Materials Today Catalysis最新文献

{"title":"Facet-specific nitrogen vacancy engineering in BaMO2N (M = Ta, Nb) for enhanced electrochemical ammonia production: Insights from first-principles calculations","authors":"Santhanamoorthi Nachimuthu ,&nbsp;Che-Chih Chu ,&nbsp;Zhong-Lun Li ,&nbsp;Kenta Hongo ,&nbsp;Ryo Maezono ,&nbsp;Yuji Masubuchi ,&nbsp;Jyh-Chiang Jiang","doi":"10.1016/j.mtcata.2025.100125","DOIUrl":"10.1016/j.mtcata.2025.100125","url":null,"abstract":"<div><div>Developing efficient electrocatalysts for the electrochemical nitrogen (N₂) reduction reaction (eNRR) under ambient conditions is essential for sustainable ammonia (NH₃) production. In this study, we have used density functional theory (DFT) calculations to investigate the eNRR performance of two perovskite oxynitrides, BaTaO₂N and BaNbO₂N. We have systematically analyzed the reduction pathways and free energy profiles along both distal and alternating pathways on the (0 0 1) and (1 0 0) facets to evaluate the influence of surface orientation on catalytic performance. Our results show that the pristine surfaces exhibit weak N₂ adsorption and require a high Gibbs free energy (ΔG &gt; 1.8 eV) for the initial protonation step, thereby limiting their intrinsic catalytic activity for direct NH₃ formation. We further explore defect engineering via the Mars-van Krevelen (MvK) mechanism, wherein lattice anions (nitrogen and oxygen) participate in vacancy formation and subsequent N₂ activation. On the BaNbO₂N (0 0 1) surface, lattice nitrogen can be readily protonated and reduced to NH₃, forming nitrogen vacancies that act as catalytic sites to facilitate N₂ adsorption and activation, thereby restoring the catalytic surface for sustained NH₃ production. Notably, the nitrogen-vacant surface (N_v-BaNbO₂N (0 0 1)) exhibits significantly enhanced N₂ adsorption, with a lower Gibbs free energy change (ΔG = 0.18 eV) for the first protonation step, and a thermodynamically favorable NH₃ desorption process. Furthermore, the reduced surface strongly suppresses the competing hydrogen evolution reaction (HER), thereby promoting high selectivity for NH₃ production under ambient conditions. This theoretical study offers valuable insights into the design of perovskite oxynitride-based electrocatalysts, offering a promising strategy for sustainable and economically viable NH₃ synthesis.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"11 ","pages":"Article 100125"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145269902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Highly Selective and Efficient Aerobic Epoxidation of Cyclooctene using Electrospun Co-doped Ceria Nanofiber Membranes","authors":"Chathupama Abeyrathne ,&nbsp;Mahmoud Aboelkheir ,&nbsp;Isaac Olowookere ,&nbsp;Md Sazid B. Sadeque ,&nbsp;Haiyan Tan ,&nbsp;Tamer Uyar ,&nbsp;Mustafa S. Yavuz ,&nbsp;Steven L. Suib","doi":"10.1016/j.mtcata.2025.100127","DOIUrl":"10.1016/j.mtcata.2025.100127","url":null,"abstract":"<div><div>Herein, we present the successful synthesis of Co doped Ceria nanofiber catalysts. The synthesized catalysts exhibit uniform distributions of monomodal pore sizes and demonstrate high catalytic activities for the epoxidation of cyclooctene with high selectivity for cyclooctene epoxide and cyclooctene conversion without using any hazardous sacrificial oxidizing agents. Notably, they achieve exceptional selectivity toward cyclooctene epoxide and substantial cyclooctene conversion under aerobic conditions without using any hazardous sacrificial oxidizing agents. Additionally, this epoxidation process is both economically favorable and environmentally friendly, owing to low catalyst loading, ease of catalyst separation, and excellent reusability, yielding a unique catalyst system compared to those previously reported in the literature. Characterization of the synthesized catalysts was carried out using various analytical techniques, including Powder X-ray diffraction (PXRD), X-ray Fluorescence (XRF), Nitrogen (N₂) sorption studies, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and X-ray photoelectron spectroscopy (XPS). These analyses provided a comprehensive understanding of the structural and chemical properties of the catalysts. Among the catalysts studied, the 5CoCe nanofiber catalyst (5 wt% Co-doped) exhibited the highest catalytic efficiency under aerobic conditions, achieving ≥ 99 % selectivity for cyclooctene epoxide and 96 % conversion of cyclooctene in the present study.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"11 ","pages":"Article 100127"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145424766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of zeolite properties on catalytic hydrodeoxygenation: Spatially segregated metal-acid site engineering for enhanced cascade efficiency","authors":"Shengzhe Ding ,&nbsp;Min Hu ,&nbsp;Ushna Khalid ,&nbsp;Run Zou ,&nbsp;Carmine D’Agostino ,&nbsp;Yani Peng ,&nbsp;Qiang Zhang ,&nbsp;Yilai Jiao ,&nbsp;Christopher M.A. Parlett ,&nbsp;Xiaolei Fan","doi":"10.1016/j.mtcata.2025.100129","DOIUrl":"10.1016/j.mtcata.2025.100129","url":null,"abstract":"<div><div>To reduce the environmental impact of hydrodeoxygenation (HDO) while enhancing process economics, it is crucial to develop advanced catalytic materials that enable HDO under milder conditions, suppress decarboxylation/decarbonylation (DCOx), and eliminate auxiliaries, all while maximising target product yield. Spatial segregation of metal and acid sites has emerged as an effective strategy for improving HDO efficiency in fatty acid conversion. This study explores the influence of zeolitic carrier porosity and acidity on HDO, employing Pd nanoparticles as the metal catalyst and lauric acid as the model substrate. The findings reveal that acidity and mesoporosity are key determinants of substrate conversion, product selectivity, and overall catalytic performance within the same zeolitic framework (MFI ZSM-5). High acidity and hydrophilicity in ZSM-5 zeolites hinder lauric acid conversion by retaining water within the framework, which would adversely affect reaction equilibria in the HDO cascade, whereas mesoporosity in hierarchical ZSM-5, which enhances mass transport, is beneficial for conversion and dodecane formation. For hierarchical ZSM-5, produced via desilication, the less acidic PdNP/HMZSM5-DA25 (25 reflecting the original Si:Al ratio) yields 2.5 times more dodecane than more acidic but less mesoporous PdNP/HMZSM5-DA15 (Si:Al of 15). Expanding this investigation to different zeolitic frameworks (Pd nanoparticles supported on USY, BETA, and ZSM-5) demonstrates that larger micropores further facilitate diffusion and improve catalytic efficiency. PdNP/HUSY-DA exhibits a 32% improvement over PdNP/HMZSM5-DA25, with a dodecane production rate of 6.1 mmol_dodecane g_catalyst⁻¹ h⁻¹, ranking it among the most superior state-of-the-art HDO systems at comparable conditions. This study validates the spatial segregation of active sites as a robust strategy for stabilising Pd nanoparticles and improving catalyst durability in cascade HDO processes. Fine-tuning zeolite properties is essential for optimising catalyst design to achieve efficient and sustainable biofuel production via HDO.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"11 ","pages":"Article 100129"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145579306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrocatalytic performance in direct ethanol fuel cells: Contributions of monometallic, bimetallic, and trimetallic catalysts","authors":"Pariksha Bishnoi ,&nbsp;Kirti Mishra ,&nbsp;Urvashi Sen ,&nbsp;Samarjeet Singh Siwal","doi":"10.1016/j.mtcata.2025.100124","DOIUrl":"10.1016/j.mtcata.2025.100124","url":null,"abstract":"<div><div>Over the recent past, there has been exponential growth in the advancements of clean energy sources and fuel cell technologies. Fuel cells are the electrochemical devices that are able to convert chemical energy of a fuel into electrical energy. This paper studies the electrocatalytic activity of monometallic, bimetallic, and trimetallic catalysts in direct ethanol fuel cells (DEFCs). Monometallic catalysts, for example, platinum (Pt) and palladium (Pd), along with other transition metals, find application but have complications like poor tolerance to carbon monoxide (CO) and incomplete oxidation of ethanol. Furthermore, bimetallic catalysts, e.g., Pt-Ru and Pt-Sn, have shown significant advancements because of these synergistic enhancements, leading to improved performance, stability, and CO poisoning resistance. Another group of catalysts, trimetallic (e.g., Pt-Ru-Sn), have both high efficiency and long-lasting capabilities, making them stand out as applicable in most DEFC practical scenarios. This research proves the advantage of multi-metallic catalysts in developing the DEFC technology while solving both major factors of catalyst deterioration and their price.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"11 ","pages":"Article 100124"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study on the hydrogen storage performance mechanism of MgH2 co-modified by rare earth hydride and high entropy hydrogen storage alloy based on in-situ differentiation","authors":"Haoyuan Zheng ,&nbsp;Shuzhong Wang ,&nbsp;Chen Jin ,&nbsp;Hang Che ,&nbsp;Yuqin Zheng ,&nbsp;Shixuan He ,&nbsp;Haizhen Liu ,&nbsp;Lingchao Zhang ,&nbsp;Xinhua Wang","doi":"10.1016/j.mtcata.2025.100130","DOIUrl":"10.1016/j.mtcata.2025.100130","url":null,"abstract":"<div><div>Owing to its high hydrogen storage capacity (7.6 wt%), MgH₂ is regarded as a highly promising solid-state hydrogen storage material. Nonetheless, its commercialization is constrained by high thermodynamic stability and sluggish hydrogen sorption kinetics. Thus, catalyst introduction is essential to enhance MgH₂’s hydrogen storage performance. This study designed and synthesized a hydrogen storage high-entropy alloy, TiVCrZrNbCe. Upon doping with Ce to enhance activation, the alloy was combined with MgH₂ to fabricate a composite hydrogen storage system, thereby boosting the overall hydrogen storage properties of MgH₂. Results indicate that the Ce-doped alloy eliminates the initial long hydrogen absorption induction period and exhibits rapid hydrogen absorption capability. The optimal MgH₂/10 wt% HEA composite for hydrogen storage incorporates a Ce-doped alloy and MgH₂. MgH₂/10 wt% HEA shows initial/peak dehydrogenation temperatures of 205/270 °C, releases 6.05 wt% hydrogen, and enables rapid hydrogen absorption at room temperature. The hydrogen sorption activation energies are reduced to 40.8/76.8 kJ mol⁻¹, and the capacity maintains well over ten cycles. Microstructure and mechanism analyses reveal that during ball milling of the MgH₂-alloy, the Ce element in the alloy will interact with MgH₂ to partially absorb hydrogen to form CeH_2.51 in situ and generate a hydride FCC-MH phase. During hydrogen absorption/desorption, CeH_2.51 and the alloy serve as nucleation sites for MgH₂, effectively promoting its hydrogenation/dehydrogenation reactions and exerting a “hydrogen overflow” effect. Additionally, the alloy’s self hydrogen absorption/desorption drives MgH₂’s hydrogenation/dehydrogenation, functioning as a “hydrogen pump”. The hydrogen absorption/desorption properties of MgH₂ were notably optimized via the synergistic catalysis of CeH_2.51 and the alloy. This work offers novel insights for designing and catalytically modifying new MgH₂ catalysts.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"11 ","pages":"Article 100130"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145623527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ediorial Board","authors":"","doi":"10.1016/S2949-754X(25)00045-6","DOIUrl":"10.1016/S2949-754X(25)00045-6","url":null,"abstract":"","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"11 ","pages":"Article 100132"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145750059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reactive oxygen species in selective heterogeneous catalytic oxidations","authors":"Laura A. Achola ,&nbsp;Elsa Njeri ,&nbsp;Luisa F. Posada ,&nbsp;Steven L. Suib","doi":"10.1016/j.mtcata.2025.100126","DOIUrl":"10.1016/j.mtcata.2025.100126","url":null,"abstract":"<div><div>Heterogeneous catalysis is essential in industrial chemical processes, particularly selective oxidation reactions. Oxidative reactions are complex due to the occurrence of multiple reaction pathways, kinetic and thermodynamic effects, and the involvement of reactive oxygen species (ROS). ROS, including superoxide radical anions (O₂^{<strong>·</strong>-}), hydrogen peroxide (H₂O₂), hydroxyl radicals (^•OH), and singlet oxygen (¹O₂), can enhance selectivity or lead to overoxidation of reactants. Thus, ROS identification on a catalyst’s surface or under real-time conditions is crucial for determining mechanistic pathways and the key ROS species that contribute to high selectivity for oxidation processes. Tracking these reactive species can be challenging within heterogeneous systems. Most detection methods are hindered by the rapid decay of ROS, the complexity and cost of spin-trapping probes, lack of probe selectivity, and interference from other species in the reaction, which limits real-time ROS monitoring. There remains a need for reliable detection and scavenging methods, further combined with characterization techniques such as EPR, XPS, in situ DRIFTS, and oxygen isotope labeling. Prior review articles on ROS focus on applications in medicine, biological fields, and photocatalysis. This review examines the chemistry of molecular oxygen, generation mechanisms, and the detection of ROS in heterogeneous selective catalytic oxidations and our contribution to the field; we focus on literature published over the last five decades, highlight the specific challenges associated with studying these systems, and provide strategies for overcoming these limitations. Finally, we discuss <em>in situ</em> vs. <em>ex situ</em> ROS probing techniques and demonstrate their importance in dynamic catalytic systems.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"11 ","pages":"Article 100126"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145623531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cover","authors":"","doi":"10.1016/S2949-754X(25)00044-4","DOIUrl":"10.1016/S2949-754X(25)00044-4","url":null,"abstract":"","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"11 ","pages":"Article 100131"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145750051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thin-film approach for scalability and enhancement of solar hydrogen production with CNT integrated Ce-doped-TiO2 composite in direct sunlight","authors":"Preethi Vijayarengan ,&nbsp;Anthony Raja Maria ,&nbsp;K.S. Ashadevi ,&nbsp;Naresh Nalajala ,&nbsp;Chinnakonda S. Gopinath","doi":"10.1016/j.mtcata.2025.100115","DOIUrl":"10.1016/j.mtcata.2025.100115","url":null,"abstract":"<div><div>Solar hydrogen production by photocatalysis has long been considered as an important energy option. Whichever photocatalyst succeeds, methods should be available to scale-up in a most sustainable and cost-effective manner, and the present work addresses this specific issue. In the present study, Ce-doped in the TiO₂ lattice (Ce-TiO₂) and the same integrated with CNT (CNT-Ce-TiO₂; (CCT)) composite was synthesized and characterized. Current study demonstrates the synergistic integration of Ce-TiO₂ as a light absorber and charge generator with CNTs as efficient charge separation at heterojunctions as well as charge transporter in a thin-film configuration (lab-scale (4.7 cm²), bench-scale (500 cm²)). Improved H₂ generation under direct sunlight demonstrated in thin film form, than in particulate suspension, is attributed to efficient light absorption, particularly for electron-hole pair separation and their dispersion to redox sites. Additionally, the role of the binder is highlighted for improving H₂ yield and the sustainability of the thin-film form of photocatalyst. ∼200 mg (1 g) CCT coated over 500 cm² (2500 cm²) photocatalyst produced 21.6 mmol/h (102 mmol/h) H₂ in sunlight. Present results provides a proof of concept that the thin film form of photocatalyst displays, at least 10 times, higher H₂ yield than its powder counterpart, depending on the measurement conditions. A non-linear enhancement in H₂ yield with small and large area thin-film indicates complex underlying factors and highlights the scope for further improvements.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"10 ","pages":"Article 100115"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144888787","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comparative photoelectrochemical study of oligomeric s-heptazines nanomaterials derived from partial thermal decompositions of urea & thiourea precursors","authors":"Anupam Chowdhury ,&nbsp;Dipanwita Majumdar ,&nbsp;Moisilee Dutta ,&nbsp;Swapan Kumar Bhattacharya","doi":"10.1016/j.mtcata.2025.100112","DOIUrl":"10.1016/j.mtcata.2025.100112","url":null,"abstract":"<div><div>Thermal polymerization of urea and thiourea under closed conditions at 370 °C have been independently carried out and the derived samples were subjected to detailed characterization techniques that showed varied chemical compositions as well as distribution of functional groups despite the same C/N atomic ratio. The detailed optical, physicochemical and morphological characterizations from FTIR, RAMAN, XRD, TGA, XPS, solid-state &amp; solution-state NMR, solid state UV–visible absorption, PL, BET, FESEM, TEM and SAED revealed that urea derived U370 sample with 2D flakes-like morphology closely resembles melem-cyanuric acid complex/adduct while thiourea derived T370 sample having flat ribbon-like structure can be intimately related with oligomeric melem (s-heptazines) hydrate respectively. Solution state UV–visible absorption spectroscopy, Zeta potential and Dynamic Light Scattering (DLS) aided size distribution studies were also conducted in aqueous media with varying pH to comprehend the character of chemical functionalities and nature of prevailing interactions in acid, neutral and alkaline electrolytes which were further be correlated with their photoelectrochemical responses. Their comparative electrochemical studies were conducted in aid with CV, GCD and EIS studies both under dark as well as in presence of different and wide range light sources in acid, neutral and basic media correspondingly to design low costing, eco-friendly, smart materials for light-driven supercapacitive devices. Results revealed T370 sample with better photoelectrochemical performance in terms of higher normalized areal capacitance, better rate capacity as well as improved cyclic stability than U370 sample in aqueous alkaline electrolyte. Thus, this communication outlines a novel approach for significantly upgrading the supercapacitive responses of materials using the simple aid of electromagnetic radiation, thereby opening up new roadways in the emerging field of photoelectrochemical charge storage and conversion technology.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"10 ","pages":"Article 100112"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144738399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}