Applied Catalysis A: General最新文献

{"title":"Fabricating highly dispersed and stable LaMnO3 perovskite oxide catalysts for selective aerobic oxidation of toluene to benzoic acid under solvent-free conditions","authors":"Jiahe Shan,&nbsp;Xuemei Jing,&nbsp;Chuchu Zhang,&nbsp;Enxian Yuan,&nbsp;Guojun Shi","doi":"10.1016/j.apcata.2025.120218","DOIUrl":"10.1016/j.apcata.2025.120218","url":null,"abstract":"<div><div>Chlorination-hydrolysis of toluene or homogeneous Co/Mn/Br catalyzed liquid phase oxidation of toluene to produce benzoic acid suffers from product halogen-contamination, severe equipment corrosion, and costly wastewater treatment industrially. Direct selective oxidation of toluene to benzoic acid under non-homogeneous catalyst, molecular oxygen, and solvent-free conditions will make this transformation more efficient and environmentally friendly. In this work, LaMnO₃ perovskite oxide catalysts were fabricated by sol-gel method followed by etching and heat treatment, and tested via selective aerobic oxidation of toluene to benzoic acid under solvent-free conditions. The etched LaMnO₃ perovskite oxide catalyst possesses a good mesoporous structure, significantly increased specific surface area and pore volume, halved grain size, reduced reduction temperature, and increased density of Mn^4 + ions and oxygen vacancies on the catalyst surface. Further heat treatment significantly improved the catalyst stability while sacrificing some textural properties. The LaMnO₃ perovskite oxide catalyst fabricated under the best conditions achieved a toluene conversion of 24.8 % and a benzoic acid selectivity of 82.7 %, with stable structural properties and catalytic performance after multiple cycles of use. This study can provide beneficial exploration and thinking for the design of perovskite oxide catalysts and their application in selective toluene oxidation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120218"},"PeriodicalIF":4.7,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143611232","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":"Insights into the mechanism of plasma pretreatment-enhanced ammonia decomposition kinetics from a lattice-mediated perspective","authors":"Yuhui Du ,&nbsp;Junhui Liang ,&nbsp;Xin Yao ,&nbsp;Huayu Chen ,&nbsp;Hongming Liu ,&nbsp;Hangning Chen ,&nbsp;Chenhao Du ,&nbsp;Liuqi Wang ,&nbsp;Yuexiang Huang ,&nbsp;Da Chen","doi":"10.1016/j.apcata.2025.120204","DOIUrl":"10.1016/j.apcata.2025.120204","url":null,"abstract":"<div><div>Fe, Co, Ni and other transition metal-based catalysts are widely applied in the catalysis field due to their unique d-orbital electronic configurations. However, transition metal/oxide catalysts face challenges such as metal particle aggregation and insufficient intrinsic activity during thermocatalytic ammonia decomposition reaction (ADR), which significantly limits their practical applications. Herein, we propose a high-energy ammonia plasma pretreatment strategy to disperse aggregated metal particles and introduce nitrogen-containing intermediates (such as NH and NH₂) into the catalyst lattice. This approach is designed to increase the exposure of active sites and regulate the dehydrogenation and N<img>N recombination pathways in the ADR via NH_<em>x</em> groups within the catalyst. The regulation method introduced NH and NH₂ intermediates, significantly enhancing the catalyst's ammonia decomposition performance. Results demonstrated that at 650℃ under a gas hourly space velocity (GHSV) of 9552 h⁻¹, the ammonia plasma-pretreated catalyst (Ni/Al₂O₃-PT) exhibited an 11 % higher conversion rate compared to the untreated Ni/Al₂O₃ achieving a hydrogen production rate of 6.59 mmol·g⁻¹_cat·min⁻¹ (versus 5.97 mmol·g⁻¹_cat·min⁻¹ for Ni/Al₂O₃). When the GHSV was increased to 19104 h⁻¹ at 550℃, Ni/Al₂O₃-PT showed a 16 % higher conversion rate than Ni/Al₂O₃. Long-term stability tests conducted over 50 h confirmed the excellent operational stability of the Ni/Al₂O₃-PT catalyst. Our work presented an efficient solution to the challenges of transition metal-based catalysts while providing a theoretical framework for novel catalyst design through a lattice-mediated intermediate evolution model.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120204"},"PeriodicalIF":4.7,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143611231","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 bonding effects assisted organic ammonium polyoxometalate salts catalysis for the selective oxidation of methacrolein and mechanism study","authors":"Chen Li,&nbsp;Hong Zhang,&nbsp;Siyao Gu,&nbsp;Wenlong Lu,&nbsp;Xinyu Chen,&nbsp;Liuliu Zhong,&nbsp;Hui Wan,&nbsp;Lei Wang,&nbsp;Guofeng Guan","doi":"10.1016/j.apcata.2025.120220","DOIUrl":"10.1016/j.apcata.2025.120220","url":null,"abstract":"<div><div>The selective oxidation of methacrolein (MAL) to methacrylic acid (MAA) is a key step in C4 oxidation for polymethyl methacrylate production, but the limited catalytic activity of polyoxometalates (POMs) hinders their industrial use. Here, we synthesized POM-IL hybrid catalysts via ion exchange and calcination. Ionic liquids disrupted the POM structure through hydrogen bonding, creating oxygen vacancies that optimized adsorption energy and prevented MAL over-oxidation to COx. The hydrogen bonding between ionic liquids and polyoxometalate anions, coupled with ammonium ions derived from ionic liquids, generated a synergistic effect that markedly improves the acidity and redox properties of the catalyst. The catalyst achieved 82.9 % MAL conversion, 88.9 % MAA selectivity, and exceptional stability over 80 h. In-situ infrared spectroscopy and partial density of states (PDOS) analysis identified Mo=Od as the active site, with ester intermediate formation as the rate-determining step. This study uncovers the influence of hydrogen bonding in ionic liquids on the structure-activity relationship of polyoxometalate anions, offering crucial insights into the mechanism of methacrolein selective oxidation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120220"},"PeriodicalIF":4.7,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143637705","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":"Synergistic effects of dehydrogenation component Cu and medium base on side chain alkylation of toluene with methanol","authors":"Zheng Cui ,&nbsp;Yueli Wen ,&nbsp;Bin Wang ,&nbsp;Maohong Fan ,&nbsp;Faraz Ahmad ,&nbsp;Hui Bai ,&nbsp;Wei Huang","doi":"10.1016/j.apcata.2025.120221","DOIUrl":"10.1016/j.apcata.2025.120221","url":null,"abstract":"<div><div>Activation of hydrogen atoms of methyl in toluene and methanol is crucial for side-chain alkylation of toluene with methanol. Herein, two strategies were applied, introducing dehydrogenation component (Cu) and tailoring the catalyst acid-base property with NaOH. A series of Cu and NaOH dual-modified PAl-NaX catalysts were prepared by in-situ hydrothermal method, the synergistic effect of Cu and NaOH was investigated. It is revealed that the product of (medium base)* (weak acid) and surface Cu^δ+ percentage is crucial in controlling the total yield of side chain alkylation products by enhancing ethyl benzene selectivity. Cat-3Cu-13Na exhibits the optimal catalytic performance with an average methanol conversion of 97.25 % and an average total yield of side chain alkylation products of 77.46 % without obvious deactivation occurs in 192 h, and Cat-3Cu-19Na shows a promising styrene selectivity of 44.06 %. The decrease of weak acid sites might result in the decline in selectivity of styrene.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120221"},"PeriodicalIF":4.7,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143601048","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":"Utilization of chitin and shrimp shell for selective acetic acid production using aluminum salts in aqueous media","authors":"Xiao Du ,&nbsp;Tengfei Li ,&nbsp;Lumei Wang ,&nbsp;Dezhang Ren ,&nbsp;Wenhui He ,&nbsp;Zhibao Huo","doi":"10.1016/j.apcata.2025.120202","DOIUrl":"10.1016/j.apcata.2025.120202","url":null,"abstract":"<div><div>In this paper, an alkali-free route for the conversion of chitin and shrimp shell to acetic acid (AA) using aluminum salts in aqueous media was reported for the first time. The proposed method demonstrated several advantages, including simplicity, effectiveness, and superior environmental and economic benefits compared to previous approaches. Notably, it achieved a significant breakthrough in the yields of AA derived from chitin and shrimp shells. Under the optimal conditions, the yield of AA reached the maximum value of 81.4 %. Combined with theoretical calculation and characterization, a possible transformation mechanism was proposed, and it was proved that the presence of aluminum salts would change the main reaction pathway and participate in the preparation of AA in the form of polymers. This study provided a novel idea for the resource utilization of chitin and waste shell materials into valuable chemicals and also for the treatment of environmental pollution.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120202"},"PeriodicalIF":4.7,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578049","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":"Elucidation of the surface pathways over MnOX based 3D printed monoliths for the catalytic oxidation of toluene: In-situ DRIFTS measurements","authors":"S.I. Suárez-Vázquez ,&nbsp;J.F. Ramírez-Lomán ,&nbsp;A. Cruz-López ,&nbsp;S. Gil","doi":"10.1016/j.apcata.2025.120209","DOIUrl":"10.1016/j.apcata.2025.120209","url":null,"abstract":"<div><div>This study provides a pioneering analysis of the surface reaction pathway during the catalytic oxidation of toluene on MnO_X-based 3D-printed monolithic catalysts. Four monoliths, including green monolith (support), CeO_X, MnO_X and MnCeO_X, were evaluated by DRIFT spectroscopy. These <em>in-situ</em> measurements allow us to elucidate the reaction pathways as a function of its surface compositions. Indeed, all monoliths favored the adsorption of toluene at low temperatures and the formation of several surface intermediates such as benzyl alcohol and some carboxylate species but, complete oxidation to CO₂, was only observed over the MnCeO_X at 300 °C. MnCeO_X monolith showed a mixture of Mn₃O₄ and CeO₂ crystalline phases identified by XRD and Raman with higher concentration of lattice oxygens according to XPS measurements. Thus, the presence of abundant lattice oxygen and reduced Mn and Ce species on the surface of MnCeO_X seems to be crucial for the complete oxidation of toluene. A reaction pathway has been proposed for this monolith involving the adsorption of toluene via the methyl group, followed by the sequential formation of benzyl alcohol, benzaldehyde and benzoate. The cleavage of the aromatic ring produced formate species, which were further converted to CO and CO₂. In addition, this work demonstrates that water not only competes for the same adsorption sites as toluene molecules, but also participates in the generation of reactive species, which significantly influences the overall oxidation process and the formation of intermediate species produced by the interactions of water species with organic compounds. Finally, it is important to mention that the monoliths evaluated in this work open up new opportunities for using 3D printing as a rapid and cost-effective method to enhance catalyst activity in real-world applications and decrease VOC emissions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120209"},"PeriodicalIF":4.7,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143611233","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":"NiOOH-coated BiVO4 for selective glycerol oxidation: Surface effects and pH-Bias voltage synergy","authors":"Wanggang Zhang ,&nbsp;Biaobiao Hao ,&nbsp;Qianrui Gao ,&nbsp;Yue Wang ,&nbsp;Xingzi Bian ,&nbsp;Haomin Gong ,&nbsp;Rufeng Tian ,&nbsp;Aili Wei ,&nbsp;Jian Wang ,&nbsp;Yiming Liu","doi":"10.1016/j.apcata.2025.120205","DOIUrl":"10.1016/j.apcata.2025.120205","url":null,"abstract":"<div><div>In this study, we significantly improved the PEC performance of glycerol oxidation by introducing an amorphous NiOOH co-catalyst onto BiVO₄ photoanodes. The effects of the bias voltage and pH on the selectivity of glycerol conversion products were meticulously investigated. The research demonstrated that increasing the bias voltage promoted glycerol oxidation, with an optimal voltage of 0.7 V leading to a significant increase in both the glycerol conversion rate and DHA selectivity, reaching up to 68 %. Additionally, pH played a critical role in the selectivity of glycerol oxidation products, with neutral to slightly alkaline conditions (pH=8) being the most conducive for DHA production. This study provides a promising strategy for sustainable glycerol valorization and offers a comprehensive understanding of the factors influencing PEC glycerol oxidation on NiOOH/BiVO₄ photoanodes.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120205"},"PeriodicalIF":4.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143577974","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":"Green synthesis of furan di-Schiff bases via a one-pot tandem amination-oxidation-amination process under room temperature","authors":"Xing-Long Li ,&nbsp;Shao-Jun Qing ,&nbsp;Xun Sun ,&nbsp;Zhen Yu ,&nbsp;Rui Zhu","doi":"10.1016/j.apcata.2025.120207","DOIUrl":"10.1016/j.apcata.2025.120207","url":null,"abstract":"<div><div>Furan-based double Schiff bases (DRIF), multifunctional molecules derived from biomass, were possessed significant application potential in various fields including sensors, stabilizers, dyes, and pharmaceuticals. The synthesis of DRIF typically involves a series of steps: amination, oxidation, and subsequent amination. However, this process could encounter side reactions such as overoxidation, aldol condensation, and cross-oligomerization. Herein, an efficient TEMPOL/Cu(NO₃)₂ catalytic system for one-pot process with 5-HMF and n-butylamine as model reactant to produce 2,5-di(butyliminomethyl)furan (DBIF) at room-temperature was developed. Characterization techniques including FT-IR, ESI-MS, GC-MS, and ¹H NMR were employed to identify key intermediates and reaction mechanisms. The maximum DBIF yield of 97 % was attained. Furthermore, the study extended the amine oxidation amination reactions using HMF and furfural with various primary amines, demonstrating good substrate compatibility. Ultimately, a one-pot two-step method was successfully employed to obtain a total yield of 63 % DBIF from fructose, further highlighting the application potential of this catalytic system.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120207"},"PeriodicalIF":4.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143577973","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":"Promotion effect of Al species on silica-supported cesium oxide catalyst in the vapor-phase dehydration of 1,2-propanediol to propylene oxide","authors":"Masafumi Morooka ,&nbsp;Enggah Kurniawan ,&nbsp;Junji Okamura ,&nbsp;Yusei Nagamura ,&nbsp;Takayoshi Hara ,&nbsp;Takashi Kojima ,&nbsp;Yasuhiro Yamada ,&nbsp;Satoshi Sato","doi":"10.1016/j.apcata.2025.120208","DOIUrl":"10.1016/j.apcata.2025.120208","url":null,"abstract":"<div><div>The introduction of Al into SiO₂-supported cesium oxide (Cs/SiO₂) promoted catalytic activity for the dehydration of 1,2-propanediol (1,2-PDO) to propylene oxide (PO). This improvement was attributed to the promotion of CsNO₃ decomposition and the ability of Al to keep the morphology of the SiO₂-supported catalyst, even though the Al component slightly reduced the concentration of the base site. The optimum molar component of Al was proven to improve the activity of Cs/SiO₂ catalyst, while maintaining a low rate of side reactions, such as isomerization of PO to allyl alcohol and dehydration of 1,2-PDO to propanal. Several parameters, such as reaction temperature, contact time, Cs₈Al₂ content, and Al molar component influenced catalytic activity and product distributions. The poisoning experiment by use of CO₂ revealed the importance of the base sites of Cs₈Al₂/SiO₂ catalyst, while the role of acid sites was negligible as confirmed by the poisoning experiment with NH₃.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120208"},"PeriodicalIF":4.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143611230","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Use of a 416B-type central-hybrid experimental design to evaluate the synthesis conditions of TiO2/biochar composites on the solid-state photocatalytic degradation of polypropylene-plastic films","authors":"Deyler Castilla-Caballero ,&nbsp;Astrid Medina-Guerrero ,&nbsp;Aracely Hernandez-Ramirez ,&nbsp;Sofia Vazquez-Rodriguez ,&nbsp;José Colina-Márquez ,&nbsp;Fiderman Machuca Martínez ,&nbsp;Juan Barraza-Burgos ,&nbsp;Aicardo Roa-Espinosa ,&nbsp;Sundaram Gunasekaran","doi":"10.1016/j.apcata.2025.120196","DOIUrl":"10.1016/j.apcata.2025.120196","url":null,"abstract":"<div><div>This study presents an innovative application of solid-state photocatalysis using environmentally friendly TiO₂/biochar composites to degrade polypropylene (PP) films and reduce plastic pollution. Biochar, derived from coconut shells via controlled pyrolysis, was combined with TiO₂ to enhance photocatalytic activity. A 416B-type Central-Hybrid Experimental Design was used to optimize synthesis parameters, revealing that biochar produced at 280°C with 4.1 % v/v oxygen and a TiO₂/biochar weight ratio of 1.5 yields the best results. After 25 days of UV irradiation, films incorporated with TiO₂/biochar composites exhibited an 8.7 % weight loss and a carbonyl index of 11.4—significantly surpassing pristine PP films. These findings demonstrate the potential of biochar as a sustainable solution to reduce nanotoxicity while boosting polymer degradation efficiency. This work contributes to the development of eco-friendly materials for mitigating plastic waste challenges.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120196"},"PeriodicalIF":4.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}