Applied Catalysis A: General最新文献

{"title":"CO2 fixation reaction over pyrimidinium-based dicationic ionic liquid in MIL-101(Cr)","authors":"Seyedeh Molood Masoom Nataj ,&nbsp;Serge Kaliaguine ,&nbsp;Frédéric-Georges Fontaine","doi":"10.1016/j.apcata.2025.120186","DOIUrl":"10.1016/j.apcata.2025.120186","url":null,"abstract":"<div><div>Modified metal-organic frameworks (MOFs) encapsulating new ionic N-heterocyclic-based functional groups, prepared via a ship-in-a-bottle approach, introduce a novel catalytic system for CO₂ conversion with epoxides. The <strong>MIL-101(Cr)</strong> framework was functionalized with novel ionic liquids (ILs) such as 1,5-bis(2-aminopyrimidinium)pentane bromide (2AMP-DBrP) and 1,5-bis(2-aminopyrimidinium)ethyl ether bromide (2AMP-DBrEE), resulting in cationic pyrimidinium-containing Cr-MOFs with free bromide ions, namely <strong>MIL101–2AMP-DBrP</strong> and <strong>MIL101–2AMP-DBrEE</strong>. Although the surface area (2456 and 2408 m²/g) and pore volume (1.44 and 1.41 cm³/g) of these encapsulated materials were reduced compared to pristine <strong>MIL-101(Cr)</strong> (3425 m²/g and 1.78 cm³/g), the CO₂ adsorption capacity at low pressure was notably increased (3.51 and 4.05 mmol g⁻¹ of CO₂). These modified MOFs demonstrated exceptional catalytic performance and stability in CO₂ fixation with various epoxides, achieving a high turnover frequency (TOF) of 82.5 h⁻¹ under mild conditions (0.1 MPa, 90 °C) without the need for co-catalysts or solvents, which are essential criteria for commercial viability. Moreover, <em>in situ</em> FTIR analysis suggests that the enhanced performance is due to CO₂ activation via carbamic acid formation facilitated by primary amino groups and epoxide activation through hydrogen bonding. This dual activation mechanism is critical for achieving high catalytic efficiency under mild conditions and underscores the innovative and significant advancements presented in this work compared to existing IL-MOFs.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"697 ","pages":"Article 120186"},"PeriodicalIF":4.7,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563337","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":"High efficient production of 5-hydroxymethyl-furfural from glucose over AACH @ γ-AlOOH catalyst: Insights into structure, acidic properties and performance","authors":"Zhe Tang ,&nbsp;Jilei Liang ,&nbsp;Jianhui Su","doi":"10.1016/j.apcata.2025.120184","DOIUrl":"10.1016/j.apcata.2025.120184","url":null,"abstract":"<div><div>A easy-to-handle and bi-functional solid water-tolerant catalyst with the balance of Brønsted acid site ( BAS) and Lewis acid site (LAS) is crucial for the efficient conversion of glucose into 5-hydroxymethylfurfural (HMF). In the work, the AACH@γ-AlOOH (designated as N_y@γ-AlOOH) catalysts were synthesized through the in-situ AACH substitution of γ-AlOOH, where the AlO₆ octahedral units served as the wate - tolerant LAS with mild acid strength, while the unsaturated AlO₅ pentahedral units acted as the weak BAS, together forming Lewis - Brønsted acid pairs at molecular- level proximity. Glucose turnover and HMF selectivity were enhanced due to the rapid fructose transfer from LAS to the adjacent BAS for its dehydration to HMF, facilitating LAS liberation for another glucose turnover. Under an optimized catalyst N_4/11@γ-AlOOH, a high HMF yield of 73.8 % was obtained in biphasic system of 1-butanol / H₂O - NaCl (20 wt%) at 140 °C for 3 h.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120184"},"PeriodicalIF":4.7,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509354","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":"Role of Cu and Ni in dual sites layered electrocatalysts for ammonia electrooxidation","authors":"Sara Sumbal,&nbsp;Justyna Łuczak,&nbsp;Afaq Hassan,&nbsp;Marek Lieder","doi":"10.1016/j.apcata.2025.120181","DOIUrl":"10.1016/j.apcata.2025.120181","url":null,"abstract":"<div><div>Single metal layered α-Ni(OH)₂, β-Ni(OH)₂ or dual metal layered NiCu hydroxides were hydrothermally deposited on nickel foam (NF) and investigated for electrochemical oxidation of ammonia. Copper induced conversion of hydrotalcite (α-Ni(OH)₂) phase into the mixed hydrotalcite/brucite (α/β-NiCu) structure, which is distinguished by smaller stacks and larger interplanar distances, demonstrated the highest catalytic performance. Copper inclusion resulted in two-fold increase in the current density (to 55.2 mA/cm² at 1.55 V <em>vs</em> RHE for α/β-NiCu_(1/1)) as well as significant increase in the electrochemical active surface area (387.5 cm²) and turnover frequency (0.56 1/cm²). The presence of Cu does not affect the onset potential of the reaction but elevated the overpotential of water oxidation, thereby increasing N₂ selectivity. We proposed formation of temporary vacancies on the copper sites during AOR, which allowed the adsorption of OH followed by their coupling with hydrogen atoms derived from NH_x molecules bound to nickel sites (dual-sites mechanism).</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120181"},"PeriodicalIF":4.7,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511662","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":"Skeletal isomerization of oleic acid on silica-coated ZSM-22","authors":"Xinyu Wei,&nbsp;Mingming Peng,&nbsp;Toshiya Tsunakawa,&nbsp;Yuyang Jia,&nbsp;Kenji Kamiya,&nbsp;Eika W. Qian","doi":"10.1016/j.apcata.2025.120182","DOIUrl":"10.1016/j.apcata.2025.120182","url":null,"abstract":"<div><div>To enhance the skeletal isomerization activity of the catalyst and increase the yield of branch chain unsaturated fatty acids (BUFAs) from oleic acid, a series of silica-coated ZSM-22 with different silica content were developed by crystal overgrowth. The patterns of XRD exposed that zeolitic framework structures of ZSM-22 were kept after silica coating. 2,6-lutidine adsorption FT-IR spectroscopy revealed that the acid sites on the external surface of silica-coated ZSM-22 samples were partially covered by silica layers. Regarding the influence of silica coating amount, 20Si·HZ-22(60) with 20 % silica content had a high BUFAs yield of above 80 % and more efficiently inhibited the formation of dimer acids compared to parent ZSM-22(60) without silica coating. Additionally, the suppression of dimer acid formation makes the catalyst less prone to deactivation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120182"},"PeriodicalIF":4.7,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519958","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":"Degradation of toluene by DBD plasma catalytic technology with CoMn-BTC/ Ti3C2Tx composites","authors":"Yucheng Liu ,&nbsp;Xinzhi Zang ,&nbsp;Songjian Zhao ,&nbsp;Zixuan Wang ,&nbsp;Wenqiang Wang ,&nbsp;Jingxin Xu ,&nbsp;Sheng Wang ,&nbsp;Zhaolian Ye","doi":"10.1016/j.apcata.2025.120180","DOIUrl":"10.1016/j.apcata.2025.120180","url":null,"abstract":"<div><div>Dielectric barrier discharge (DBD) plasma catalytic technology is considered as one of the most effective methods for elimination of diluted volatile organic compounds (VOCs) due to its advantages of high efficiency, low cost, and wide applicability. The design of highly efficient catalytic materials is a notable challenge for this technology. In this study, Ti₃C₂T_x, GO, and NiMn₂O₄, which possess a large specific surface area and high electron transport properties, were introduced as catalyst supports. These materials were combined with CoMn-BTC to synthesize three types of supported composite catalysts, which were used for the DBD-assisted VOCs degradation. Characterization analyses, including XRD, FTIR and SEM, indicated that CoMn-BTC was successfully integrated with the three supports. The large specific surface area and more oxygen vacancy for CoMn-BTC/Ti₃C₂T_x than bulk CoMn-BTC explained the enhanced toluene removal efficiency and mineralization, CO₂ selectivity, along with suppression of undesirable O₃ and NO_x. Characterization of CoMn-BTC/Ti₃C₂T_x catalysts before and after the plasma catalytic process indicated that high adsorbed oxygen species and the redox cycles between Co^3 +/Co²⁺ and Mn²⁺/(Mn⁴⁺, Mn³⁺) species can effectively promote toluene and intermediates oxidation. Furthermore, GC-MS analysis of the organic by-products in the effluent gas revealed that the amounts of intermediates such as nitrophenol reduced in the CoMn-BTC/Ti₃C₂T_x compared with CoMn-BTC, further demonstrating that CoMn-BTC/Ti₃C₂T_x had excellent catalytic activity. At last, the possible reaction pathways of toluene degradation in plasma-catalytic system was proposed in combination with analysis results of GC-MS, optical emission spectroscopy and properties of the catalyst before and after discharge reaction.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"695 ","pages":"Article 120180"},"PeriodicalIF":4.7,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143480443","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":"Electron-deficient boronic acid catalyzed cyclization of CO2 and epoxides","authors":"Xiaolin Jiang ,&nbsp;Liguang Zhang ,&nbsp;Shenglong Jiang ,&nbsp;Liwei Sun ,&nbsp;Yaru Zou ,&nbsp;Yuehui Li","doi":"10.1016/j.apcata.2025.120170","DOIUrl":"10.1016/j.apcata.2025.120170","url":null,"abstract":"<div><div>Utilizing CO₂ as an abundant and low-cost C1 resource for the production of value-added chemicals is of significant industrial interest. This work introduces a metal-free cyclization of CO₂ and epoxides into cyclic carbonates, catalyzed by electron-deficient, fluorine-substituted boronic acids under mild conditions. The catalysts demonstrate high activity and selectivity under mild condtions in non-polar solvents, with excellent compatibility with various functional groups such as heterocycle, alkene, phthalimide and chloride (13 examples, 53–95 % yields). The electron deficiency by F-substitution and the use of non-polar solvents enhance B-O interactions, allowing excellent catalytic performance and 6 times of catalyst recycling. This work highlights an effective strategy for CO₂ utilization, advancing recyclable boronic acid catalysts in green chemistry.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"695 ","pages":"Article 120170"},"PeriodicalIF":4.7,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463713","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":"Effect of Co occurrence state on catalytic and coke resistance performance of SAPO-34 in MTO reaction","authors":"Ning Li ,&nbsp;Jingbo Li ,&nbsp;Jianqiao Zhao ,&nbsp;Huili Liu ,&nbsp;Jiayun Tang ,&nbsp;Ruizhi Chu ,&nbsp;Xianliang Meng ,&nbsp;Weisong Li ,&nbsp;Xiao Li","doi":"10.1016/j.apcata.2025.120171","DOIUrl":"10.1016/j.apcata.2025.120171","url":null,"abstract":"<div><div>This paper prepared two different occurrence state of cobalt-modified SAPO-34 by impregnation and in situ synthesis, investigating effects on methanol-to-olefin reaction performance. The results showed that the Co modification improved the pore structure, increased the weak acid concentration, and extended the catalytic lifetime of SAPO-34. Among them, the framework-substituted Co-based zeolite has higher olefin selectivity and longer life than SAPO-34 with metal Co on the surface. Besides, the key coke precursors like methyl-substituted benzenes were preferentially deposited in micropores and strong acid sites, and significantly promote the generation of condensed ring aromatic hydrocarbons. While the relatively large mesopore volume and slightly lower strong acid concentration of the framework-substituted Co-based zeolite can synergize reduce the formation rate of coke and inhibit the formation of polycyclic aromatic hydrocarbons, thus improving SAPO-34's anti-coking performance. This revelation sparked a novel concept aimed at enhancing the anti-coking capabilities of metal-based zeolites.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"695 ","pages":"Article 120171"},"PeriodicalIF":4.7,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463712","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":"Modification of TiO2 anatase-rutile mixed-phase properties using Sn4+ doping for photocatalytic brilliant green degradation","authors":"Dorah Kawira Muthee ,&nbsp;Francis Birhanu Dejene ,&nbsp;Lawrence Kioko Munguti","doi":"10.1016/j.apcata.2025.120166","DOIUrl":"10.1016/j.apcata.2025.120166","url":null,"abstract":"<div><div>Compared to single-phase, the anatase-rutile TiO₂ phase has piqued researchers' interest. Incorporating a dopant into the microstructures of TiO₂ improves its properties. In contrast to the annealing method, incorporating Sn⁴⁺ into the lattice of TiO₂ allows the transformation from anatase to rutile at low temperature. The findings showed that ions containing the sulfate Sn⁴⁺ substituted that of Ti⁴⁺ in the TiO₂ lattice and dispersed in the matrix. The substitution caused the lattice structure to deform at low temperatures, causing the transformation of the phases. The increase in the mol% of Sn in TiO₂ lattice favored the rutile phase content. The narrowing of the bandgap caused by Sn doping significantly increases photocatalytic operation in the visible light. Consequently, near-contact phase junctions in between the anatase and rutile phase have been established, taking into consideration the charge separations. The sample at 5.5 mol% of Sn exhibited the highest photoactivity.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"695 ","pages":"Article 120166"},"PeriodicalIF":4.7,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143445190","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":"The alkylation of phenol with methanol: Conversion of anisole and two-step reaction process on X zeolites","authors":"Lei Li ,&nbsp;Xianlong Gao ,&nbsp;Fangtao Huang ,&nbsp;Lei Miao ,&nbsp;Guoqing Zhao ,&nbsp;Zhirong Zhu","doi":"10.1016/j.apcata.2025.120168","DOIUrl":"10.1016/j.apcata.2025.120168","url":null,"abstract":"<div><div>The alkylation of phenol with methanol reaction and anisole rearrangement were investigated on NaX zeolite and ion-exchange modified X zeolites with H⁺, K⁺, Cs⁺ and Mg²⁺. The product distribution of anisole rearrangement closely resembles that of the product distribution in the alkylation of phenol with methanol. This indicates that anisole is not only the primary product of the phenol alkylation reaction, but also serves as a key “intermediate” in the conversion of phenol to cresol. Based on the above results, a possible reaction pathway is proposed: the alkylation of phenol with methanol initially generates O-alkylation products, which then undergo rearrangement to form C-alkylation products. By employing a simple layered loading approach, the alkylation of phenol with methanol reaction was divided into two sequential steps. The results provided additional evidence for the feasibility of initially generating O-alkylation products in the alkylation of phenol with methanol and then converting them into C-alkylation products.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120168"},"PeriodicalIF":4.7,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509499","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":"Lanthanum incorporation in H-MOR zeolite to improve shape selectivity and stability against coke formation during the alkylation of toluene with isopropanol","authors":"Nabihan B. Abdul Rahman ,&nbsp;Ismaeel Alalq ,&nbsp;Matthew J. Wulfers ,&nbsp;Dan K. Nielsen ,&nbsp;Daniel E. Resasco ,&nbsp;Steven P. Crossley","doi":"10.1016/j.apcata.2025.120150","DOIUrl":"10.1016/j.apcata.2025.120150","url":null,"abstract":"<div><div>In aromatic alkylation over acidic zeolites, an optimal catalyst must exhibit shape selectivity for desirable products and resistance to coke formation, both of which can be enhanced by additives like lanthanum (La). This study examines the incorporation of La into H-MOR and its effects on shape selectivity and catalyst stability during the alkylation of toluene with isopropanol. La modifies the zeolite’s pore size and Brønsted acidity, improving reaction selectivity and coke resistance. The results show that La enhances para-selectivity while suppressing ortho-selectivity by inhibiting the formation of bulkier products, either by altering transition states in isomer formation or restricting isomer diffusion within the zeolite channels. Additionally, La-MOR demonstrates greater coke resistance, as La promotes hydrogen transfer from coke precursors to surface carbenium ions and titrates Brønsted acid sites, reducing olefin oligomerization. These findings highlight La’s potential for tuning zeolite properties to enhance catalytic performance.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"695 ","pages":"Article 120150"},"PeriodicalIF":4.7,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143445189","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}