Applied Catalysis A: General最新文献

{"title":"Enhanced low-temperature activity of CO2 methanation: Effect of metal oxide support on the performance of Ni-based catalysts","authors":"Cristina Italiano,&nbsp;Lidia Pino,&nbsp;Domenico Maccarrone,&nbsp;Antonio Vita","doi":"10.1016/j.apcata.2025.120529","DOIUrl":"10.1016/j.apcata.2025.120529","url":null,"abstract":"<div><div>The methanation of carbon dioxide via the Sabatier process is attracting growing attention for power-to-gas (P2G) application. In the current study, a series of 25 wt% Ni-based catalysts were synthesized using solution combustion synthesis (SCS) to investigate the influence of the support on the methanation performance. The results showed that Ni/CeO₂-ZrO₂ catalyst exhibited superior activity, achieving 72.5 % and 95.5 % CO₂ conversion at 250 °C and 300 °C, respectively, while maintaining excellent stability over 100 h of time-on-stream. CO₂-TPD analysis revealed that weak-to-moderate basic sites played a key role in enhancing catalytic activity. This is consistent with XPS results, which indicated a high concentration of surface hydroxyl groups and oxygen vacancies, responsible for the enhanced basicity of the CeO₂-ZrO₂ support. Additionally, the CO-chemisorption measurements confirmed improved Ni dispersion, further contributing to efficient H₂ activation. In situ DRIFT-MS studies identified a reaction pathway involving CO₂ adsorption as carbonate and bicarbonate species, followed by stepwise hydrogenation to methane via formate intermediates. The correlation between turnover frequency (TOF) and the number of weak-to-moderate basic sites supports a dual-site reaction mechanism, where basic sites facilitate CO₂ activation and Ni sites promote H₂ dissociation, both contributing to the remarkable low-temperature carbon dioxide methanation activity.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120529"},"PeriodicalIF":4.8,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144926188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrogen-free catalytic conversion of highly concentrated glycerol solution: Influence of Si/Al molar ratio in Cu/SBA-15 catalysts","authors":"Jorge Gajardo ,&nbsp;Julio Colmenares-Zerpa ,&nbsp;A.F. Peixoto ,&nbsp;D.S.A. Silva ,&nbsp;F. Gispert-Guirado ,&nbsp;J. Llorca ,&nbsp;E.A. Urquieta-Gonzalez ,&nbsp;J.B.O. Santos ,&nbsp;M.G. Álvarez ,&nbsp;R.J. Chimentão","doi":"10.1016/j.apcata.2025.120528","DOIUrl":"10.1016/j.apcata.2025.120528","url":null,"abstract":"<div><div>Catalytic conversion of glycerol to C₃ products using advanced functional materials is an economical and efficient approach to promoting sustainable energy development. Selective glycerol dehydration to hydroxyacetone (HA) is one such alternative and requires an appropriate balance of catalyst texture, structure, and acidity. In this study, different Cu-based catalysts supported on SBA-15 with different Si/Al molar ratios (2, 10, 15 and ∞) were prepared using the “pH-adjusting” method and ammonia evaporation method and they were evaluated for the dehydration of glycerol at high concentration (80 wt%.) in liquid phase to hydroxyacetone under inert N₂ atmosphere. The formation of 1,2-propanediol (1,2-PDO) was also observed even under N₂ inert atmosphere conditions. The catalysts were characterized by ICP-MS, N₂ adsorption-desorption, XRD, HRTEM, H₂-TPR, passivation of N₂O, NH₃-TPD, TPO, FTIR, FTIR-OH, Py-FTIR and XPS. The Al chemical environment and the Si/Al molar ratio of the supports show a remarkable effect on the catalytic performance. The highest catalytic activity was obtained with the SiAl = 15 molar ratio, reaching a conversion of around 35 % at 120 min of reaction and a selectivity of 84 % to hydroxyacetone at 90 min of reaction. While lower Si/Al molar ratios led to a decrease in catalytic activity and an increase in product distribution. The isomorphic incorporation of Al into the SBA-15 promotes the interlinking cooperative between the properties of textural, acidity, structural, and stability of the catalyst. HRTEM and HAADF-STEM images show a well-defined hexagonal arrangement even when the CuO phase is added to the mesoporous materials with high Al loadings. At high heteroatom loadings, the typical hexagonal arrangement of the mesostructure was preserved but a decrease in the long-range order was observed. The presence of mononuclear and oligonuclear Cu^δ+ species, which is related to their coordination environment and their position in the mesoporous network, was dependent on the variation of the Si/Al molar ratio. The prominent catalytic performance at the SiAl = 15 ratio can be attributed to an optimal cooperative effect of the structural defects and electronic promotion produced by the Al species, which favors the conversion of glycerol to HA. While the increase in the selectivity of 1,2-PDO observed with the molar ratio SiAl = 2 is associated with a conjugation between the higher availability of acid sites on the surface that promote the dehydration of glycerol and the domain size of copper species which would be acting as dehydrogenating sites of glycerol, forming H₂ <em>in</em>-<em>situ</em> leading to the conversion of HA into 1,2-PDO.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120528"},"PeriodicalIF":4.8,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997715","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Active species trapping test for the mechanism study of photocatalytic dye degradation: A critical examination","authors":"Peng Zhang ,&nbsp;Nan Xiao ,&nbsp;Lei Yang ,&nbsp;Songli Liu ,&nbsp;Jiankang Wang ,&nbsp;Jinyu Hu ,&nbsp;Zhibo Tong ,&nbsp;Guoqing Zhang ,&nbsp;Shimin Ding ,&nbsp;Youqing Yu","doi":"10.1016/j.apcata.2025.120527","DOIUrl":"10.1016/j.apcata.2025.120527","url":null,"abstract":"<div><div>In recent years, active species trapping technique was widely employed to identify the dominant reactive species involved in photocatalytic processes. Although well recognized by most researchers, the reliability, validity, and accuracy of this technique have never undergone systematic investigation. In this study, a series of experiments were conducted to examine the application of active species trapping technique in photocatalytic dye degradation. Control experiments were performed to study the direct reactions between dyes and quenchers. Active species trapping tests were carried out to compare the trapping effect of different quenchers in various photodegradation reactions. Benzoquinone (BQ) was chosen as the model quencher to understand the interactions between quenchers and photocatalysts. The etching characteristics of titanium dioxide and graphitic carbon nitride were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) method, Fourier transform-infrared (FTIR) spectroscopy, and Electron spin resonance spectroscopy (ESR). The experimental findings indicated that active species trapping is a complex process involving several major participants, including light, photocatalyst, contaminant (or product), and quencher, rather than a simple interaction between quenchers and the photo-induced active species.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120527"},"PeriodicalIF":4.8,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cr-modified CeMo/SiO2 as the efficient and stable supported catalyst for dehydrogenation of methanol to anhydrous formaldehyde","authors":"Xiao Xu ,&nbsp;Ziqiang Duan ,&nbsp;Yuanjie Huang ,&nbsp;Xiuzhang Lan ,&nbsp;Xin Teng ,&nbsp;Hongyu Zhang ,&nbsp;Jimmy Yun ,&nbsp;Zuobo Yang ,&nbsp;Hong Zhao ,&nbsp;Jie Zhang","doi":"10.1016/j.apcata.2025.120526","DOIUrl":"10.1016/j.apcata.2025.120526","url":null,"abstract":"<div><div>Direct dehydrogenation of methanol to co-produce hydrogen and formaldehyde represents a promising chemical technology for generating clean fuel and critical chemical intermediates. However, the harsh reaction conditions pose significant challenges in developing efficient and durable catalysts for this process. In this research, Cr-modified CeMo/SiO₂ supported catalyst (Cr-Ce₁Mo₆/SiO₂) that achieves exceptional performance in methanol-to-anhydrous-formaldehyde conversion is reported. Strategic Cr doping with optimal metal loading and Ce/Mo ratio introduces customized oxygen vacancies, which is beneficial for catalytic kinetics. In addition, the interplay between Cr and Mo species not only weakens surface acidity but concurrently reinforces the Brønsted acid characteristics of Mo^6 + centers. This dual functionality facilitates rapid desorption of carbon-containing intermediates during catalytic cycles, thereby mitigating surface coking and suppressing the reductive deactivation of high-valence Mo species. The achieved acid activity control/high-speed desorption/anti-coke synergy establishes a self-sustaining beneficial cycle that perpetuates catalytic efficiency. This synergistic mechanism fundamentally underpins the exceptional catalytic performance and long-term durability of the material. The optimized catalyst delivers 89.6 % methanol conversion with 92.9 % formaldehyde selectivity at 300 ℃. Remarkably, it retains 85.7 % conversion and 89.0 % selectivity over 240 h of continuous operation. This study effectively optimized the directional activity and durability of the supported catalyst through ingenious modification strategy, providing valuable insights for direct dehydrogenation of methanol and other similar catalytic processes.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120526"},"PeriodicalIF":4.8,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145156024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Kinetic consequences of carbon deposition in CH₄ steam and dry reforming on Rh via operando Raman spectroscopy and microkinetic analysis","authors":"Riccardo Colombo,&nbsp;Gianluca Moroni,&nbsp;Mauro Bracconi,&nbsp;Matteo Maestri","doi":"10.1016/j.apcata.2025.120523","DOIUrl":"10.1016/j.apcata.2025.120523","url":null,"abstract":"<div><div>This study presents a comparative investigation of Methane Steam Reforming (MSR) and Methane Dry Reforming (MDR) over a Rh/α-Al₂O₃ catalyst, with specific focus on the role of carbon deposition in catalyst deactivation. Catalytic tests combined with time-resolved operando Raman spectroscopy reveal that carbon accumulation is strongly affected by the co-reactant-to-CH₄ ratio and significantly more pronounced under MDR conditions. Although MSR exhibits similar deactivation trends, these occur at lower co-reactant concentrations, highlighting the superior effectiveness of water in suppressing carbon formation. To rationalize these observations, a detailed C₁-based microkinetic model was employed to simulate the complete set of experiments. The model incorporates an activity parameter representing the available Rh surface area per reactor volume. Using the initial Rh active surface of the fresh catalyst (α₀) as a constant input led to a systematic overestimation of CH₄ conversion, up to + 30 %, for tests affected by carbon deposition. Therefore, a TOS-dependent α parameter was introduced to account for the progressive loss of active surface due to carbon coverage. The resulting α/α₀ trends are fully consistent with both spectroscopic and kinetic evidence of carbon formation, confirming the link between surface carbon accumulation and catalyst deactivation. Finally, the model yielded spatial profiles of C* coverage consistent with the decreasing carbon trends observed along the reactor axis via spatially resolved operando Raman analysis. These results confirm the mechanistic role of C* as a carbon precursor and demonstrate that the model effectively captures both the macroscopic performance and the microscopic complexity of the reforming environment.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120523"},"PeriodicalIF":4.8,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144908939","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Design of ammonia synthesis Ru catalysts with mesoporous structures through the Si-doping of cerium–lanthanum oxide","authors":"Masashi Kikugawa ,&nbsp;Yoshihiro Goto ,&nbsp;Kiyoshi Yamazaki ,&nbsp;Yuichi Manaka ,&nbsp;Tetsuya Nanba ,&nbsp;Hideyuki Matsumoto ,&nbsp;Akinori Sato ,&nbsp;Masakazu Aoki","doi":"10.1016/j.apcata.2025.120525","DOIUrl":"10.1016/j.apcata.2025.120525","url":null,"abstract":"<div><div>Green ammonia has attracted growing attention as an energy carrier to facilitate the storage and transport of hydrogen that is derived from renewable energy sources. It is therefore necessary to develop catalysts that can efficiently synthesize ammonia under milder conditions (&lt;10 MPa) than those required by conventional catalysts (15–30 MPa). In this study, Si is doped into Ru/CeO₂-La₂O₃ catalysts prepared via a polymerization complexation method to promote the synthesis of ammonia over the generated mesoporous structure. Scanning electron microscopy, X-ray diffractometry, N₂ adsorption, attenuated total reflection–Fourier transform infrared spectrometry, and CO adsorption measurements revealed that for the CeO₂-La₂O₃ support, Si doping at levels of ≤ 10 mol% created a mesoporous structure (10–50 nm range) through aggregation of the CeO₂-La₂O₃-SiO₂ solid solution with a smaller particle size than that of undoped particles. Consequently, this resulted in an enhanced Ru dispersion and an improved catalytic activity. However, Si doping at levels &gt; 10 mol% led to the formation of isolated SiO₂ particles bearing inactive Ru species, thereby resulting in a lower catalytic activity. Notably, compared to the catalyst without Si doping, the 10 mol% Si-doped Ru/CeO₂-La₂O₃-SiO₂ catalyst exhibited a 3.5-fold higher rate for ammonia synthesis at a reaction pressure of 5.1 MPa. This system is therefore expected to promote ammonia synthesis under mild conditions, ultimately contributing to the transition from a fossil fuel-based society to a hydrogen-based society.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120525"},"PeriodicalIF":4.8,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144895706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Deciphering catalyst failure: Sulphur–palladium interplay in the one-pot conversion of furfural to isopropyl levulinate","authors":"Marina Ronda-Leal ,&nbsp;Alberto Ricchebuono ,&nbsp;Susana Ramos-Terrón ,&nbsp;Antonio Pineda Pineda ,&nbsp;Antonio A. Romero ,&nbsp;Elena Groppo","doi":"10.1016/j.apcata.2025.120524","DOIUrl":"10.1016/j.apcata.2025.120524","url":null,"abstract":"<div><div>Understanding why multifunctional catalysts fail is critical to advancing biomass valorisation strategies. In this study, we systematically investigate the dynamic deactivation mechanisms that limit the one-pot cascade conversion of furfural (FF) to alkyl levulinates via sequential hydrogenation and alcoholysis. To this end, we designed a series of bifunctional Pd/SO₄²^--ZrO₂–carbon composites derived from NH₂-UiO-66(Zr) through pyrolysis, followed by mechanochemical functionalization. Rather than focusing on catalytic performance, our goal was to elucidate how variations in synthetic protocol – specifically the sequence of pyrolysis, sulphation, calcination atmosphere, and reduction steps – influence structural evolution, Pd–sulphur interactions, and active site accessibility. Through a broad multi-technique characterization campaign, we reveal that Pd deactivation by sulphur is a gradual and reversible process, closely related to the catalyst’s thermal history. While high-temperature H₂ treatments can restore Pd accessibility, they also strip Brønsted acidity by removing surface SO_4^2— groups, revealing a compromise between hydrogenation and alcoholysis functions. These findings highlight the complexity of designing truly cooperative multifunctional catalysts and the importance of integrated synthetic–reactive strategies that move beyond performance optimization alone.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120524"},"PeriodicalIF":4.8,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced ruthenium utilization via succinamic acid-functionalized SiO₂ supports for efficient hydrogen storage in toluene-based LOHC systems","authors":"Tatiana M. Bustamante ,&nbsp;Santiago Bedoya ,&nbsp;Yenlis Rodríguez-Aballi ,&nbsp;Diego Sanhueza-Rosales ,&nbsp;J.N.Díaz de León ,&nbsp;Cristian H. Campos","doi":"10.1016/j.apcata.2025.120518","DOIUrl":"10.1016/j.apcata.2025.120518","url":null,"abstract":"<div><div>Toluene is a representative liquid organic hydrogen carrier (LOHC) with favorable thermodynamic and physical properties for reversible hydrogen storage. In this study, we report the synthesis of Ru-based catalysts supported on SiO₂ materials (SBA-15 and commercial SiO₂), surface-functionalized with succinamic acid to improve nanoparticle anchoring and metal utilization. Characterization confirmed the successful incorporation of carboxylic groups via a ring-opening grafting approach, leading to significant enhancements in Ru dispersion and stabilization. The Ru/SBA15-AC catalyst exhibited a narrow particle size distribution centered at 4 nm and a dispersion of 32 %. Catalytic tests revealed high activity and total toluene hydrogenation, with the Ru/SBA15-AC system achieving, after 3 h of reaction, a hydrogen storage capacity of 5.2 wt% and a TOF of 639 min⁻¹—outperforming most reported Ru-based catalysts under comparable conditions. Apparent activation energies (Eₐₐ) for all catalysts, determined from Arrhenius analysis, revealed that Ru/SBA15-AC exhibited the lowest value (41 kJ mol⁻¹). The combination of mesoporosity and carboxylic functionality appears to synergistically promote both Ru dispersion and the stabilization of highly active Ru species, which is reflected in the lower energy barrier for hydrogenation. Notably, the catalyst retained its structural integrity and activity over ten consecutive reaction cycles, as confirmed by post-reaction HR-TEM and recyclability assays. In addition to toluene, the Ru/SBA15-AC catalyst also demonstrated effective hydrogenation of other relevant LOHCs, including naphthalene, 2-methylindole, and 9-ethylcarbazole, highlighting its versatility across structurally diverse hydrogen carriers. While a complete LOHC cycle requires both hydrogenation and dehydrogenation steps, this work focused on the hydrogenation half-cycle to elucidate the role of support functionalization on catalyst efficiency and durability.These findings demonstrate that succinamic acid-modified SiO₂ supports represent a robust platform for designing recyclable, atom-efficient Ru catalysts, offering a promising pathway for practical hydrogen storage in LOHC systems.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120518"},"PeriodicalIF":4.8,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144890170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning iron loading and specific surface area in iron-containing clays for the oxidative photodegradation of 4-nitrophenol","authors":"Keltoum Tiar ,&nbsp;Ahcène Soualah ,&nbsp;Chiara Bisio ,&nbsp;Stefano Marchesi ,&nbsp;Valeria Pappalardo ,&nbsp;Stefano Econdi ,&nbsp;Matteo Guidotti","doi":"10.1016/j.apcata.2025.120522","DOIUrl":"10.1016/j.apcata.2025.120522","url":null,"abstract":"<div><div>The photocatalytic degradation of the persistent organic pollutant 4-nitrophenol (4-NP) was evaluated using a series of iron-containing clays, including montmorillonite K10 (M-K10), iron-exchanged M-K10 (Fe-MMT), natural mineral bentonite (raw bentonite), and acid-activated bentonite, prepared under various treatment conditions. The highest conversion of 4-NP under UV light and in the presence of H₂O₂ reached 96 %, 94 % and 90 % for M-K10, Fe-MMT and BAN1 (bentonite treated with HNO₃ for 1 h), respectively, after 90 min of reaction. The rate of 4-NP removal followed pseudo-first order kinetics with constants of 3.519 × 10⁻² min⁻¹, 3.325 × 10⁻² min⁻¹ and 2.803 × 10⁻² min⁻¹ for M-K10, Fe-MMT and BAN1, respectively. The high efficiency of the catalysts tested is attributed to the specific surface area and iron content of the clays. Free radical quenching experiments confirmed the involvement of hydroxyl (^.OH) and superoxide anion (^.O₂^-) radicals in the photocatalytic degradation process, indicating the occurrence of heterogeneous photo-Fenton-like reactions. Furthermore, M-K10 exhibited excellent stability and reusability over five consecutive reaction cycles without significant loss in activity. These findings demonstrate the potential of iron-containing clays as efficient, non-toxic, and low-cost catalysts for the photocatalytic degradation of recalcitrant pollutants in sustainable and green wastewater treatment processes.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120522"},"PeriodicalIF":4.8,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144893060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective hydrogenolysis of methylcyclopentane with excess methylcyclohexane over Ir-encapsulated silicalite-1","authors":"Satoshi Inagaki ,&nbsp;Keiju Tokita ,&nbsp;Kento Kondo ,&nbsp;Taishi Miura ,&nbsp;Yuko Nishi ,&nbsp;Norihito Sakaguchi ,&nbsp;Toru Murayama ,&nbsp;Yoshihiro Kubota","doi":"10.1016/j.apcata.2025.120517","DOIUrl":"10.1016/j.apcata.2025.120517","url":null,"abstract":"<div><div>The catalytic interconversion between methylcyclohexane (MCH) and toluene is highly promising for utilization as a liquid organic hydrogen carrier (LOHC) system. However, the inevitable isomerization of MCH promoted over the Pt/Al₂O₃ catalyst yields undesirable five-membered ring compounds such as dimethylcyclopentanes (DMCPs) and ethylcyclopentane (ECP). In this study, we developed a method for the preparation of Ir-encapsulated silicalite-1 catalyst for the selective hydrogenolysis of methylcyclopentane (MCP), a model compound of five-membered ring isomers, in the presence of excess MCH. Ir^<em>n</em>+/silicalite-1 was synthesized hydrothermally using tetra-<em>n</em>-propylammonium (^<em>n</em>Pr₄N⁺) hydroxide as the organic structure-directing agent. The as-prepared sample was treated under H₂ flow at 400 °C to promote the reduction of cationic Ir to highly dispersed Ir⁰ clusters in the micropores, and the Ir⁰ clusters then catalyze the hydrogenolysis of the ^<em>n</em>Pr₄N⁺ molecules inside the micropores, yielding Ir⁰/silicalite-1 catalyst with adequate microporosity. The diffusion coefficient of MCP in the 10-ring channels is two orders of magnitude greater than that of MCH, resulting in the molecular-sieving effect for the mixture of MCP and MCH over the silicalite-1 particles. Therefore, Ir⁰/silicalite-1 catalyst prepared in this study promoted selective hydrogenolysis of MCP even in the presence of excess MCH at 200 °C and showed lower deactivation, making it highly promising for the removal for DMCPs and ECPs from MCH to enable its use as an LOHC in hydrogen transportation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120517"},"PeriodicalIF":4.8,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144895705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}