Reaction Kinetics, Mechanisms and Catalysis最新文献

{"title":"N-heterocyclic carbene-palladium complex immobilized on Co-MOF 74 microrods as a highly selective catalyst for Suzuki–Miyaura cross-coupling","authors":"Duygu Hacıefendioğlu,&nbsp;Ali Tuncel","doi":"10.1007/s11144-024-02777-w","DOIUrl":"10.1007/s11144-024-02777-w","url":null,"abstract":"<div><p>A new reusable, heterogeneous catalyst for Suzuki–Miyaura cross-coupling (SMC) was designed. For the synthesis of catalyst carrying Pd(II)-NHC complex as the active site, Co(II)-2,5-dihydroxyterephthalic acid based metal–organic framework microrods (Co-MOF 74 MRs) was selected as the support. Highly porous Co-MOF 74 microrods with a surface area of 407.6 m²/g was obtained by a hydrothermal protocol conducted at 100 °C, using Co(NO₃)₂⋅6H₂O and 2,5-dihydroxyterephthalic acid (DHTPA) as the metal salt and the organic linker with two hydroxyl functionalities. Co-MOF 74 microrods was particularly selected as the support since two hydroxyl functionalities allowed the generation of Pd(II)-N-heterocyclic carbene complex (Pd(II)-NHC) on their surface via a facile chemical route started by silanization. Hence, Pd(II)-NHC complex was obtained on Co-MOF 74 MRs via silanization of Co-MOF-74 using 3-chloropropyltrimethoxysilane, quaternization of bound chlorine moiety with 1-methylimidazole and the reaction of Pd(II) salt with the quaternary ammonium functionality obtained at the last stage. The effects of cross-coupling conditions such as Pd(II) loading, mass of catalyst, temperature, base type, and type of substituent on arylbenzene or phenylboronic acid on biphenyl (BP) formation yield were investigated with the synthesized catalyst. BP formation yields ranging between 90 and 100% w/w, indicating high selectivity in SMC reaction were achieved in most of the entries performed with different combinations of experimental conditions using Pd(II)-NHC@Co-MOF 74 as the heterogeneous catalyst. The cross-coupling reaction rates calculated at different reaction times demonstrated that the rate of obtained using Pd(II)-NHC@Co-MOF 74 as the catalyst was high, particularly in the first 10 min and the reaction largely completed in one hour with high biphenyl formation yields when the catalyst amount was satisfactorily high. No significant decrease was observed in BP formation yield over six consecutive catalytic runs. The selected MOF based support with multiple hydroxyl functionality and the silanization route proposed for generation of active site is also a promising configuration that can be evaluated for the synthesis of new heterogeneous catalysts for various organic reactions including SMC.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 3","pages":"1363 - 1380"},"PeriodicalIF":1.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144135320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comparative impact of acidified glycerol pretreatment on the thermal degradation kinetics of crude wheat straw for potential sustainable valorization","authors":"Hamayoun Mahmood,&nbsp;Ali Raza,&nbsp;Muhammad Raashid,&nbsp;Atif Khan,&nbsp;Saqib Mehmood","doi":"10.1007/s11144-024-02790-z","DOIUrl":"10.1007/s11144-024-02790-z","url":null,"abstract":"<div><p>The relative impact of acidified glycerol pretreatment on thermal disintegration kinetics and thermodynamic parameters of crude wheat straw (WS) was studied using thermogravimetric analysis coupled with Horowitz-Metzger kinetic method under numerous reaction models. The WS fiber was dissolved in acidified glycerol solution under gentle pretreatment conditions of 90 °C for 30 min and was also pretreated by conventional methods including dilute alkaline, acid and hot water to foster a better insight and compare the capability of acidified glycerol for pretreatment of WS fiber. The apparent activation energy values of 27.8–31.8 kJ/mol and 32.3–38.2 kJ/mol were obtained for untreated and glycerol treated WS fibers, whereas the highest values, ranging from 36.2 to 42 kJ/mol, were obtained for alkali treated fiber. The change in enthalpy (ΔH°) for untreated WS fiber was within the range of 50.9 to 59.3 kJ/mol. This was enhanced to 59.8–71.6 kJ/mol, 63.6–74.0 kJ/mol and 63.1–74.9 kJ/mol for acidified glycerol, acid and alkali treated WS fibers. Pretreatment with acidified glycerol and alkali reagents increased the ΔG° values of WS fiber to 181.2 kJ/mol and 178.6 kJ/mol, in contrast to the value of 167.7 kJ/mol for untreated sample.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 3","pages":"1409 - 1425"},"PeriodicalIF":1.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144135322","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Limonene oxide isomerization: a broad study of acid catalyst effects","authors":"Anna Rejzková,&nbsp;Eliška Vyskočilová","doi":"10.1007/s11144-024-02774-z","DOIUrl":"10.1007/s11144-024-02774-z","url":null,"abstract":"<div><p>In this work, a broad screening of possible catalysts for limonene oxide isomerization was performed. The catalysts included both Brønsted and Lewis acids as homogeneous or heterogeneous catalysts. The aim was to show the efficiency of different catalysts in the studied reaction and use one homogeneous (methanesulfonic acid) and two heterogeneous (zeolite beta-25, montmorillonite K10) catalysts to evaluate the influence of the acid site type on the selectivity. When the selected catalysts were used, almost total conversion up to 1 h was observed (2?50% of the catalyst was based on type, 80 °C, and 16.6 V% of the solution was limonene oxide in toluene). The strength of the acid/acid catalyst influenced the composition of the products. When a strong acid (methanesulfonic acid) was used, the products formed by dehydration (<i>p</i>-cymene) and isomerization of the double bond (carvenone) were detected in large amounts. Using the majority of catalysts, the main products were <i>cis</i>- and <i>trans</i>-dihydrocarvone, and the minor products were carveols and carvone. The water content of the acid catalyst strongly affected the selectivity. Limonene diol was formed as a hydration product, which decreased the selectivity for the desired products. We have described a wide spectrum of possible catalysts for limonene isomerization. Moreover, our study enables the simple choice of catalyst on the basis of the desired composition of the products.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 1","pages":"47 - 69"},"PeriodicalIF":1.7,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11144-024-02774-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"N-doped carbon dots/MnO2 composite for the efficient catalytic reduction of malachite green and methyl violet","authors":"M. Shanti,&nbsp;S. Shylaja,&nbsp;Gaddameedi Hima Bindu,&nbsp;Mohammed Areef","doi":"10.1007/s11144-024-02767-y","DOIUrl":"10.1007/s11144-024-02767-y","url":null,"abstract":"<div><p>Here in, N-doped carbon dots/MnO₂ (NCDs/MnO₂) composite was synthesized via a facile one-pot method, utilizing the reducing properties of NCDs to convert KMnO₄ into MnO₂. Characterization techniques, including XPS, TEM, FTIR, and XRD, confirmed the successful formation of the composite. The catalytic performance of the NCDs/MnO₂ composite was evaluated for the reduction of malachite green (MG) and methyl violet (MV) dyes in the presence of NaBH₄. The composite exhibited excellent catalytic activity with over 96.0% MV reduction in 14 min and 96.5% MG was reduced in 12 min. Kinetic studies revealed pseudo-first-order reaction kinetics, with rate constants of 0.2087 ± 0.0113 min⁻¹ for MV and 0.1288 ± 0.0083 min⁻¹ for MG. Moreover, the composite demonstrated excellent reusability, maintaining high catalytic efficiency over multiple cycles. These findings highlight the potential of the NCDs/MnO₂ composite as a promising and sustainable catalyst for the treatment of dye-contaminated wastewater, contributing to environmental remediation efforts.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 1","pages":"347 - 359"},"PeriodicalIF":1.7,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular dynamics simulation of methane dehydrogenation on clusters of Cu4 and Cu3M (M@Fe,Co,Ni) alloys","authors":"Hong-Xia Liu,&nbsp;Xiaoze Sun,&nbsp;Ling Fu,&nbsp;Chao-Zheng He","doi":"10.1007/s11144-024-02773-0","DOIUrl":"10.1007/s11144-024-02773-0","url":null,"abstract":"<div><p>In this study, density functional theory was used to study the adsorption and activation capacity of methane dehydrogenation catalyzed by tetramer metal and tetramer metal alloy. The calculation results showed that Cu₃M (M@Fe, Co, Ni) alloy enhanced the adsorption capacity of reactants and intermediates compared with Cu₄. The energy barriers of methane dehydrogenation on Cu₄, Cu₃Fe, Cu₃Co and Cu₃Ni are calculated as 34.1, 21.3, 10.4 and 16.2 kJ/mol. The doping of Fe, Co and Ni improves the catalytic reduction ability of Cu₄, in which Cu₃Fe, Cu₃Co and Cu₃Ni alloys are beneficial to the dehydrogenation of methane to H₂. The kinetic calculation results show that the methane dehydrogenation reaction is endothermic under the action of Cu₄ and Cu₃M alloy catalysts. These theoretical results provide theoretical reference data for finding new methane dehydrogenation catalysts, and have theoretical and application value.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 3","pages":"1887 - 1902"},"PeriodicalIF":1.7,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144135483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nitrogen doping of materials with melamine for proton exchange membrane fuel cells: Pre-treatment of carbon support or post treatment of the electrocatalyst","authors":"Pınar Çelik,&nbsp;Ayşe Bayrakçeken","doi":"10.1007/s11144-024-02775-y","DOIUrl":"10.1007/s11144-024-02775-y","url":null,"abstract":"<div><p>In this study, two different routes were followed for nitrogen doping and compared with each other. In the first route, carbon support was nitrogen doped (Method 1). In the second route, firstly, carbon supported Pt catalysts were synthesized, and then these electrocatalysts were nitrogen doped (Method 2). Physical characterizations including elemental analysis, inductively coupled plasma mass spectrometer (ICP-MS), Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, Brunauer–Emmett–Teller (BET) analysis, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), contact angle measurement, and PEM fuel cell performance tests were performed. In Method 1, Pt/C:M-4:1/Pre catalyst showed the current density of 235.5 mA/cm² @0.6 V and a max. power density of 160.5 mW/cm². In Method 2, Pt/C:M-1:1/Post electrocatalyst had the current density of 626.0 mA/cm² @0.6 V and a max. power density of 374.3 mW/cm². Maximum power density obtained for Method 2 was 2.3 times higher than the electrocatalyst prepared with Method 1. Overall, it was observed that nitrogen doping of the electrocatalyst gave better result than nitrogen doping of the support material.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 3","pages":"1241 - 1258"},"PeriodicalIF":1.7,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144135480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Observation of an order change during the course of a reaction in a kinetic study of the reduction of trans-dicyanodibromoaurate(III) by octacyanotungstate(IV) in an acidic medium","authors":"Jannie C. Swarts,&nbsp;C. Robert Dennis","doi":"10.1007/s11144-024-02743-6","DOIUrl":"10.1007/s11144-024-02743-6","url":null,"abstract":"<div><p>The reduction of dibromodicyanoaurate(III) ion by octacyanotungstate(IV) ions was studied under near stoichiometric conditions in an acidic medium. An order change occurred during the course of the reaction. The reaction was first order in Au(CN)₂(Br)₂^– and second order in W(CN)₈^4– for the first half-life, but after ca. 60% conversion became first order in both reactants. The order change is ascribed to two different Au^II intermediates that form during the reaction course. A third order rate constant of k₃ = 7.80 × 10⁵ M⁻² min⁻¹ and a second order rate constant of k₂ = 108 M⁻¹ min⁻¹ was found at [H⁺] = 1.633 × 10^–3 M, an ionic strength of I = 0.11 M (NaBr) and at 25.0 ± 0.1 °C for the reaction. The reaction rate decreases with increasing [H⁺] in the reaction mixture at low pH and an experimental pK_a of 1.80 ± 0.03 was found at 25.0 ± 0.1 °C for the deprotonation of HW(CN)₈^3–. The reaction rate is independent of [Br⁻] and decrease with addition of W(CN)₈^3– in the reaction mixture. Activation parameters have been obtained by a least-squares fit of the temperature data directly to the Eyring equation.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 1","pages":"31 - 45"},"PeriodicalIF":1.7,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11144-024-02743-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404255","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Steam-treated SAPO-18 with well-regulated acidity and excellent dimethyl ether to olefin conversion performance","authors":"You Gyong Ho,&nbsp;Song Chol Jong,&nbsp;Un Yong Paek,&nbsp;Songchol Hong","doi":"10.1007/s11144-024-02749-0","DOIUrl":"10.1007/s11144-024-02749-0","url":null,"abstract":"<div><p>The hydrothermally synthesized SAPO-18 catalyst was steam treated to investigate the catalytic performance in dimethyl ether to olefins (DTO) reaction. After steam treatment, micropores and mesopores were created on the SAPO-18 catalyst. To evaluate the catalytic activity of steamed SAPO-18, the DTO reaction was carried out at 673 K with weight hourly space velocity (WHSV) of 3.546 h⁻¹, and the steamed SAPO-18 (S-773) at 773 K exhibited excellent DTO conversion performance (single-run lifetime 5.5 h, light olefin selectivity 95.9%) with BET surface area of 737 m² g⁻¹, mesopore volume of 125 mm³ g⁻¹, total amount of acid sites of 533 µmol g⁻¹, and Brønsted/Lewis ratio of 0.97. The improvement of DTO stability can be attributed to the increased mesoporosity and significantly reduced total amount of acid sites (well- regulated Brønsted/Lewis ratio) after steam treatment of SAPO-18 catalyst.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 2","pages":"817 - 829"},"PeriodicalIF":1.7,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Controlled hydrogenation of furfural to furfuryl alcohol or cyclopentanone over Ni–P under mild conditions","authors":"Cheng-Long Wen,&nbsp;Ya-Lu Zhu,&nbsp;Liu-Jun Jin,&nbsp;Ji-Li Hou,&nbsp;Ping Liu","doi":"10.1007/s11144-024-02771-2","DOIUrl":"10.1007/s11144-024-02771-2","url":null,"abstract":"<div><p>Ni–P catalysts were synthesized by a simple method in an open system that could catalyze the conversion of furfural efficiently under mild conditions. Especially, furfuryl alcohol or cyclopentanone can be produced with high selectivity using Ni–P as the catalyst by adjusting the reaction conditions. Moreover, the effect of the initial P/Ni molar ratio in Ni–P on their furfural catalytic hydrogenation performance was investigated, and Ni–P-5 presents high selectivities to furfuryl alcohol (98.2%) and cyclopentanone (85.8%) under mild conditions. Compared with the reported series of Ni catalysts, Ni–P had a simple composition, easier preparation, and better catalytic performances.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 3","pages":"1427 - 1438"},"PeriodicalIF":1.7,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144135285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oxidative esterification of 1, 2-propanediol to methyl lactate over Au/CuxAlOy catalysts in methanol without the presence of a base","authors":"Weiguo Fang,&nbsp;Xiaohu Xie,&nbsp;Guixian Li,&nbsp;Yingying Fan,&nbsp;Junying Tian,&nbsp;Dongqiang Zhang","doi":"10.1007/s11144-024-02772-1","DOIUrl":"10.1007/s11144-024-02772-1","url":null,"abstract":"<div><p>A series of Au catalysts supported on different CuAl composite oxide supports were designed for the oxidative esterification of 1,2-propanediol to methyl lactate in an alkali-free methanol system. A conversion of 52.8% and a methyl lactate selectivity of 67.0% were obtained over the optimized Au/Cu_1.5AlO₃ catalyst under the conditions of 140 °C and 1.0 MPa O₂. The Au in the catalyst was revealed to be pivotal, providing the essential active sites necessary for the oxidative esterification of 1,2-propanediol. Moreover, the inclusion of Cu in the CuAl composite oxide support was discovered to markedly enhance the catalytic performance of the Au catalysts. The synergistic interaction between Au and Cu is posited to alter the electronic and geometric properties of the gold sites, thereby enhancing the catalyst's ability to oxidize the primary hydroxyl group of 1,2-propanediol. This strategic modification of the Au sites by Cu is instrumental in improving the selectivity for methyl lactate during the oxidative esterification process.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 2","pages":"947 - 965"},"PeriodicalIF":1.7,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}