Materials Advances最新文献

{"title":"Chiral bioderived supercapacitor electrodes based on cellulose nanocrystals†","authors":"Sai Gowtham Allu, Mirina E. Enderlin and Paraskevi Flouda","doi":"10.1039/D5MA00475F","DOIUrl":"https://doi.org/10.1039/D5MA00475F","url":null,"abstract":"<p >The advancement of high-performance thin-film electrodes for next-generation supercapacitors is often hindered by the high cost and aggregation behavior of two-dimensional nanomaterials such as reduced graphene oxide (rGO). Here, we demonstrate that integrating rGO into a chiral, bio-derived matrix of cellulose nanocrystals (CNCs) <em>via</em> evaporation-induced self-assembly can simultaneously improve electrochemical performance and reduce rGO loading. Specifically, we investigate how CNC chirality directs rGO dispersion and modulates ionic transport pathways through hydrogen bonding and structural templating. The resulting CNC/rGO nanocomposites retain key features of chiral organization and exhibit reduced rGO restacking. The optimized CNC/10 wt% rGO composite achieved a specific capacitance of 209 F g<small>⁻¹</small> at 20 mV s<small>⁻¹</small> and 224 F g<small>⁻¹</small> at 2.0 A g<small>⁻¹</small>, representing a 93% improvement over pure rGO, along with a volumetric energy density of 17.6 W h L<small>⁻¹</small> at 204 W L<small>⁻¹</small> and stable performance across a wide power range. This work offers a scalable and sustainable route to engineer nanostructured electrodes, revealing how chirality in bio-based materials can be harnessed to enhance charge storage and ion accessibility.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 15","pages":" 5159-5170"},"PeriodicalIF":5.2,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d5ma00475f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716412","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Substitution-induced changes in the structure, vibrational, and magnetic properties of BiFeO3","authors":"I. Kallel, Z. Abdelkafi, N. Abdelmoula, H. Khemakhem, N. Randrianantoandro and E. K. Hlil","doi":"10.1039/D4MA00805G","DOIUrl":"https://doi.org/10.1039/D4MA00805G","url":null,"abstract":"<p >To address practical progress and prospective applications of BiFeO<small>₃</small>, particularly in the development of data storage devices, we substituted it with the perovskite BaTi<small>_0.9</small>Zr<small>_0.1</small>O<small>₃</small> to form the system (1 − <em>x</em>)BiFeO<small>₃</small>-(<em>x</em>)BaTi<small>_0.9</small>Zr<small>_0.1</small>O<small>₃</small>, limiting <em>x</em> to the range of 0–0.4. We prepared these compositions using the solid-state reaction method, highlighting the correlation between their structure, vibrational properties, and magnetic response. X-ray diffraction and Raman scattering spectra reveal the structural transition from the <em>R</em>3<em>c</em> rhombohedral to <em>Pm</em><img><em>m</em> cubic with increasing the content of BaTi<small>_0.9</small>Zr<small>_0.1</small>O<small>₃</small>. Mössbauer spectroscopy investigation indicates that the substitution of Fe<small>³⁺</small> ions with Ti<small>⁴⁺</small> and Zr<small>⁴⁺</small> weakens the Dzyaloshinskii–Moriya (DM) interaction. Thus, the DM interaction becomes subordinate to the exchange interaction in the G-type antiferromagnetic order of Fe<small>³⁺</small> ions within the BFO structure, potentially suppressing the cycloidal spin configuration in the samples <em>x</em> = 0.1, 0.2, and 0.3. The mean hyperfine magnetic fields decreased with the increasing (<em>x</em>) of BaTi<small>_0.9</small>Zr<small>_0.1</small>O<small>₃</small>, and a paramagnetic phase was observed for <em>x</em> = 0.4. The decrease of quadrupole splitting/shift (Δ<em>E</em><small>_Q</small>/2<em>ε</em>) for <em>x</em> = 0.1, 0.2, and 0.3 indicates a transition toward a higher-symmetry environment around Fe<small>³⁺</small> due to the substitution. This result proves the structural transition from the <em>R</em>3<em>c</em> rhombohedral to <em>Pm</em><img><em>m</em> cubic observed by X-ray diffraction and Raman spectroscopy as the content of BaTi<small>_0.9</small>Zr<small>_0.1</small>O<small>₃</small> increases. Using Rietveld refinement data of X-ray diffraction, the calculation of the tilt angle (<em>ω</em>) reveals a decrease in the level of the rhombohedral structure. For compositions exceeding <em>x</em> = 0.1, the decrease in <em>ω</em> with the substitution rate leads to a reduction in remanent magnetization. However, the enhancement of remanent magnetization (<em>M</em><small>_r</small> ∼ 0.34 emu g<small>⁻¹</small>) was observed for <em>x</em> = 0.1. Moreover, hysteresis loops for the compositions <em>x</em> = 0.1 and 0.2 exhibit smaller field coercivity at 2 K compared to 300 K, which could identify the presence of magnetoelectric coupling in this system.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 14","pages":" 4893-4904"},"PeriodicalIF":5.2,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma00805g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144634946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Natural dielectrics for organic field effect transistors: a study on resins derived from larch, spruce and Atlas cedar Pinaceae trees.","authors":"Corina Schimanofsky, Andreas Petritz, Boyuan Ban, Cristian Vlad Irimia, Rosarita D'Orsi, Cigdem Yumusak, Felix Mayr, Yasin Kanbur, Sunwoo Kim, Alessandra Operamolla, Klara Saller, Manuela Schiek, Yolanda Salinas, Oliver Brüggemann, Christian Teichert, Chunlin Xu, Bong Sup Shim, Clemens Schwarzinger, Barbara Stadlober, Niyazi Serdar Sariciftci, Mihai Irimia-Vladu","doi":"10.1039/d5ma00401b","DOIUrl":"10.1039/d5ma00401b","url":null,"abstract":"<p><p>Three Pinaceae resins originating from trees of high industrial significance-European larch, European spruce, and Atlas cedar-were examined in this work. These resins exhibited ease of processing using ethyl alcohol solutions, exceptional film formation, and great dielectric qualities with measured breakdown fields in the range of 5-7.3 MV cm^-1. Because their film surface was essentially trap-free, it was possible to fabricate organic field effect transistors that are hysteresis-free and have outstanding stability under 12-hour bias stress at working voltages below 10 V, with current retention approaching 90% of the original value and transfer curve recovery occurring within 90 minutes. These environmentally friendly materials, which are freely available, are a great option for applications aiming to produce sustainable electronics.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" ","pages":""},"PeriodicalIF":5.2,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12226973/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144575767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Improving the adsorption efficiency of a low-cost natural adsorbent for the removal of an organic pollutant: optimization and mechanism study†","authors":"Yahia Saghir, Ayoub Chaoui, Salaheddine Farsad, Aboubakr Ben Hamou, Asma Amjlef, Mohamed Benafqir, Noureddine El Alem and Mohamed Ez-zahery","doi":"10.1039/D5MA00253B","DOIUrl":"https://doi.org/10.1039/D5MA00253B","url":null,"abstract":"<p >Water scarcity and contamination due to organic pollutants (dyes, antibiotics, pesticides, <em>etc.</em>) have constituted a major problem for humanity in recent decades. In this context, the present work explores the adsorption capacity of modified clay as an adsorbent for the removal of crystal violet (CV) dye from aqueous solutions. The modification combines the basic activation and thermal treatment processes at various temperatures (350 °C to 750 °C). The adsorption performance of the chosen adsorbent was systematically evaluated through batch adsorption experiments using the RSM-Doehlert methodology. The effect of different factors, namely, the adsorbent dose (AD), contact time (CT), and initial CV concentration (IC), at natural pH (pH = 5.29) and room temperature (<em>T</em> = 23 ± 2 °C) on the adsorption capacity of CV was evaluated. The significance of the model was assessed using analysis of variance (ANOVA). Results indicate that the optimum conditions for maximum removal are as follows: AD = 0.5 g L<small>⁻¹</small>, CT = 95 min, and IC = 118.8 mg L<small>⁻¹</small>. Kinetics and isotherms suggest that the experimental data are better described by the nonlinear pseudo-second-order (PSO) model and nonlinear Langmuir isotherm. The adsorption capacity obtained based on the Langmuir isotherm was 1199.93 mg g<small>⁻¹</small>. Moreover, the adsorption process is spontaneous and exothermic, as determined through the thermodynamic study. The proposed adsorption mechanism involves hydrogen bonding, n–π interactions, and cationic substitutions in the interfoliar space of the AC-750 °C adsorbent. This approach offers a promising pathway for incorporating sorbents derived from natural resources, such as clays, into advanced water treatment engineering practices, achieving high adsorption capacity for various organic pollutants, including cefazolin and tetracycline.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 14","pages":" 4857-4873"},"PeriodicalIF":5.2,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d5ma00253b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144634943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sensing of ultra-ppm level NO2 gas via synergistic effects of Cr doping and e-beam irradiation in WO3 nanostructures†","authors":"Anusha, P. Poornesh, Vikash Chandra Petwal, Vijay Pal Verma and Jishnu Dwivedi","doi":"10.1039/D5MA00330J","DOIUrl":"https://doi.org/10.1039/D5MA00330J","url":null,"abstract":"<p >Herein, we report the effects of Cr doping and electron beam irradiation (EBI) on WO<small>₃</small> thin films towards low-level detection of NO<small>₂</small>. Structural, morphological, and defect correlations are presented to provide a comprehensive understanding of the film's properties. XRD and Raman analyses confirmed the formation of well-crystallized WO<small>₃</small> films due to doping and irradiation. Photoluminescence analysis validated the presence of oxygen vacancy (V<small>_o</small>) defects in the films which was further corroborated by XPS studies. The EBI Cr–WO<small>₃</small> film exhibited a higher concentration of V<small>_o</small> defects and smaller grain sizes, contributing to enhanced sensing performance. A maximum sensor response of 3.43 was achieved at an NO<small>₂</small> concentration of 5 ppm. Theoretical limit of detection (LOD) calculations indicated ultra-low NO<small>₂</small> detection capability at 0.4 ppm (400 ppb), highlighting the potential of the prepared film for applications in environmental monitoring, healthcare diagnostics, and industrial settings.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 15","pages":" 5100-5113"},"PeriodicalIF":5.2,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d5ma00330j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bactericidal activity of ZnO nanoparticles–anti-TB drug combination towards the H37Rv strain and multidrug-resistant isolates of Mycobacterium tuberculosis via SufB splicing inhibition†","authors":"Deepak Kumar Ojha, Ashwaria Mehra, Sunil Swick Rout, Sidhartha Giri and Sasmita Nayak","doi":"10.1039/D4MA01224K","DOIUrl":"https://doi.org/10.1039/D4MA01224K","url":null,"abstract":"<p >Tuberculosis (TB) remains a significant global health threat, claiming millions of lives annually. Despite advancements in treatment, the emergence of drug-resistant strains has hindered effective TB control. The current management of TB involves prolonged treatment duration with severe side effects, leading to poor patient compliance. Metal-based nanoparticles are shown to manage drug-sensitive TB when combined with anti-TB drugs. However, the mycobactericidal potential of nanoparticles towards drug-resistant TB is not confirmed yet. This work explores the bactericidal potential of zinc oxide nanoparticles (ZnONPs, 40 nm) in managing both drug-sensitive and drug-resistant TB in combination with anti-TB drugs. It was found that ZnONPs inhibit the generation of active SufB protein <em>via</em> splicing inhibition, an essential event for <em>Mycobacterium tuberculosis</em> (<em>Mtb</em>) survival. While TEM and UV-visible spectroscopy identified NPs–protein interaction, SEM visualised extensive membrane damage in H37Rv and multidrug-resistant (MDR) <em>Mtb</em> cells. Alamar blue assay and the spread plate method detected minimum inhibitory concentration and minimum bactericidal concentration of ZnONPs towards the H37Rv strain and MDR <em>Mtb</em> isolates. <em>In vitro</em> studies identified a combination with ZnONPs that reduced effective doses for anti-TB drugs towards H37Rv and MDR <em>Mtb</em> isolates. A correlation to splicing inhibition was made by performing Alamar blue assay in an SufB intein-less microbe, <em>Mycobacterium smegmatis</em>. A similar drug combination attenuated the mycobacterial load and inflammation in the spleen and lungs and protected against <em>Mtb</em> induced splenomegaly in infected mice. Thus, ZnONPs can be used as a potent additive in the anti-TB regimen to manage drug-susceptible and drug-resistant TB, addressing challenges such as prolonged therapy, drug toxicity and poor patient compliance.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 15","pages":" 5242-5259"},"PeriodicalIF":5.2,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma01224k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photo-crosslinked persistent micelle templates with near universal solvent compatibility†","authors":"Coby S. Collins, Mengxue Zhang, CJ Sturgill, Christian X. Ruff, Bryce Melton and Morgan Stefik","doi":"10.1039/D5MA00327J","DOIUrl":"https://doi.org/10.1039/D5MA00327J","url":null,"abstract":"<p >The controlled preparation of porous nanomaterials from block polymer templates is important for diverse applications from energy devices to optical coatings and sorbents. The architectural dimensions determine the overall performance for many of these applications, however the independent control of these dimensions has remained limited to a narrow range of solvent conditions for kinetically trapped (“persistent”) micelle templates. Polymers with a photo-reactive chemistry are shown to enable cross-linked micelle templates that universally remain persistent under diverse solvent conditions. Specifically, poly(poly(ethylene glycol methacrylate))-<em>b</em>-poly(butyl methacrylate-<em>co</em>-coumarin methacrylate) (OBC) was prepared by RAFT polymerization and the resulting micelles were crosslinked with UV light (X-OBC). TEM images revealed that crosslinking in MeOH-only led to a mixture of micelles and unimers whereas crosslinking in MeOH–H<small>₂</small>O led to pure micelles. Absorbance measurements indicated 50% coumarin dimerization (crosslinking) occurred after 180 min of UV exposure. The near universal solvent compatibility of X-OBC persistent micelles is demonstrated with DLS measurements in toluene, DCM, DMF, THF, EtOH, and MeOH, whereas OBC is shown to release unimers in DCM, DMF, THF, and toluene, or precipitate from EtOH due to a morphology change. Spectroscopic testing of micelle crosslinking occurred at each templating step. Micelle entrapment was also validated with SAXS and SEM measurements after nanomaterial templating where X-OBC enabled sample series with constant pore size whereas OBC did not. Furthermore, the results uniquely show X-OBC micelle persistence when processed from non-selective solvents. These results highlight how molecular engineering and tailored processing can enable the generalized synthesis of controlled porous nanomaterials.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 14","pages":" 4881-4892"},"PeriodicalIF":5.2,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d5ma00327j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144634945","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Extrusion-based additive manufacturing of complex three-dimensional ultra-lightweight materials using the basidiomycete Fomes fomentarius†","authors":"Huaiyou Chen, Bertram Schmidt, Andrew Gennett, Paul H. Kamm, Aleksander Gurlo, Vera Meyer and Ulla Simon","doi":"10.1039/D5MA00320B","DOIUrl":"https://doi.org/10.1039/D5MA00320B","url":null,"abstract":"<p >Fungal mycelium-based materials harness the full potential of lignocellulosic resources in a sustainable way. Additive manufacturing can enhance design flexibility and reduce the use of plastic moulds in producing fungal mycelium-based materials. Here, we explored additive manufacturing of living <em>Fomes fomentarius</em> for precise fabrication of fungal mycelium-based materials. Using a 1.6 mm nozzle, we extruded a paste containing living fungal mycelium, rapeseed straw, and sodium alginate into various sizes and shapes. The aerial mycelium (consisting of fungal hyphae that grow away from the substrate surface into the air) formed was manually compressed during growth to maintain the desired shapes. For inactivation, freeze drying was found to maintain the original dimensions and shapes of the printed structures more effectively than convection oven drying. In addition to the printed composite materials, pure three-dimensional fungal mycelium skins could also be produced. Electron scanning microscopy, Fourier transform infrared spectroscopy, X-ray microtomography, hydrophobicity testing, compressive and tensile testing were used to investigate the morphological, physical and mechanical characteristics of the printed structures. Our results demonstrate that living <em>F. fomentarius</em> mycelium can be successfully used to manufacture lignocellulose–fungal mycelium-based materials with defined growth and hydrophobicity, which further expands its potential for future application as renewable biomaterials.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 15","pages":" 5149-5158"},"PeriodicalIF":5.2,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d5ma00320b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716411","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Near blue light emitting benzimidazol-2-thione†","authors":"Bikash Lahkar, Gopendra Muduli, Suman Mandal, Arushi Rawat, Abhilash Sahu, Kohsuke Matsumoto, Osamu Tsutsumi and Ganesan Prabusankar","doi":"10.1039/D5MA00344J","DOIUrl":"https://doi.org/10.1039/D5MA00344J","url":null,"abstract":"<p >The discrete organosulfur molecule possessing a high quantum yield with blue luminescence properties has significant potential as an optically active material for future applications. In this context, the sulfoxide or sulfone-based fused heterocyclic materials are known as the new generation of luminogens. The first sulfur-fused heterocyclic thioketone luminogen consisting of a donor–acceptor structure has been reported in this work, with benzimidazole and sulfur acting as the donor, whereas anthracene and pyridine moieties act as the acceptor. Herewith, we report the synthesis of 1-(9-methyl anthracene)-2-(2-methyl pyridine)-benzimidazol-2-thione (<strong>APBT</strong>). The donor and acceptor are connected through a methyl linker. Molecule <strong>APBT</strong> emits at <em>λ</em><small>_em</small> = 494 nm in the crystalline state and <em>λ</em><small>_em</small> = 410 nm in the solution state. Besides, molecule <strong>APBT</strong> showed an aggregation-induced emission due to its molecular packing in the crystalline state. The molecule emits in the near blue region in the crystalline state with a quantum yield of 17.82% and a luminescent lifetime of 47.19 ns. The light-emitting behaviour of crystalline <strong>APBT</strong> is comparable with <strong>APBT</strong>-coated LED. DFT calculations were performed to determine the energy of frontier molecular orbitals, and the HOMO–LUMO gap (HLG) was found to be 3.45 eV.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 15","pages":" 5056-5063"},"PeriodicalIF":5.2,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d5ma00344j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring metal nanocomposites for asphaltene removal: the role of Cu-BTC, CoMn2O4 and K-OMS-2 in the adsorption and oxidation of asphaltenes†","authors":"Abhishek Nayak, Shanon Viegas, Nithya Rajagopal, Adrian Marcel Rodrigues, Harshini Dasari and Nethaji Sundarabal","doi":"10.1039/D5MA00106D","DOIUrl":"https://doi.org/10.1039/D5MA00106D","url":null,"abstract":"<p >Asphaltenes, the most polar and complex class of compounds in petroleum crude oils, pose significant challenges in refining processes due to their tendency to precipitate, causing fouling, clogging, and corrosion in pipelines and reactors. These issues are further increased by their solubility behaviour, making their removal difficult. The present study investigates the synthesis of metal nanocomposites focused on a metal–organic framework (Cu-BTC), a spinel oxide (CoMn<small>₂</small>O<small>₄</small>) and an octahedral molecular sieve (K-OMS-2) for the adsorption and oxidation of asphaltenes from model solutions. The prepared nanocomposites were characterised using FE-SEM, EDX, HR-TEM, FT-IR, XRD, and BET surface area analysis. Furthermore, they were tested for their ability to adsorb asphaltenes using batch adsorption studies, and the equilibrium data obtained were interpreted using Langmuir, Freundlich, Temkin, Redlich–Peterson, and Hill isotherm models. Thermodynamic studies were performed, and changes in enthalpy (Δ<em>H</em><small>⁰</small>), entropy (Δ<em>S</em><small>⁰</small>) and free energy (Δ<em>G</em><small>⁰</small>) were determined from the data. Kinetic studies were conducted, and the data were analysed using pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich, intraparticle diffusion, and Boyd diffusion models. Adsorption studies revealed that asphaltenes’ adsorption onto Cu-BTC was best explained by the Freundlich adsorption isotherm, while CoMn<small>₂</small>O<small>₄</small> followed the Langmuir model and K-OMS-2 was governed by the Hill isotherm. The monolayer adsorption capacities of the prepared nanocomposites varied in the order: K-OMS-2 (245 mg g<small>⁻¹</small>) &gt; CoMn<small>₂</small>O<small>₄</small> (77 mg g<small>⁻¹</small>) &gt; Cu-BTC (50 mg g<small>⁻¹</small>). Kinetic studies indicated that the adsorption process was rapid, and the Boyd diffusion model suggested that the rate-limiting step was the external mass transfer of asphaltenes onto the adsorbent. CoMn<small>₂</small>O<small>₄</small> exhibited the highest catalytic activity among the prepared nanocomposites for asphaltene oxidation, achieving a 140 °C reduction in oxidation temperature. The findings indicated that K-OMS-2 is an effective material for adsorption, while CoMn<small>₂</small>O<small>₄</small> is efficient in the catalytic oxidation of asphaltenes.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 15","pages":" 5114-5125"},"PeriodicalIF":5.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d5ma00106d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}