Startseite Excellent catalytic performance over reduced graphene-boosted novel nanoparticles for oxidative desulfurization of fuel oil
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Excellent catalytic performance over reduced graphene-boosted novel nanoparticles for oxidative desulfurization of fuel oil

  • Tasmia Irshad , Muhammad Saeed , Mamoona Munir , Rehana Kousar , Azeem Intisar EMAIL logo , Muhammad Imran Din , Hadia Ahsan , Muhammad Amin Abid , Muhammad Irfan und Sameh M. Osman EMAIL logo
Veröffentlicht/Copyright: 16. Dezember 2024
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Nanotechnology Reviews
Aus der Zeitschrift Nanotechnology Reviews Band 13 Heft 1

Abstract

Three new inorganic–organic hybrid nanocomposites (In–WO3@rGO, Mo–WO3@rGO, and Mn–WO4@rGO) were synthesized by hydrothermal method and applied for recoverable and efficacious ODS process of real oil. The physicochemical analysis of novel nanocatalysts was conducted by various techniques, i.e., powder X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy and thermogravimetric analysis. XRD and SEM analyses depicted that the nanoparticles (In–WO3, Mn–WO4, and Mo–WO3) were well embellished on the exterior of reduced GO with an amazing morphology, having a crystallite size of less than 40 nm. The catalytic activity of nanocomposites was scrutinized for real fuel (diesel and kerosene) and model fuel (DBT) using the radical initiator mechanism of the ODS pathway. Excellent efficiency can be obtained under optimized conditions using 0.1 g catalyst, 1 mL oxidant (H2O2), and100 ppm DBT at 40°C with a time duration of 180 min. Various factors such as time, DBT concentration, catalyst amount, oxidant amount, and temperature that affect catalytic activity directly or indirectly were also studied. A pseudo-first-order kinetics model was followed, and due to spontaneous reaction, a negative value of ΔG was observed with an activation energy of 6.54 kJ/mol for Mo–WO3@rGO, which is lower than that of the other two hybrids. The synthesized nanohybrids showed remarkable durability and recovery up to five times for the ODS process without significant change in proficiency.

Keywords: hybrid materials; oxidative desulfurization; model fuel; dibenzothiophene; real fuel

1 Introduction

With the increasing world population, the sulfur content in the atmosphere is increasing day by day because of the emission of gases as a result of excessive human activities such as transportation, electricity, and construction of materials. This increase in sulfur-containing particles causes air pollution and is depleting our environment. The issue of the environment is becoming more severe day by day due to industrialization, urbanization, etc., which are negatively affecting our ecosystem. According to UNO legislation, the limit of sulfur content in HCSs is not to be more than 10 ppm for gasoline and 15 ppm for diesel. Fuel is one of the important sources of energy that is essential for human growth and development. Hence, desulfurization has become one of the worldwide concerns [1,2]. The sulfur contents in fuel are generally classified as disulfides, thiophenes, BT, DBT, mercaptans, etc., which convert sulfur in fuel into SO x after combustion [3]. In addition, it causes acid rain that contributes to the occurrence of London smog (sulfurous smog), which causes headaches and eye irritation; however, long-term exposure may ultimately cause death. Nowadays, in fuel refineries, the main challenge is the removal of sulfur content and its compounds because of strict legislation on environmental remediation [4]. Hydrodesulfurization was the traditional desulfurization technology, which requires hydrogen under high temperature and pressure to eliminate cyclic compounds, i.e., DBT, BT, etc. Therefore, an efficient desulfurization technology needs to be developed that will remove sulfur compounds from fuel to achieve environmental sustainability [5]. Technologies that have been proposed for fuel oil desulfurization, such as adsorptive desulfurization [6], extractive desulfurization [7], bio-desulfurization, and oxidative desulfurization (ODS) [8], are under development [9]. Among all, ODS is gaining colossal attention for the removal of sulfur due to its low cost, higher adaptability for the selectivity of aromatic compounds, high efficiency, and eco-friendly behavior. The scientific community is paying top-tier importance to ODS, as it is the best methodology to liberate sulfur-based ring substances from fluid. This technology requires an oxidative reaction to convert organo-sulfur compounds into sulfones and sulfoxides in the presence of oxidizing agents, such as H2O2, under the influence of a suitable catalyst. Then, oxidized compounds are separated by using polar solvents, such as acetonitrile (extractant), through a solvent extraction technique [10]. Over time, this method has evolved into a more beneficial and remarkably cost-effective process, as it now demands microscopic quantities of oxidants and elementary equipment or conditions.

In the past, oxidative catalysis was used in various fields such as water splitting, desulfurization of oil, and pollutant degradation, etc. [11]. Desulfurization assisted by ODS is an easily accessible process for the removal of aromatic sulfur compounds from fuel oil owing to mild operating conditions with no consumption of H2 [12]. ODS is a two-step process: oxidation followed by elimination of sulfones and sulfoxide through extraction using the extractant MeCN. Among the recently used catalysts for ODS, the newly emerging class of modern material POM@MOF-based composites [13], such as supported metal oxides, titanate nanotubes [14], and phase transfer materials, are used as the best choice of catalyst for deep oil desulfurization.

TBA-Si2W18Mn4@SAB with CH3COOH/H2O2 as an oxidizing agent was found to be an excellent catalyst for ODS, having 97% removal of sulfur content from gasoline following a first-order reaction. The oxidation reactivity of sulfur compounds is designated in decreasing order as DBT > BT > Th [15]. The nanocomposites for the efficient removal of DBT using Bi2WO6@rGo and CuWO4@rGo catalysts obtained 90% efficiency under optimal reaction conditions via ODS. The kinetics were a pseudo-first-order reaction with optimum energies of 16.91 and 14.57 kJ/mol [16]. (Gly)3PMo12O40@MnFe2O4 hybrid nanocomposites were used in the CAT-ODS reaction for the withdrawal of dangerous organo-sulfur contents from model fuel oil and gasoline. The removal efficiency was 95% under optimized conditions at a temperature of 35°C with a contact time of 1 h following the kinetics of a pseudo-first-order reaction model. The substrates such as DBT, BT, and Th were catalytically removed with efficiency yields of 98.3, 97.6, and 96.4%, respectively [17]. MOF-derived nanocomposites were used as an efficient catalyst for ODS and ODN.

PTA@H2N-MIL-101-Cr showed excellent efficiency for the removal of DBT from n-heptane in the presence of MeCN and H2O2 with high reaction rates. Among DBT, 4,6-DMBT, and BT, DBT shows the highest efficiency of 99.6%, followed by 88.2 and 70.5%, respectively [18]. CoW(20)/rGO hybrid nanocomposites were utilized as an efficient catalyst for impressive ODS performance for the model as well as real fuel in the manifestation of hydrogen peroxide [19]. Recent studies show that the rGO-based catalyst for the removal of sulfur compounds effectively contributes to cleaner energy production and a safer environment. Moreover, the importance of hybrid Ni/Fe3O4/rGO is its large surface area and electrical conductivity that facilitate the effective adsorption and activation of sulfur-containing compounds [20]. This catalyst showed excellent sulfur removal efficiency in model diesel fuel, surpassing traditional catalysts in terms of activity and durability. Another heterogeneous catalyst, FeW11V@CTAB-MMT, used for ODS of gasoline following pseudo-first-order kinetics, has the best removal efficiency of DBT, BT, and Th with more than 97% efficiency at 35°C after 1 h [21]. This catalyst is perfectly used to remove hazardous sulfur compounds from gasoline. Homogeneous and heterogeneous polyoxometalates are used as efficient catalysts for the ODS process of fuel by removing refractory sulfur compounds, e.g., DBT and BT, under mild reaction conditions but with high efficacy [22]. The heterogeneous catalyst Fe6W18O70 ⊂ CuFe2O4 exhibited an extraordinarily high efficiency with the removal of thiophene 98%, DBT 99%, and BT 99% when used in ultra-deep ODS of real gasoline and simulated fuel. The reaction occurs under optimized conditions of a temperature of 35°C with a contact time of 1 h and shows an oxidation reaction efficiency of 95% [23].

In recent years, carbon materials, particularly graphene oxide, have been utilized as catalyst support for ODS because of their special surface properties, unique interlayer structure, and extremely large surface area. Reduced graphene oxide (rGO) is a two-dimensional, crystalline allotrope possessing a six-membered ring, lattice structure made from pure carbon atom, sp2 hybridization, with unique electrical and thermal properties [24]. A high surface area results in more active sites for the catalytic reaction, allowing effective adsorption of sulfur-containing compounds. While rGO-based nanocomposites play a vital function in this process, immense research concerning the ODS of oil by hybrid materials needs to be paid attention to. Researchers have reported rGO-supported TM-modified catalysts, mesoporous silica, and MOF@POM hybrid materials for efficient and green ODS. 2D-GO not only possesses great thermal and electrical properties but also contains functional groups having oxygen that play an essential role in chemical modifications. These hybrid nanocomposites have found applications in diverse fields of interest, playing a decisive role in advancing modernization breakthroughs and facilitating innovation in the realms of energy and environment. As a result, their utilization spans various sectors within these environmental domains [24]. Moreover, owing to rGO, chemical stability is enhanced, ensures long-term stability of catalysts, and reduces operational cost.

The current work includes fabrication of Mo–WO3@rGO, Mn–WO4@rGO, and In–WO3@rGO nanocomposites (recoverable, TM-free) and their catalytic testing for the ODS process for oils. The characterization of the prepared materials is performed using scanning electron microscopy (SEM), XRD (powder X-ray diffractometer), energy dispersive X-ray spectroscopy (EDX), IR spectroscopy, and thermogravimetric analysis (TGA) study. Various parameters, including the concentration of sulfur content, time interval of absorption–desorption equilibrium, temperature, and catalyst concentration, were investigated to regulate the ODS process. Furthermore, the recovery of the catalyst, mechanism and testing of oil were inspected, and detailed insights into these aspects are provided in the subsequent analysis.

2 Materials and methods

2.1 Materials

KMnO4 99.9%, H2SO4 98%, graphite powder, H2O2 30% by weight, prepared catalysts (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO), hydrochloric acid (HCl, 37%), Na2WO4·2H2O 99%, and dibenzothiophene (DBT) were purchased from Sigma-Aldrich Co., and indium sulfate [In2(SO4)3], manganese acetate C4H14MnO8, and ammonium molybdate 4-hydrate[(NH4)3 Mo7O24·4H2O] were acquired from Merck.

2.2 Production of GO, exfoliated GO, and reduced GO

rGO was prepared following an earlier method with a few minor modifications [24]. An ice bath was used for half an hour to maintain the temperature <5°C while mixing continuously, and 4 g of powdered graphite was weighed and placed in a beaker with 100 mL of pure sulfuric acid. The main purpose of using an ice bath was to maintain temperature to avoid thermal degradation of the GO precursor material, as high temperature may lead to incomplete synthesis or degradation of the desired product. Thus, cooling the reaction media helps to obtain better control of reaction conditions. The mixture was constantly stirred after introducing 12 g of KMnO4 while keeping the temperature below 10°C in a cold pot. Later, it was diluted by the addition of 100 mL of deionized H2O with constant shaking. H2O2 (30 wt%) was added to the mixture to reduce the remaining KMnO4. Then, screening was completed, the deposit was separated by filtration, and it was rinsed with 5% aqueous solution of HCl and water till the pH remained 6 to further guarantee that ions were eradicated. Hydrogen peroxide played a vital role as an oxidizing agent, often used to oxidize graphene to GO by initiating oxygen-containing groups, i.e., hydroxyl groups, epoxide to the graphene sheet, and transforming sp2 carbon atoms to sp3 hybrid form. Dehydration of the GO product was carried out at 45°C for 1 day in a furnace.

Exfoliation of the product was performed by dissolution of 2 g of GO in 500 mL of deionized water with constant stirring for 6 h. As unexfoliated nanocomposite piped out during the reaction, the synthesized XGO was then dehydrated for a day at 45°C, and centrifugation and ultrasonication were performed to remove any unexfoliated GO. XGO (1 g) was introduced to 0.5 L of distilled water to synthesize rGO by heating and stirring at 90°C for 4 days. The prepared rGO at 120°C was dried in an oven.

2.3 Synthesis of In–WO3, Mn–WO4, and Mo–WO3, In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO

For the preparation of In–WO3, 1 g of Na2WO4 and 1 g of In2(SO4)3 were mixed in a 250 mL beaker containing 100 mL of deionized water. The mixture was stirred for 25–30 min. After agitation, sodium borohydride (NaBH4) was added to the beaker containing the previous mixture till the formation of bubbles stopped. Later, it was placed in a Teflon-assisted steam vessel/cylinder and kept in a furnace for 6 h at 155°C. The same procedure was adopted for Mn–WO4 and Mo–WO3 using manganese and molybdenum salts, i.e., manganese acetate and ammonium molybdate, respectively. A combination of TMs (indium, manganese, and molybdenum) supported on rGO was created by incorporating ∼20% TMs-WO3 onto ∼80% rGO. The fabrication was done using an autoclave at 150°C for 7–8 h. These parameters of time and temperature conditioning are very crucial as this temperature range allows the uniformity of composite structures and also increases the diffusion of the precursor. Moreover, all MOs required a specific range of optimal temperatures for the synthesis of the desired hybrid oxides. In addition, the duration of the autoclave gives the overall reaction time and extent of interaction between rGO sheets and TMs-WO3. These two factors depict the overall morphology, phase composition, and crystallinity of nanohybrids, and their adjustments control the synthesis mechanism. After filtration, the products (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO) were heated for 6 h at 300°C.

2.4 Characterization techniques

The prepared materials (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO) were subjected to characterization using multiple techniques, such as FT-IR spectroscopy using IR-TRACER-100, a wavelength of 4,000–400/cm with a scanning speed of 15/cm; powder X-ray diffraction of Cu-kα (0.154 nm or 1.54 Å) with a range of 5°–70° and a scanning speed of 2°/min; SEM for morphology was performed using NOVA NANO together with EDX and TGA under an inert atmosphere in the range of 400–800°C. Furthermore, the properties of fuel were assessed using PETRA-XRF, a total sulfur tester ASTM D-4294, an H2O content analyzer (China PT-D4006-8929A, volume %, ASTM D-4006), a hydrometer (density analyzer) at 15.6°C @gmol−1, ASTM D-1298), and a Distillation Tester (ASTM D-86, PAC, PMD 110).

2.5 ODS procedure

Catalytic testing was inspected using 1,000 ppm DBT in n-hexane and 40 mL of an extractant using 0.1 g of the catalyst (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO) under ideal conditions, and the conditions for the catalytic reaction were optimized to achieve the best possible performance. The mixture (model fuel, extractant, and catalyst) was poured into a cone-shaped flask and kept in the absence of light for 15 min to obtain as adsorption–desorption stability curve. Later on, 1 mL of 30 wt% oxidant H2O2 was added to the flask. The reaction converts sulfur compounds in model fuel to sulfones. Then, sulfoxides were liberated in a polar medium containing extractants; thus, other rested sulfur in the non-polar medium can be calculated using an ultraviolet-visible spectrometer with λ max = 285 nm (transition from n to π*). Moreover, a total sulfur analyzer (PETRA XRF) was utilized to measure the amount of rested sulfur in the liquid phase at various time spans. The effectiveness of model fuel elimination could be determined using the mathematical equation:

Desulfurization ( % ) = C i – C f / C i × 100 .

Here, C f is the final amount of DBT in model fuel, and C i is the original amount of DBT in the fuel determined by ultraviolet-visible spectroscopy.

3 Results and discussion

3.1 Characterization

3.1.1 FT-IR spectroscopy

FT-IR spectroscopy is majorly concerned with the vibration of molecules that correspond to specific vibrational energy levels. FT-IR studies were performed to investigate the vibrational band stretching of functional groups present in the prepared rGO and its hybrid materials, Mo–WO3@rGO, Mn–WO4@rGO, and In–WO3@rGO in the range between 4,000 and 400/cm, as shown in Figure 1. In rGO, the characteristic peaks were observed: 3,600–3,200/cm (–OH stretching), 3,050/cm (sp2 CH stretching), 2,915/cm (sp3 CH stretching), 1,730/cm (C═O stretching), 1,600–1,500/cm (C═C stretching of aromatic ring), 1,200–1,100/cm (C–O stretching), and 1,030/cm (C–C stretching), all these crests are the clear verification of the formation of rGO material successfully. All the peaks are similar in rGO-supported nanocomposites with just one extra peak owing to the M–O bond peak at 600–500/cm (M = W), which confirms the formation of composites fruitfully.

Figure 1 IR vibrational analysis of (a) rGO, (b) In-WO3@rGO, (c) Mn-WO4@rGO, and (d) Mo-WO3@rGO.
Figure 1

IR vibrational analysis of (a) rGO, (b) In-WO3@rGO, (c) Mn-WO4@rGO, and (d) Mo-WO3@rGO.

3.1.2 XRD

X-ray diffraction of Cu-kα (0.154 nm) with a span of 2θ = 5°–70° was used to verify the XRD spectrum of rGO and In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO to measure the average crystallite size, basal plane, and crystal system, as shown in Figure 2. There is just a single characteristic peak in the XRD spectra of rGO at 2θ = 26.3° having a basal plane of the (002) plane with a d-space of 0.34 nm, consistent with the JCPDS Card No. 75-2078. The (002) plane, ascribed to the lighter films of rGO due to greater extent of flaking as well as phase of rGO, is quite comparable to g–C3N4. It is confirmed that graphitic coatings may be diminished after loading with nanocomposites of In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO that leads to stacking in an irregular pattern when the intensity of the peak with a basal plane of (002) decreased. Graphene strips are separated into thinner layers with varying latticework, differentiating them from both GO and graphite flakes, as documented in earlier studies. The notable peaks in nanoparticles are as follows: In–WO3@rGO: 2θ = 20.1 (020), 31.5 (222), 63.47 (622); Mn–WO4@rGO: 2θ = 20.23 (100), 32.73 (111), 35.81 (002), 45.21 (211), 62.01 (113); and Mo–WO3@rGO: 2θ = 17.37 (110), 27.81 (300), 34.21 (310), 49.37 (002), 52.32 (211), in which (002), (222), and (020) are correlated with WO3 (JCPDS card no. 72-1465) [25]. As indicated by JCPDS card no. 72-1465, pure WO4 demonstrates the monoclinic crystal structure as outlined in the previous literature, and after successful loading of In and Mo into WO3 makes an orthorhombic geometry. In the XRD pattern of Mn–WO4@rGO, (100), (111), and (113) planes are due to the presence of Mn. Moreover, impurity related peaks have not been found in hybrid materials that depicted the loading of M onto the W latticework rather than the interstitial sites [19]. The average crystallite size was determined through the Debye–Scherrer equation (D = (kλ)/(β cos θ)), where Scherrer constant (k) is equal to 0.9, λ is the wavelength of Cu-kα (0.154 nm), β is the full width at half-maximum, and θ is the Bragg’s angle. The mean crystallite size of rGO, In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO are 18.78, 37.66, 23.41 and 21.26 nm, respectively. Notably, the intensity of the rGO peak is lowered in composites due to doping effect, structural changes, inference, and interaction with other materials in the composites. Composites have diffraction peaks that overlap with rGO peaks, making it hard to distinguish them separately.

Figure 2 XRD pattern of (a) rGO, (b) In-WO3@rGO, (c) Mn-WO4@rGO, and (d) Mo-WO3@rGO.
Figure 2

XRD pattern of (a) rGO, (b) In-WO3@rGO, (c) Mn-WO4@rGO, and (d) Mo-WO3@rGO.

3.1.3 SEM and EDX

SEM uses an intensive beam of energized electrons, instead of light, that investigates the morphology and chemical composition for imaging by scanning and normally for micrometer or nanometer particulates. The micrographs of rGO (Figure 3(a)) and rGO-supported novel nanocomposites of In–WO3@rGO (Figure 3(b) and (c)), Mn–WO4@rGO (Figure 3(d) and (e)), and Mo–WO3@rGO (Figure 3(f) and (g)) were collected using a NOVA NANO SEM. The results revealed that rGO is primarily composed of wrinkled, thin, overlapped sheets, and agglomerated solids were placed willy-nilly with precise and well-defined edges [26]. The indefinite rGO sheets exemplify a clear and apparent manifestation of GO flaking as the length between sheets reduced; however, in composites of rGO, due to doping phenomena, random particles were visible on the exterior of rGO [27]. At elevated magnification, an even dispersion on the exterior of rGO in the case of nanocomposites confirms that rGO granules are not single, but some of them are accumulated between overlapped and agglomerated rGO sheets [28,29]. The particles of In, Mn and Mo are decorated very well on the surface of the rGO sheets and showed interesting morphology, which increased its catalytic activity by increasing the surface area and change in morphology. Furthermore, EDX analysis was used to explore the component pattern in rGO-based materials with X-rays. The occupancy of In, Mn, Mo, and W together with carbon and oxygen atom vertex confirm that In–WO3, Mn–WO4, and Mo–WO3 are successfully doped onto rGO (Figure 3(h), (i) and (j)).

Figure 3 SEM micrographs of rGO (a), In-WO3@rGO (b) and (c), Mn-WO4@rGO (d) and (e), and Mo-WO3@rGO (f) and (g). EDX of In-WO3@rGO (h), Mn-WO4@rGO (i), and Mo-WO3@rGO (j).
Figure 3

SEM micrographs of rGO (a), In-WO3@rGO (b) and (c), Mn-WO4@rGO (d) and (e), and Mo-WO3@rGO (f) and (g). EDX of In-WO3@rGO (h), Mn-WO4@rGO (i), and Mo-WO3@rGO (j).

3.1.4 TGA

TGA was performed to observe the heat endurance and disintegration activity of the synthesized materials in the range of 40–800°C, with a scan rate of 5°C/min under inert (He) environments. As shown in Figure 4, at 100–150°C, due to the vaporization of water molecules or other impurities present in rGO, a slight mass loss of 20% was observed [30]. However, for composites (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO), only 9% weight loss was observed up to 200°C, which depicts the loss of remaining oxygen molecules and removal of water molecules that are connected with the surface of rGO. Next, in the range of 300–450°C, 49% mass loss is associated with the removal of carbonaceous material for composites (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO). After 550°C, no significant weight loss was observed for composites and unchangeable mass is reduced to 800°C. Moreover, up to 800°C, almost 80–85% decomposition of rGO took place, which confirmed that temperature had a remarkable effect on the thermal properties of the composites. Pure rGO has a greater weight loss compared to composites in the range of 500–700°C, which proves that nanocomposites are more efficient and reliable for catalytic activity. The hardness, modulus of elasticity, yield strength, and durability of alloy and metal increased as the temperature decreased. In addition, the composites (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO) show significant affinity and high thermal stability with rGO.

Figure 4 TGA weight loss curves of rGO, In-WO3@rGO, Mn-WO4@rGO, and Mo-WO3@rGO.
Figure 4

TGA weight loss curves of rGO, In-WO3@rGO, Mn-WO4@rGO, and Mo-WO3@rGO.

All characterization techniques complement each other by giving in-depth information about the structure of the material, properties, composition, and nature of the composite. IR spectroscopy gives an in-depth understanding of the functional group identification that helps us to correlate the crystallinity determined by XRD. SEM informs about the shape, particle size, and surface topography, while EDX confirms the composition of specific regions identified in SEM images. Overall, all these allow researchers to know about materials’ potential, synthesis, optimization, quality control, and applications.

3.2 Optimization

Experiments at different temperatures and times were conducted to determine the effect of temperature (25, 45, 60, and 90°C) and time (30, 60, 90, 120, and 180 min), where other parameters were kept constant such as the catalyst, DBT concentration, and amount of H2O2. Illustrating from the graph (temperature versus efficacy), it is unambiguous that temperature had an inverse effect on the activity of the catalyst, which means an increase in temperature decreases the catalytic activity [31]. However, in the case of the time vs efficiency plot, time is directly related to the activity of the stimulant [32]. This is evident that with an increase in temperature, the activity of the catalyst and reaction rate decrease due to the decomposition of the oxidant, as shown in Figure 5(a) and (b). Hence, optimized parameters of time of 2 h and temperature of 45°C were used for subsequent study.

Figure 5 Impact of time (a), temperature (b), DBT dose (c), catalyst amount (d) and oxidant amount (e) on desulfurization of DBT.
Figure 5

Impact of time (a), temperature (b), DBT dose (c), catalyst amount (d) and oxidant amount (e) on desulfurization of DBT.

Regarding the effect of DBT amount, as shown in Figure 5(c) (50, 100, 200, and 500 mg/L), it is clear that it has an indirect effect with efficiency as a constant catalyst dose is insufficient to provide catalytic sites to oxidize 500 mg/L in 2 h. Hence, a prolonged duration is recommended to oxidize sulfur containing compounds thoroughly at high concentrations. It was investigated that if lower the dose of DBT molecules, the more effective the desulfurization under optimized conditions. As the catalyst amount has foremost effect on catalytic effectiveness, as shown in Figure 5(d), it is clearly investigated that the stimulant dose effects on efficacy (0.05–0.2 g of In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO) has positive effect on the catalytic activity while keeping other parameters constant, i.e., the time interval, temperature, DBT extent, and quantity of oxidant. The efficiency of materials (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO) enhanced to 99.8% when the catalyst amount increased from 0.05 to 0.2 g. A greater amount of DBT remained unoxidized due to a small dose of catalyst, as there were few catalytic sites available to perform the reaction [33]. Moreover, further increase in the catalyst dosage decreased the catalyst efficiency due to catalyst agglomeration, which blocked the active sites. It is clear from the figure that greater efficiency was achieved by Mo–WO3@rGO compared to the other TMs-WO3 hybrids (Mn–WO4@rGO and In–WO3@rGO), and the highest DBT conversion through Mo–WO3@rGO because of changes in auxiliary/secondary metal performance from regulator to opponent and excellent metal-supported interactions. Moreover, TM molybdenum (Mo)-based hybrid material have low adsorption energy, which results ultimately in lower Ea compared to manganese (Mn) and indium (In). Hydrogen peroxide, which is an oxidant, has a main role in the desulfurization of DBT as it was used as an initiator in reaction media. By maintaining other parameters steady (0.1 g catalyst, 100 mg/L DBT model fuel, 45°C, and time 120 min), the amount of oxidant was changed (0.5, 1.0, 2.0, and 3.0 mL) to determine the effect of the oxidant on the efficacy, as depicted in Figure 5(e). Concluding the optimized conditions, a greater quantity of catalyst will lower the DBT content (1 mL of oxidant at approximately 40–45°C), as high concentrations of catalyst may raise the probability of maximum oxidation of sulfur content in the fuel. The study clearly investigated that the H2O2 oxidant has a positive impact on efficiency as it expedites by increasing the amount of initiator/oxidant. Further, no effect was observed when the amount exceeds 2 mL. In this reaction medium, H2O2 acts as an initiator, which confirms its positive behavior by depicting that with the increase in the promoter amount, the efficiency of the catalyst also increases. In the ODS process, hydrogen peroxide as an oxidizing agent has the potential to selectively oxidize sulfur and sulfur-containing compounds (lower oxidation state) under ambient conditions of pressure and temperature and convert them into polar compounds of sulfones and sulfoxides (higher oxidation states).

3.3 Kinetics, thermodynamics, and the ODS mechanism

Kinetic studies provided strong evidence in support of speed and oxidative processes, as they follow the pseudo-first-order kinetic model. From this, the value of the constant is measured, which helps in the estimation of the kinetics of the oxidation reaction [34]. A plot of C F/C I versus time (min) at various temperatures is demonstrated only for Mo–WO3@rGO, as it showed the highest efficiency compared to In–WO3@rGO and Mn–WO4@rGO (Figure S1) and the coherence coefficient (R 2) was ∼1, where C I is the initial concentration and C F is the final concentration of the DBT solution, indicating that the ODS reaction followed pseudo-first-order kinetics at temperatures of 30, 35, 40 and 45°C. Moreover, the optimum energy in the ODS process of DBT can be estimated via the Arrhenius plot by drafting coordinates ln K vs 1/T. The values are calculated using the Arrhenius equation and it was 6.540 kJ/mol for Mo–WO3@rGO. The Arrhenius equation is given as

K = A e − Ea / R T .

To understand the effect of temperature on DBT oxidation, a curve was plotted between ln K c and 1/RT to calculate the standard Gibbs free energy (ΔG), enthalpy of activation (ΔH°), and entropy of activation (ΔS) via the Eyring equation [35]

ln K c = − Δ H R T + Δ S R .

In this equation, T denotes absolute temperature, K and K c denotes equilibrium constant where ΔG (the standard Gibbs free energy) can be evaluated using [36,37]

Δ G = − R T ln K c .

From the plot ln K c vs 1/RT, the given outcomes show positive values of ΔS and ΔH depicting an endothermic process and haphazardness in the reaction medium, respectively, as listed in Table 1. However, negative values of the standard Gibbs free energy indicate that DBT removal via In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO is a stable and thermodynamically useful ODS process.

Table 1

Thermodynamic factors affecting the removal of sulfur content (DBT) through oxidative desulfurization

Novel catalyst ΔG (kJ/mol) ΔH (kJ/mol) ΔS (kJ/mol K)
298.5 K 303.5 K 308.5 K 313.5 K
Mo–WO3@rGO −0.506 −2.551 −5.193 −14.016 260.27 0.854

3.4 ODS of real fuel oils

Catalytic testing of synthesized nano-composites (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO) was carried out for fuel samples available in the market using 0.2 g catalyst, 3 mL of H2O2, 50 mL of fuel sample, and time span of 180 min at 45°C. To determine the sulfur content, pre- and post-ODS processes were completed via PETRA XRF. Moreover, other fuel properties such as distillation (ASTM D-86), moisture content (ASTM D-4006), and relative gravity (ASTM D-1298) were also investigated before and after ODS and provided in Table 2. A slight difference was noted before and after ODS in fuel properties, which is a clear confirmation that the catalytic system does not impact the characteristics of oil except specific elimination of sulfur species [38,39]. From the ODS of oil (In–WO3@rGO, Mn–WO4@rGO, and Mo–WO3@rGO), results declared that Mo–WO3@rGO is slightly more efficient than In–WO3@rGO and Mn–WO4@rGO for both real and model fuel. Besides this, all nanocomposites proved optimistic and robust for the effective removal of DBT.

Table 2

ODS of real oil via In–WO3@rGO, Mn–WO4@rGO and Mo–WO3@rGO

Specific gravity (g/mL at 15.6°C) Total sulfur by petra X-ray (ppm) Water content (vol%) Distillation (°C)
Fuel and catalysts 50% 90%
Kerosene Before ODS 0.831 1,525 Nil 241 304
After ODS In–WO3@rGO 0.830 135 Nil 236 302
Mn–WO4@rGO 0.828 144 Nil 238 299
Mo–WO3@rGO 0.827 152 Nil 238 298
Diesel Before ODS 0.885 4,596 Nil 286 345
After ODS In–WO3@rGO 0.882 425 Nil 279 337
Mn–WO4@rGO 0.879 433 Nil 279 342
Mo–WO3@rGO 0.877 449 Nil 280 338

3.5 Reusability of catalyst

Catalysts speed up the reaction mechanism, depriving of a structural or compositional modification, i.e., help to cause a reaction at a faster rate by reducing the activation energy of the chemical reaction. The reusability of the catalyst plays an important role due to its practical uses as it assesses the financial viability of the newly created catalyst scheme. To test restoration and recovery of catalysts (Mo–WO3@rGO, Mn–WO4@rGO, and In–WO3@rGO) via simple filtration technique, first, it is detached from the reaction medium, rinsed with n-hexane/dichloromethane (any non-polar solvents), dried, and reused. After the evaluation test of reusability was performed, results indicated no significant alteration in the efficacy of the catalyst for the conversion rate of DBT even after five times. A slight loss in efficiency was noted after five cycles, and this occurred due to a decrease in catalytic sites and mass damage of the catalyst during the purification process. The catalysts (Mo–WO3@rGO, Mn–WO4@rGO, and In–WO3@rGO) showed excellent stability and maintained its potency up to five catalytic rounds. Previously reported studies for ODS using rGO-based catalysts are provided in Table 3. The reported literature confirmed that there is no report on rGO as supported TMs (Mo, Mn, and In) doped tungstate. This study consisting of newly synthesized hybrids of Mo–WO3@rGO, Mn–WO4@rGO, and In–WO3@rGO have been certified for the first time for the oxidative process for the extraction of DBT. Moreover, there are sufficient reported data on rGO-assisted transition metal-based catalysts.

Table 3

Comparison with other reported studies

Material Oxidant Sulfur specie DBT concentration (ppm) Efficiency (%) References
Bi2WO6@rGO H2O2 DBT 100 97 [16]
CuWO4@rGO DBT 100 99
NiWO3@g–C3N4 H2O2 DBT 100 97 [2]
Kerosene 1,635 91.5
Diesel 4,630 89.5
WO3/g–C3N4 H2O2 DBT 500 91.2 [40]
NiW/rGO H2O2 DBT 500 >90 [19]
CoW/rGO H2O2 DBT 500 ∼100
CoMo/rGO H2O2 DBT 500 99 [41]
g–C3N4 TBHP DBT 500 >10 [42]
MoO2/g–C3N4 TBHP DBT 500 ∼100
Mo–WO3@rGO H2O2 DBT 500 99.8 Current study
Mn–WO4@rGO H2O2 DBT 500 99.5 Current study
In–WO3@rGO H2O2 DBT 500 99 Current study

4 Conclusion

The fruitful hydrothermal treatment of rGO-supported nanohybrids was carried out for the first time for ODS of real as well as model fuel. Out of these three hybrids, remarkable desulfurization efficiency of model fuel was accompanied by Mo–WO3@rGO 98.5% using H2O2 as an oxidant. XRD results revealed an average crystallite size of less than 40 nm, and morphology observed through SEM indicated that hybrids are well embellished on the exterior of rGO. The activity for real fuel oil was scrutinized by using these three catalyst and removal efficiencies were 90.23 and 90.03% for diesel and kerosene oil for In–WO3@rGO; for Mo–WO3@rGO, 90.7 and 91.15%; for Mn–WO4@rGO, 90.57 and 90.55%, respectively, under optimum conditions. Multiple parameters such as time, catalyst amount, oxidant amount, and concentration were determined and found that all had a direct relationship with efficiency, except the DBT concentration that followed a pseudo-first order with a negative value of ΔG, depicting thermodynamic stability at 298.5, 303.5, 308.5, and 313.5 K. In addition, five times reusability of the catalyst confirmed its stability, with little reduction in effectiveness for the ODS process. Therefore, complete novel innovation depicts the eminence of the synthesized nanomaterials for the green generation of sulfur-free fluid.

Acknowledgments

The authors are grateful to the University of the Punjab for assistance.

  1. Funding information: The authors state no funding involved.

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

  4. Data availability statement: Data sharing is not applicable to this article as no datasets were generated or analyzed during the current study.

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Received: 2023-12-05
Revised: 2024-05-22
Accepted: 2024-10-17
Published Online: 2024-12-16

© 2024 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  100. A review of ternary polymer nanocomposites containing clay and calcium carbonate and their biomedical applications
  101. Recent advancements in polyoxometalate-functionalized fiber materials: A review
  102. Special contribution of atomic force microscopy in cell death research
  103. A comprehensive review of oral chitosan drug delivery systems: Applications for oral insulin delivery
  104. Cellular senescence and nanoparticle-based therapies: Current developments and perspectives
  105. Cyclodextrins-block copolymer drug delivery systems: From design and development to preclinical studies
  106. Micelle-based nanoparticles with stimuli-responsive properties for drug delivery
  107. Critical assessment of the thermal stability and degradation of chemically functionalized nanocellulose-based polymer nanocomposites
  108. Research progress in preparation technology of micro and nano titanium alloy powder
  109. Nanoformulations for lysozyme-based additives in animal feed: An alternative to fight antibiotic resistance spread
  110. Incorporation of organic photochromic molecules in mesoporous silica materials: Synthesis and applications
  111. A review on modeling of graphene and associated nanostructures reinforced concrete
  112. A review on strengthening mechanisms of carbon quantum dots-reinforced Cu-matrix nanocomposites
  113. Review on nanocellulose composites and CNFs assembled microfiber toward automotive applications
  114. Nanomaterial coating for layered lithium rich transition metal oxide cathode for lithium-ion battery
  115. Application of AgNPs in biomedicine: An overview and current trends
  116. Nanobiotechnology and microbial influence on cold adaptation in plants
  117. Hepatotoxicity of nanomaterials: From mechanism to therapeutic strategy
  118. Applications of micro-nanobubble and its influence on concrete properties: An in-depth review
  119. A comprehensive systematic literature review of ML in nanotechnology for sustainable development
  120. Exploiting the nanotechnological approaches for traditional Chinese medicine in childhood rhinitis: A review of future perspectives
  121. Twisto-photonics in two-dimensional materials: A comprehensive review
  122. Current advances of anticancer drugs based on solubilization technology
  123. Recent process of using nanoparticles in the T cell-based immunometabolic therapy
  124. Future prospects of gold nanoclusters in hydrogen storage systems and sustainable environmental treatment applications
  125. Preparation, types, and applications of one- and two-dimensional nanochannels and their transport properties for water and ions
  126. Microstructural, mechanical, and corrosion characteristics of Mg–Gd–x systems: A review of recent advancements
  127. Functionalized nanostructures and targeted delivery systems with a focus on plant-derived natural agents for COVID-19 therapy: A review and outlook
  128. Mapping evolution and trends of cell membrane-coated nanoparticles: A bibliometric analysis and scoping review
  129. Nanoparticles and their application in the diagnosis of hepatocellular carcinoma
  130. In situ growth of carbon nanotubes on fly ash substrates
  131. Structural performance of boards through nanoparticle reinforcement: An advance review
  132. Reinforcing mechanisms review of the graphene oxide on cement composites
  133. Seed regeneration aided by nanomaterials in a climate change scenario: A comprehensive review
  134. Surface-engineered quantum dot nanocomposites for neurodegenerative disorder remediation and avenue for neuroimaging
  135. Graphitic carbon nitride hybrid thin films for energy conversion: A mini-review on defect activation with different materials
  136. Nanoparticles and the treatment of hepatocellular carcinoma
  137. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part II
  138. Highly safe lithium vanadium oxide anode for fast-charging dendrite-free lithium-ion batteries
  139. Recent progress in nanomaterials of battery energy storage: A patent landscape analysis, technology updates, and future prospects
  140. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part II
  141. Calcium-, magnesium-, and yttrium-doped lithium nickel phosphate nanomaterials as high-performance catalysts for electrochemical water oxidation reaction
  142. Low alkaline vegetation concrete with silica fume and nano-fly ash composites to improve the planting properties and soil ecology
  143. Mesoporous silica-grafted deep eutectic solvent-based mixed matrix membranes for wastewater treatment: Synthesis and emerging pollutant removal performance
  144. Electrochemically prepared ultrathin two-dimensional graphitic nanosheets as cathodes for advanced Zn-based energy storage devices
  145. Enhanced catalytic degradation of amoxicillin by phyto-mediated synthesised ZnO NPs and ZnO-rGO hybrid nanocomposite: Assessment of antioxidant activity, adsorption, and thermodynamic analysis
  146. Incorporating GO in PI matrix to advance nanocomposite coating: An enhancing strategy to prevent corrosion
  147. Synthesis, characterization, thermal stability, and application of microporous hyper cross-linked polyphosphazenes with naphthylamine group for CO2 uptake
  148. Engineering in ceramic albite morphology by the addition of additives: Carbon nanotubes and graphene oxide for energy applications
  149. Nanoscale synergy: Optimizing energy storage with SnO2 quantum dots on ZnO hexagonal prisms for advanced supercapacitors
  150. Aging assessment of silicone rubber materials under corona discharge accompanied by humidity and UV radiation
  151. Tuning structural and electrical properties of Co-precipitated and Cu-incorporated nickel ferrite for energy applications
  152. Sodium alginate-supported AgSr nanoparticles for catalytic degradation of malachite green and methyl orange in aqueous medium
  153. An environmentally greener and reusability approach for bioenergy production using Mallotus philippensis (Kamala) seed oil feedstock via phytonanotechnology
  154. Micro-/nano-alumina trihydrate and -magnesium hydroxide fillers in RTV-SR composites under electrical and environmental stresses
  155. Mechanism exploration of ion-implanted epoxy on surface trap distribution: An approach to augment the vacuum flashover voltages
  156. Nanoscale engineering of semiconductor photocatalysts boosting charge separation for solar-driven H2 production: Recent advances and future perspective
  157. Excellent catalytic performance over reduced graphene-boosted novel nanoparticles for oxidative desulfurization of fuel oil
  158. Special Issue on Advances in Nanotechnology for Agriculture
  159. Deciphering the synergistic potential of mycogenic zinc oxide nanoparticles and bio-slurry formulation on phenology and physiology of Vigna radiata
  160. Nanomaterials: Cross-disciplinary applications in ornamental plants
  161. Special Issue on Catechol Based Nano and Microstructures
  162. Polydopamine films: Versatile but interface-dependent coatings
  163. In vitro anticancer activity of melanin-like nanoparticles for multimodal therapy of glioblastoma
  164. Poly-3,4-dihydroxybenzylidenhydrazine, a different analogue of polydopamine
  165. Chirality and self-assembly of structures derived from optically active 1,2-diaminocyclohexane and catecholamines
  166. Advancing resource sustainability with green photothermal materials: Insights from organic waste-derived and bioderived sources
  167. Bioinspired neuromelanin-like Pt(iv) polymeric nanoparticles for cancer treatment
  168. Special Issue on Implementing Nanotechnology for Smart Healthcare System
  169. Intelligent explainable optical sensing on Internet of nanorobots for disease detection
  170. Special Issue on Green Mono, Bi and Tri Metallic Nanoparticles for Biological and Environmental Applications
  171. Tracking success of interaction of green-synthesized Carbopol nanoemulgel (neomycin-decorated Ag/ZnO nanocomposite) with wound-based MDR bacteria
  172. Green synthesis of copper oxide nanoparticles using genus Inula and evaluation of biological therapeutics and environmental applications
  173. Biogenic fabrication and multifunctional therapeutic applications of silver nanoparticles synthesized from rose petal extract
  174. Metal oxides on the frontlines: Antimicrobial activity in plant-derived biometallic nanoparticles
  175. Controlling pore size during the synthesis of hydroxyapatite nanoparticles using CTAB by the sol–gel hydrothermal method and their biological activities
  176. Special Issue on State-of-Art Advanced Nanotechnology for Healthcare
  177. Applications of nanomedicine-integrated phototherapeutic agents in cancer theranostics: A comprehensive review of the current state of research
  178. Smart bionanomaterials for treatment and diagnosis of inflammatory bowel disease
  179. Beyond conventional therapy: Synthesis of multifunctional nanoparticles for rheumatoid arthritis therapy
https://doi.org/10.1515/ntrev-2024-0116
Schlagwörter für diesen Artikel
hybrid materials; oxidative desulfurization; model fuel; dibenzothiophene; real fuel
Creative Commons
BY 4.0

Artikel in diesem Heft

  1. Research Articles
  2. Tension buckling and postbuckling of nanocomposite laminated plates with in-plane negative Poisson’s ratio
  3. Polyvinylpyrrolidone-stabilised gold nanoparticle coatings inhibit blood protein adsorption
  4. Energy and mass transmission through hybrid nanofluid flow passing over a spinning sphere with magnetic effect and heat source/sink
  5. Surface treatment with nano-silica and magnesium potassium phosphate cement co-action for enhancing recycled aggregate concrete
  6. Numerical investigation of thermal radiation with entropy generation effects in hybrid nanofluid flow over a shrinking/stretching sheet
  7. Enhancing the performance of thermal energy storage by adding nano-particles with paraffin phase change materials
  8. Using nano-CaCO3 and ceramic tile waste to design low-carbon ultra high performance concrete
  9. Numerical analysis of thermophoretic particle deposition in a magneto-Marangoni convective dusty tangent hyperbolic nanofluid flow – Thermal and magnetic features
  10. Dual numerical solutions of Casson SA–hybrid nanofluid toward a stagnation point flow over stretching/shrinking cylinder
  11. Single flake homo p–n diode of MoTe2 enabled by oxygen plasma doping
  12. Electrostatic self-assembly effect of Fe3O4 nanoparticles on performance of carbon nanotubes in cement-based materials
  13. Multi-scale alignment to buried atom-scale devices using Kelvin probe force microscopy
  14. Antibacterial, mechanical, and dielectric properties of hydroxyapatite cordierite/zirconia porous nanocomposites for use in bone tissue engineering applications
  15. Time-dependent Darcy–Forchheimer flow of Casson hybrid nanofluid comprising the CNTs through a Riga plate with nonlinear thermal radiation and viscous dissipation
  16. Durability prediction of geopolymer mortar reinforced with nanoparticles and PVA fiber using particle swarm optimized BP neural network
  17. Utilization of zein nano-based system for promoting antibiofilm and anti-virulence activities of curcumin against Pseudomonas aeruginosa
  18. Antibacterial effect of novel dental resin composites containing rod-like zinc oxide
  19. An extended model to assess Jeffery–Hamel blood flow through arteries with iron-oxide (Fe2O3) nanoparticles and melting effects: Entropy optimization analysis
  20. Comparative study of copper nanoparticles over radially stretching sheet with water and silicone oil
  21. Cementitious composites modified by nanocarbon fillers with cooperation effect possessing excellent self-sensing properties
  22. Confinement size effect on dielectric properties, antimicrobial activity, and recycling of TiO2 quantum dots via photodegradation processes of Congo red dye and real industrial textile wastewater
  23. Biogenic silver nanoparticles of Moringa oleifera leaf extract: Characterization and photocatalytic application
  24. Novel integrated structure and function of Mg–Gd neutron shielding materials
  25. Impact of multiple slips on thermally radiative peristaltic transport of Sisko nanofluid with double diffusion convection, viscous dissipation, and induced magnetic field
  26. Magnetized water-based hybrid nanofluid flow over an exponentially stretching sheet with thermal convective and mass flux conditions: HAM solution
  27. A numerical investigation of the two-dimensional magnetohydrodynamic water-based hybrid nanofluid flow composed of Fe3O4 and Au nanoparticles over a heated surface
  28. Development and modeling of an ultra-robust TPU-MWCNT foam with high flexibility and compressibility
  29. Effects of nanofillers on the physical, mechanical, and tribological behavior of carbon/kenaf fiber–reinforced phenolic composites
  30. Polymer nanocomposite for protecting photovoltaic cells from solar ultraviolet in space
  31. Study on the mechanical properties and microstructure of recycled concrete reinforced with basalt fibers and nano-silica in early low-temperature environments
  32. Synergistic effect of carbon nanotubes and polyvinyl alcohol on the mechanical performance and microstructure of cement mortar
  33. CFD analysis of paraffin-based hybrid (Co–Au) and trihybrid (Co–Au–ZrO2) nanofluid flow through a porous medium
  34. Forced convective tangent hyperbolic nanofluid flow subject to heat source/sink and Lorentz force over a permeable wedge: Numerical exploration
  35. Physiochemical and electrical activities of nano copper oxides synthesised via hydrothermal method utilising natural reduction agents for solar cell application
  36. A homotopic analysis of the blood-based bioconvection Carreau–Yasuda hybrid nanofluid flow over a stretching sheet with convective conditions
  37. In situ synthesis of reduced graphene oxide/SnIn4S8 nanocomposites with enhanced photocatalytic performance for pollutant degradation
  38. A coarse-grained Poisson–Nernst–Planck model for polyelectrolyte-modified nanofluidic diodes
  39. A numerical investigation of the magnetized water-based hybrid nanofluid flow over an extending sheet with a convective condition: Active and passive controls of nanoparticles
  40. The LyP-1 cyclic peptide modified mesoporous polydopamine nanospheres for targeted delivery of triptolide regulate the macrophage repolarization in atherosclerosis
  41. Synergistic effect of hydroxyapatite-magnetite nanocomposites in magnetic hyperthermia for bone cancer treatment
  42. The significance of quadratic thermal radiative scrutinization of a nanofluid flow across a microchannel with thermophoretic particle deposition effects
  43. Ferromagnetic effect on Casson nanofluid flow and transport phenomena across a bi-directional Riga sensor device: Darcy–Forchheimer model
  44. Performance of carbon nanomaterials incorporated with concrete exposed to high temperature
  45. Multicriteria-based optimization of roller compacted concrete pavement containing crumb rubber and nano-silica
  46. Revisiting hydrotalcite synthesis: Efficient combined mechanochemical/coprecipitation synthesis to design advanced tunable basic catalysts
  47. Exploration of irreversibility process and thermal energy of a tetra hybrid radiative binary nanofluid focusing on solar implementations
  48. Effect of graphene oxide on the properties of ternary limestone clay cement paste
  49. Improved mechanical properties of graphene-modified basalt fibre–epoxy composites
  50. Sodium titanate nanostructured modified by green synthesis of iron oxide for highly efficient photodegradation of dye contaminants
  51. Green synthesis of Vitis vinifera extract-appended magnesium oxide NPs for biomedical applications
  52. Differential study on the thermal–physical properties of metal and its oxide nanoparticle-formed nanofluids: Molecular dynamics simulation investigation of argon-based nanofluids
  53. Heat convection and irreversibility of magneto-micropolar hybrid nanofluids within a porous hexagonal-shaped enclosure having heated obstacle
  54. Numerical simulation and optimization of biological nanocomposite system for enhanced oil recovery
  55. Laser ablation and chemical vapor deposition to prepare a nanostructured PPy layer on the Ti surface
  56. Cilostazol niosomes-loaded transdermal gels: An in vitro and in vivo anti-aggregant and skin permeation activity investigations towards preparing an efficient nanoscale formulation
  57. Linear and nonlinear optical studies on successfully mixed vanadium oxide and zinc oxide nanoparticles synthesized by sol–gel technique
  58. Analytical investigation of convective phenomena with nonlinearity characteristics in nanostratified liquid film above an inclined extended sheet
  59. Optimization method for low-velocity impact identification in nanocomposite using genetic algorithm
  60. Analyzing the 3D-MHD flow of a sodium alginate-based nanofluid flow containing alumina nanoparticles over a bi-directional extending sheet using variable porous medium and slip conditions
  61. A comprehensive study of laser irradiated hydrothermally synthesized 2D layered heterostructure V2O5(1−x)MoS2(x) (X = 1–5%) nanocomposites for photocatalytic application
  62. Computational analysis of water-based silver, copper, and alumina hybrid nanoparticles over a stretchable sheet embedded in a porous medium with thermophoretic particle deposition effects
  63. A deep dive into AI integration and advanced nanobiosensor technologies for enhanced bacterial infection monitoring
  64. Effects of normal strain on pyramidal I and II 〈c + a〉 screw dislocation mobility and structure in single-crystal magnesium
  65. Computational study of cross-flow in entropy-optimized nanofluids
  66. Significance of nanoparticle aggregation for thermal transport over magnetized sensor surface
  67. A green and facile synthesis route of nanosize cupric oxide at room temperature
  68. Effect of annealing time on bending performance and microstructure of C19400 alloy strip
  69. Chitosan-based Mupirocin and Alkanna tinctoria extract nanoparticles for the management of burn wound: In vitro and in vivo characterization
  70. Electrospinning of MNZ/PLGA/SF nanofibers for periodontitis
  71. Photocatalytic degradation of methylene blue by Nd-doped titanium dioxide thin films
  72. Shell-core-structured electrospinning film with sequential anti-inflammatory and pro-neurogenic effects for peripheral nerve repairment
  73. Flow and heat transfer insights into a chemically reactive micropolar Williamson ternary hybrid nanofluid with cross-diffusion theory
  74. One-pot fabrication of open-spherical shapes based on the decoration of copper sulfide/poly-O-amino benzenethiol on copper oxide as a promising photocathode for hydrogen generation from the natural source of Red Sea water
  75. A penta-hybrid approach for modeling the nanofluid flow in a spatially dependent magnetic field
  76. Advancing sustainable agriculture: Metal-doped urea–hydroxyapatite hybrid nanofertilizer for agro-industry
  77. Utilizing Ziziphus spina-christi for eco-friendly synthesis of silver nanoparticles: Antimicrobial activity and promising application in wound healing
  78. Plant-mediated synthesis, characterization, and evaluation of a copper oxide/silicon dioxide nanocomposite by an antimicrobial study
  79. Effects of PVA fibers and nano-SiO2 on rheological properties of geopolymer mortar
  80. Investigating silver and alumina nanoparticles’ impact on fluid behavior over porous stretching surface
  81. Potential pharmaceutical applications and molecular docking study for green fabricated ZnO nanoparticles mediated Raphanus sativus: In vitro and in vivo study
  82. Effect of temperature and nanoparticle size on the interfacial layer thickness of TiO2–water nanofluids using molecular dynamics
  83. Characteristics of induced magnetic field on the time-dependent MHD nanofluid flow through parallel plates
  84. Flexural and vibration behaviours of novel covered CFRP composite joints with an MWCNT-modified adhesive
  85. Experimental research on mechanically and thermally activation of nano-kaolin to improve the properties of ultra-high-performance fiber-reinforced concrete
  86. Analysis of variable fluid properties for three-dimensional flow of ternary hybrid nanofluid on a stretching sheet with MHD effects
  87. Biodegradability of corn starch films containing nanocellulose fiber and thymol
  88. Toxicity assessment of copper oxide nanoparticles: In vivo study
  89. Some measures to enhance the energy output performances of triboelectric nanogenerators
  90. Reinforcement of graphene nanoplatelets on water uptake and thermomechanical behaviour of epoxy adhesive subjected to water ageing conditions
  91. Optimization of preparation parameters and testing verification of carbon nanotube suspensions used in concrete
  92. Max-phase Ti3SiC2 and diverse nanoparticle reinforcements for enhancement of the mechanical, dynamic, and microstructural properties of AA5083 aluminum alloy via FSP
  93. Advancing drug delivery: Neural network perspectives on nanoparticle-mediated treatments for cancerous tissues
  94. PEG-PLGA core–shell nanoparticles for the controlled delivery of picoplatin–hydroxypropyl β-cyclodextrin inclusion complex in triple-negative breast cancer: In vitro and in vivo study
  95. Conduction transportation from graphene to an insulative polymer medium: A novel approach for the conductivity of nanocomposites
  96. Review Articles
  97. Developments of terahertz metasurface biosensors: A literature review
  98. Overview of amorphous carbon memristor device, modeling, and applications for neuromorphic computing
  99. Advances in the synthesis of gold nanoclusters (AuNCs) of proteins extracted from nature
  100. A review of ternary polymer nanocomposites containing clay and calcium carbonate and their biomedical applications
  101. Recent advancements in polyoxometalate-functionalized fiber materials: A review
  102. Special contribution of atomic force microscopy in cell death research
  103. A comprehensive review of oral chitosan drug delivery systems: Applications for oral insulin delivery
  104. Cellular senescence and nanoparticle-based therapies: Current developments and perspectives
  105. Cyclodextrins-block copolymer drug delivery systems: From design and development to preclinical studies
  106. Micelle-based nanoparticles with stimuli-responsive properties for drug delivery
  107. Critical assessment of the thermal stability and degradation of chemically functionalized nanocellulose-based polymer nanocomposites
  108. Research progress in preparation technology of micro and nano titanium alloy powder
  109. Nanoformulations for lysozyme-based additives in animal feed: An alternative to fight antibiotic resistance spread
  110. Incorporation of organic photochromic molecules in mesoporous silica materials: Synthesis and applications
  111. A review on modeling of graphene and associated nanostructures reinforced concrete
  112. A review on strengthening mechanisms of carbon quantum dots-reinforced Cu-matrix nanocomposites
  113. Review on nanocellulose composites and CNFs assembled microfiber toward automotive applications
  114. Nanomaterial coating for layered lithium rich transition metal oxide cathode for lithium-ion battery
  115. Application of AgNPs in biomedicine: An overview and current trends
  116. Nanobiotechnology and microbial influence on cold adaptation in plants
  117. Hepatotoxicity of nanomaterials: From mechanism to therapeutic strategy
  118. Applications of micro-nanobubble and its influence on concrete properties: An in-depth review
  119. A comprehensive systematic literature review of ML in nanotechnology for sustainable development
  120. Exploiting the nanotechnological approaches for traditional Chinese medicine in childhood rhinitis: A review of future perspectives
  121. Twisto-photonics in two-dimensional materials: A comprehensive review
  122. Current advances of anticancer drugs based on solubilization technology
  123. Recent process of using nanoparticles in the T cell-based immunometabolic therapy
  124. Future prospects of gold nanoclusters in hydrogen storage systems and sustainable environmental treatment applications
  125. Preparation, types, and applications of one- and two-dimensional nanochannels and their transport properties for water and ions
  126. Microstructural, mechanical, and corrosion characteristics of Mg–Gd–x systems: A review of recent advancements
  127. Functionalized nanostructures and targeted delivery systems with a focus on plant-derived natural agents for COVID-19 therapy: A review and outlook
  128. Mapping evolution and trends of cell membrane-coated nanoparticles: A bibliometric analysis and scoping review
  129. Nanoparticles and their application in the diagnosis of hepatocellular carcinoma
  130. In situ growth of carbon nanotubes on fly ash substrates
  131. Structural performance of boards through nanoparticle reinforcement: An advance review
  132. Reinforcing mechanisms review of the graphene oxide on cement composites
  133. Seed regeneration aided by nanomaterials in a climate change scenario: A comprehensive review
  134. Surface-engineered quantum dot nanocomposites for neurodegenerative disorder remediation and avenue for neuroimaging
  135. Graphitic carbon nitride hybrid thin films for energy conversion: A mini-review on defect activation with different materials
  136. Nanoparticles and the treatment of hepatocellular carcinoma
  137. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part II
  138. Highly safe lithium vanadium oxide anode for fast-charging dendrite-free lithium-ion batteries
  139. Recent progress in nanomaterials of battery energy storage: A patent landscape analysis, technology updates, and future prospects
  140. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part II
  141. Calcium-, magnesium-, and yttrium-doped lithium nickel phosphate nanomaterials as high-performance catalysts for electrochemical water oxidation reaction
  142. Low alkaline vegetation concrete with silica fume and nano-fly ash composites to improve the planting properties and soil ecology
  143. Mesoporous silica-grafted deep eutectic solvent-based mixed matrix membranes for wastewater treatment: Synthesis and emerging pollutant removal performance
  144. Electrochemically prepared ultrathin two-dimensional graphitic nanosheets as cathodes for advanced Zn-based energy storage devices
  145. Enhanced catalytic degradation of amoxicillin by phyto-mediated synthesised ZnO NPs and ZnO-rGO hybrid nanocomposite: Assessment of antioxidant activity, adsorption, and thermodynamic analysis
  146. Incorporating GO in PI matrix to advance nanocomposite coating: An enhancing strategy to prevent corrosion
  147. Synthesis, characterization, thermal stability, and application of microporous hyper cross-linked polyphosphazenes with naphthylamine group for CO2 uptake
  148. Engineering in ceramic albite morphology by the addition of additives: Carbon nanotubes and graphene oxide for energy applications
  149. Nanoscale synergy: Optimizing energy storage with SnO2 quantum dots on ZnO hexagonal prisms for advanced supercapacitors
  150. Aging assessment of silicone rubber materials under corona discharge accompanied by humidity and UV radiation
  151. Tuning structural and electrical properties of Co-precipitated and Cu-incorporated nickel ferrite for energy applications
  152. Sodium alginate-supported AgSr nanoparticles for catalytic degradation of malachite green and methyl orange in aqueous medium
  153. An environmentally greener and reusability approach for bioenergy production using Mallotus philippensis (Kamala) seed oil feedstock via phytonanotechnology
  154. Micro-/nano-alumina trihydrate and -magnesium hydroxide fillers in RTV-SR composites under electrical and environmental stresses
  155. Mechanism exploration of ion-implanted epoxy on surface trap distribution: An approach to augment the vacuum flashover voltages
  156. Nanoscale engineering of semiconductor photocatalysts boosting charge separation for solar-driven H2 production: Recent advances and future perspective
  157. Excellent catalytic performance over reduced graphene-boosted novel nanoparticles for oxidative desulfurization of fuel oil
  158. Special Issue on Advances in Nanotechnology for Agriculture
  159. Deciphering the synergistic potential of mycogenic zinc oxide nanoparticles and bio-slurry formulation on phenology and physiology of Vigna radiata
  160. Nanomaterials: Cross-disciplinary applications in ornamental plants
  161. Special Issue on Catechol Based Nano and Microstructures
  162. Polydopamine films: Versatile but interface-dependent coatings
  163. In vitro anticancer activity of melanin-like nanoparticles for multimodal therapy of glioblastoma
  164. Poly-3,4-dihydroxybenzylidenhydrazine, a different analogue of polydopamine
  165. Chirality and self-assembly of structures derived from optically active 1,2-diaminocyclohexane and catecholamines
  166. Advancing resource sustainability with green photothermal materials: Insights from organic waste-derived and bioderived sources
  167. Bioinspired neuromelanin-like Pt(iv) polymeric nanoparticles for cancer treatment
  168. Special Issue on Implementing Nanotechnology for Smart Healthcare System
  169. Intelligent explainable optical sensing on Internet of nanorobots for disease detection
  170. Special Issue on Green Mono, Bi and Tri Metallic Nanoparticles for Biological and Environmental Applications
  171. Tracking success of interaction of green-synthesized Carbopol nanoemulgel (neomycin-decorated Ag/ZnO nanocomposite) with wound-based MDR bacteria
  172. Green synthesis of copper oxide nanoparticles using genus Inula and evaluation of biological therapeutics and environmental applications
  173. Biogenic fabrication and multifunctional therapeutic applications of silver nanoparticles synthesized from rose petal extract
  174. Metal oxides on the frontlines: Antimicrobial activity in plant-derived biometallic nanoparticles
  175. Controlling pore size during the synthesis of hydroxyapatite nanoparticles using CTAB by the sol–gel hydrothermal method and their biological activities
  176. Special Issue on State-of-Art Advanced Nanotechnology for Healthcare
  177. Applications of nanomedicine-integrated phototherapeutic agents in cancer theranostics: A comprehensive review of the current state of research
  178. Smart bionanomaterials for treatment and diagnosis of inflammatory bowel disease
  179. Beyond conventional therapy: Synthesis of multifunctional nanoparticles for rheumatoid arthritis therapy
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