-11-10T02:37:15+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"196668930847106563190323864381702861249","date":"2025-11-09T15:54:37+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-11-09T15:13:30+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-11-07T04:49:24+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-11-07T04:48:08+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Porous Materials","date":"2025-11-06T12:51:11+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-porous-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jopo","sideBox":"Learn more about [Journal of Porous Materials](http://link.springer.com/journal/10934)","snPcode":"10934","submissionUrl":"https://submission.nature.com/new-submission/10934/3","title":"Journal of Porous Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"ae001c45-081a-4114-8ed4-d64e2145e6ac","owner":[],"postedDate":"November 18th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-01-12T16:13:54+00:00","versionOfRecord":{"articleIdentity":"rs-8048202","link":"https://doi.org/10.1007/s10934-025-01911-w","journal":{"identity":"journal-of-porous-materials","isVorOnly":false,"title":"Journal of Porous Materials"},"publishedOn":"2026-01-10 15:57:06","publishedOnDateReadable":"January 10th, 2026"},"versionCreatedAt":"2025-11-18 22:51:41","video":"","vorDoi":"10.1007/s10934-025-01911-w","vorDoiUrl":"https://doi.org/10.1007/s10934-025-01911-w","workflowStages":[]},"version":"v1","identity":"rs-8048202","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8048202","identity":"rs-8048202","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}