Pub Date : 2026-01-02DOI: 10.1016/j.apcata.2026.120768
Claudio Araya-López , Claudio Contreras-Diaz , Juan Seguel , Adriana Blanco , Catherine Sepúlveda , Christoph Kubis , Christine Rautenberg , Stephan Bartling , Francisco Gracia , Néstor Escalona
In this work, Ni₂P supported on SiO₂ was investigated to evaluate the influence of particle size on the reductive amination of levulinic acid. The catalysts were prepared by incipient wetness impregnation and characterized by N₂ adsorption–desorption, H₂-TPD, XRD, CO-chemisorption, pyridine-FTIR, and XPS. Catalytic tests were carried out using aniline and 1-octylamine to produce the corresponding 5-methyl-1-substituted-2-pyrrolidones. The hydrogenation steps showed a clear volcano-type dependence on Ni₂P particle size. The catalyst containing 5 wt% Ni (8.8 nm) exhibited the highest hydrogenation turnover frequencies (TOFs) for both amines. However, the highest hydrogenation rate for the formation of 5-methyl-1-phenyl-2-pyrrolidone was obtained with the 5 wt% Ni catalyst, whereas the maximum rate for 5-methyl-1-octyl-2-pyrrolidone was achieved with the 3 wt% Ni catalyst (4.9 nm). These differences are attributed to particle-size-dependent hydrogen adsorption: smaller particles bind hydrogen too weakly, while larger particles adsorb it too strongly. Optimal catalytic performance is therefore obtained at intermediate particle sizes, where hydrogen adsorption and surface reactivity are balanced.
{"title":"Nickel phosphide catalysts for reductive amination reaction of levulinic acid into 5-methyl-1-substituted-2-pyrrolidones: Effect of nickel content","authors":"Claudio Araya-López , Claudio Contreras-Diaz , Juan Seguel , Adriana Blanco , Catherine Sepúlveda , Christoph Kubis , Christine Rautenberg , Stephan Bartling , Francisco Gracia , Néstor Escalona","doi":"10.1016/j.apcata.2026.120768","DOIUrl":"10.1016/j.apcata.2026.120768","url":null,"abstract":"<div><div>In this work, Ni₂P supported on SiO₂ was investigated to evaluate the influence of particle size on the reductive amination of levulinic acid. The catalysts were prepared by incipient wetness impregnation and characterized by N₂ adsorption–desorption, H₂-TPD, XRD, CO-chemisorption, pyridine-FTIR, and XPS. Catalytic tests were carried out using aniline and 1-octylamine to produce the corresponding 5-methyl-1-substituted-2-pyrrolidones. The hydrogenation steps showed a clear volcano-type dependence on Ni₂P particle size. The catalyst containing 5 wt% Ni (8.8 nm) exhibited the highest hydrogenation turnover frequencies (TOFs) for both amines. However, the highest hydrogenation rate for the formation of 5-methyl-1-phenyl-2-pyrrolidone was obtained with the 5 wt% Ni catalyst, whereas the maximum rate for 5-methyl-1-octyl-2-pyrrolidone was achieved with the 3 wt% Ni catalyst (4.9 nm). These differences are attributed to particle-size-dependent hydrogen adsorption: smaller particles bind hydrogen too weakly, while larger particles adsorb it too strongly. Optimal catalytic performance is therefore obtained at intermediate particle sizes, where hydrogen adsorption and surface reactivity are balanced.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120768"},"PeriodicalIF":4.8,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920724","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}
Pub Date : 2026-01-02DOI: 10.1016/j.apcata.2026.120769
Fatma Kizil , Halil İbrahim Önal , Khadichakhan Rafikova , Filiz Koyuncu , Nurgul Satybaldi̇yeva , Akbota Aronkyzy Aronova , Bagadat Selenova , Feyyaz Durap , Murat Aydemir
Transfer hydrogenation-mediated reduction of ketones to yield secondary alcohols, which leads to the production of commercially important fine chemicals, is more favorable compared to conventional hydrogenation reactions. This research explores the effects of different Ru(0) nanoparticle loadings synthesized by treating a cryptomelane-type manganese oxide framework (K-OMS-2), which were characterized by advanced analytical methods including FT-IR, XRD, XPS, BET, SEM-EDX, and HR-TEM-EDX. The catalytic activity of Ru(0)@K-OMS-2 nanocatalyst was investigated in the transfer hydrogenation reaction of ketones. According to the catalytic results, Ru(0)@K-OMS-2 (3.0 %) catalyst containing 3 wt% Ru showed higher efficiency, high selectivity and high conversion (97 %) in transfer hydrogenation compared to other catalysts prepared in this study.
{"title":"Catalytic performance of Ru(0) nanoparticles supported on K-OMS-2 in transfer hydrogenation reactions","authors":"Fatma Kizil , Halil İbrahim Önal , Khadichakhan Rafikova , Filiz Koyuncu , Nurgul Satybaldi̇yeva , Akbota Aronkyzy Aronova , Bagadat Selenova , Feyyaz Durap , Murat Aydemir","doi":"10.1016/j.apcata.2026.120769","DOIUrl":"10.1016/j.apcata.2026.120769","url":null,"abstract":"<div><div>Transfer hydrogenation-mediated reduction of ketones to yield secondary alcohols, which leads to the production of commercially important fine chemicals, is more favorable compared to conventional hydrogenation reactions. This research explores the effects of different Ru(0) nanoparticle loadings synthesized by treating a cryptomelane-type manganese oxide framework (K-OMS-2), which were characterized by advanced analytical methods including FT-IR, XRD, XPS, BET, SEM-EDX, and HR-TEM-EDX. The catalytic activity of Ru(0)@K-OMS-2 nanocatalyst was investigated in the transfer hydrogenation reaction of ketones. According to the catalytic results, Ru(0)@K-OMS-2 (3.0 %) catalyst containing 3 wt% Ru showed higher efficiency, high selectivity and high conversion (97 %) in transfer hydrogenation compared to other catalysts prepared in this study.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120769"},"PeriodicalIF":4.8,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920723","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}
Pub Date : 2025-12-31DOI: 10.1016/j.apcata.2025.120764
Xiang Li , Li Zhu , Biyuan Liu , Akther Umma Habiba , Junjun Wang , Xianliang Fu , Man Xu
Compared to the traditional thermal catalyst, the exploration of the photocatalyst carriers has not attracted much attention. This will be detrimental to the application of photocatalytic technology from the perspective of the cost and the convenience. For this consideration, ZnSn(OH)6 (ZHS), which exhibits high activity for the degradation of benzene homologs, was used as a photocatalyst prototype. The loading of ZHS on a promising support, fused quartz sands (FQS), was then prepared using a hydrothermal method. The resulted samples showed higher activity for the degradation of gaseous toluene than other supports-loaded samples, including activated carbon, TiO2, and quartz sands, and even better than the self-supported pristine ZHS. For 200 ppm gaseous toluene, it can be fully degraded over 5 % ZHS/FQS sample under flow reaction mode (30 mL/min) with the residence time of only 1.8 s and the corresponding conversion and mineralization efficiencies are as high as 100 % and 82 %, respectively. The superior performance can be ascribed to the high dispersion of ZHS on FQS and the enhanced UV absorption capacity. The oxidation of toluene is triggered by ·OH and ·O₂⁻· radicals, proceeding through a sequential pathway where toluene is first converted to benzyl alcohol, then to benzaldehyde and benzoic acid, and ultimately oxidized to CO₂ and H2O. Through this strategy, the supported photocatalyst can be readily used in practical scenarios with only a small loading amount of 5 % ZHS. We believed that, besides ZHS, FQS would also be competent as a carrier for other photocatalysts.
{"title":"A promising photocatalyst support based on fused quartz sands: Loading ZnSn(OH)₆ for gaseous toluene abatement","authors":"Xiang Li , Li Zhu , Biyuan Liu , Akther Umma Habiba , Junjun Wang , Xianliang Fu , Man Xu","doi":"10.1016/j.apcata.2025.120764","DOIUrl":"10.1016/j.apcata.2025.120764","url":null,"abstract":"<div><div>Compared to the traditional thermal catalyst, the exploration of the photocatalyst carriers has not attracted much attention. This will be detrimental to the application of photocatalytic technology from the perspective of the cost and the convenience. For this consideration, ZnSn(OH)<sub>6</sub> (ZHS), which exhibits high activity for the degradation of benzene homologs, was used as a photocatalyst prototype. The loading of ZHS on a promising support, fused quartz sands (FQS), was then prepared using a hydrothermal method. The resulted samples showed higher activity for the degradation of gaseous toluene than other supports-loaded samples, including activated carbon, TiO<sub>2</sub>, and quartz sands, and even better than the self-supported pristine ZHS. For 200 ppm gaseous toluene, it can be fully degraded over 5 % ZHS/FQS sample under flow reaction mode (30 mL/min) with the residence time of only 1.8 s and the corresponding conversion and mineralization efficiencies are as high as 100 % and 82 %, respectively. The superior performance can be ascribed to the high dispersion of ZHS on FQS and the enhanced UV absorption capacity. The oxidation of toluene is triggered by ·OH and ·O₂⁻· radicals, proceeding through a sequential pathway where toluene is first converted to benzyl alcohol, then to benzaldehyde and benzoic acid, and ultimately oxidized to CO₂ and H<sub>2</sub>O. Through this strategy, the supported photocatalyst can be readily used in practical scenarios with only a small loading amount of 5 % ZHS. We believed that, besides ZHS, FQS would also be competent as a carrier for other photocatalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120764"},"PeriodicalIF":4.8,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880358","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}
The efficient utilization of red light, which is characterized by its relatively low energy, minimal health risks, high penetration depth in the reaction medium, and high abundance in the solar spectrum, represents a significant and challenging task in the field of organic transformations. In this study, a novel composite consisting of lead-free Cs3Bi2Br9 (CBB) perovskite and PCN-224 was successfully synthesized and comprehensively characterized through a series of standard techniques. The as-designed CBB/PCN-224 heterojunction exhibits remarkable catalytic activity for the red-light-induced acetylation of aryl diazonium salts with acetonitrile. In this reaction, acetonitrile serves as the acylating agent, and the entire process can be carried out at room temperature. This mild synthetic protocol features a broad substrate scope, enabling the synthesis of a wide range of N-arylacetamides with high to excellent yields. Furthermore, the CBB/PCN-224 composite demonstrates good recyclability. It can be reused for up to five consecutive reaction cycles without a significant loss of its photocatalytic activity, highlighting its potential for practical applications in photo-redox chemical reactions.
{"title":"Near-infrared light-driven synthesis of N-arylacetamides over Cs3Bi2Br9 perovskite/PCN-224","authors":"Shuai-Zheng Zhang, Jia-Hao Li, Ming-Ming Li, Zhan-Hui Zhang","doi":"10.1016/j.apcata.2025.120763","DOIUrl":"10.1016/j.apcata.2025.120763","url":null,"abstract":"<div><div>The efficient utilization of red light, which is characterized by its relatively low energy, minimal health risks, high penetration depth in the reaction medium, and high abundance in the solar spectrum, represents a significant and challenging task in the field of organic transformations. In this study, a novel composite consisting of lead-free Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub> (CBB) perovskite and PCN-224 was successfully synthesized and comprehensively characterized through a series of standard techniques. The as-designed CBB/PCN-224 heterojunction exhibits remarkable catalytic activity for the red-light-induced acetylation of aryl diazonium salts with acetonitrile. In this reaction, acetonitrile serves as the acylating agent, and the entire process can be carried out at room temperature. This mild synthetic protocol features a broad substrate scope, enabling the synthesis of a wide range of <em>N</em>-arylacetamides with high to excellent yields. Furthermore, the CBB/PCN-224 composite demonstrates good recyclability. It can be reused for up to five consecutive reaction cycles without a significant loss of its photocatalytic activity, highlighting its potential for practical applications in photo-redox chemical reactions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120763"},"PeriodicalIF":4.8,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880359","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}
Pub Date : 2025-12-30DOI: 10.1016/j.apcata.2025.120766
Yi Gan , Fangli Duan
In steel friction system, interfacial reactions can lead to the generation of atomic hydrogen that diffuses into the metal lattice, thereby inducing hydrogen embrittlement and significantly compromising service reliability. In this study, reactive force field molecular dynamics simulations were employed to investigate the friction-induced dehydrogenation behavior of 1-octene on iron (α-Fe(100)), iron sulfide (FeS), and amorphous iron oxide (a-Fe₂O₃) surfaces. The results revealed that on α-Fe(100) surfaces, 1-octene molecules can form Fe–C bonds with surface atoms, thereby catalyzing C–H bond cleavage and hydrogen release, exhibiting the lowest activation energy and the highest dehydrogenation yield. On the FeS surface, the partial passivation of active iron sites by sulfur atoms leads to a slight increase in the activation energy, resulting in a moderate reaction yield. Both geometric and electronic effects contribute to the largest activation volume observed for FeS. On a-Fe₂O₃ surfaces, the reactions proceeded primarily via two mechanisms, namely surface-stabilized and radical-like pathways. The facile dissociation of hydrogen atoms through the radical-like pathway results in the highest energy barrier and the lowest dehydrogenation yield. This study provides insights into the catalytic and passivation behaviors of iron and its compounds toward hydrocarbon molecules in lubricating oils under sliding friction conditions.
{"title":"Tribochemical dehydrogenation of 1-octene confined between iron-based surfaces: A ReaxFF molecular dynamics study","authors":"Yi Gan , Fangli Duan","doi":"10.1016/j.apcata.2025.120766","DOIUrl":"10.1016/j.apcata.2025.120766","url":null,"abstract":"<div><div>In steel friction system, interfacial reactions can lead to the generation of atomic hydrogen that diffuses into the metal lattice, thereby inducing hydrogen embrittlement and significantly compromising service reliability. In this study, reactive force field molecular dynamics simulations were employed to investigate the friction-induced dehydrogenation behavior of 1-octene on iron (α-Fe(100)), iron sulfide (FeS), and amorphous iron oxide (a-Fe₂O₃) surfaces. The results revealed that on α-Fe(100) surfaces, 1-octene molecules can form Fe–C bonds with surface atoms, thereby catalyzing C–H bond cleavage and hydrogen release, exhibiting the lowest activation energy and the highest dehydrogenation yield. On the FeS surface, the partial passivation of active iron sites by sulfur atoms leads to a slight increase in the activation energy, resulting in a moderate reaction yield. Both geometric and electronic effects contribute to the largest activation volume observed for FeS. On a-Fe₂O₃ surfaces, the reactions proceeded primarily via two mechanisms, namely surface-stabilized and radical-like pathways. The facile dissociation of hydrogen atoms through the radical-like pathway results in the highest energy barrier and the lowest dehydrogenation yield. This study provides insights into the catalytic and passivation behaviors of iron and its compounds toward hydrocarbon molecules in lubricating oils under sliding friction conditions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120766"},"PeriodicalIF":4.8,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880351","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}
Pub Date : 2025-12-30DOI: 10.1016/j.apcata.2025.120762
Qianran Sun , Yufan Ma , Qinqin Wang, Yuli Hou, Dekai Yuan, Bin Dai
The hydration of acetylene reaction represents a pathway with long-standing industrial strategic value in coal chemistry. However, the catalytic efficiency is hampered by inherent challenges such as the high inherent reactivity of acetylene, competitive adsorption on active sites, and an intricate network of parallel reactions that lead to byproducts. These factors make precise catalytic control over reaction selectivity paramount for achieving high target product yields. To address this, the classic metal-organic framework ZIF-8 and its pyrolytically derived Zn-N-C material were synthesized and systematically evaluated as catalysts for this transformation. Experimental results demonstrated that ZIF-8, featuring a Zn-N4 coordination structure, achieved an acetone selectivity of 87 %, whereas the Zn-NC material with a Zn-N3 coordination structure exhibited a acetaldehyde selectivity of 70 % under identical reaction conditions. XPS and XAFS analyses revealed that pyrolysis induced a transformation in the coordination environment of ZIF-8 from Zn-N4 to Zn-N3. DFT calculations further clarified the structure-selectivity relationship between coordination geometry and product distribution. Specifically, for ZIF-8 with Zn-N4 sites, β-ketobutyraldehyde decarbonylation served as the rate-determining step, featuring a lower energy barrier that favors acetone formation. In contrast, for Zn-NC with Zn-N3 sites, acetylene activation becomes the rate-determining step, and its lower energy barrier promotes acetaldehyde production. This work underscores the critical role of local coordination structures in acetylene hydration and offers a novel strategy for enhancing catalytic selectivity through precise modulation of the metal active center coordination environment.
{"title":"Switching the product selectivity of acetylene hydration by engineering the local coordination of Zn-Nx sites","authors":"Qianran Sun , Yufan Ma , Qinqin Wang, Yuli Hou, Dekai Yuan, Bin Dai","doi":"10.1016/j.apcata.2025.120762","DOIUrl":"10.1016/j.apcata.2025.120762","url":null,"abstract":"<div><div>The hydration of acetylene reaction represents a pathway with long-standing industrial strategic value in coal chemistry. However, the catalytic efficiency is hampered by inherent challenges such as the high inherent reactivity of acetylene, competitive adsorption on active sites, and an intricate network of parallel reactions that lead to byproducts. These factors make precise catalytic control over reaction selectivity paramount for achieving high target product yields. To address this, the classic metal-organic framework ZIF-8 and its pyrolytically derived Zn-N-C material were synthesized and systematically evaluated as catalysts for this transformation. Experimental results demonstrated that ZIF-8, featuring a Zn-N<sub>4</sub> coordination structure, achieved an acetone selectivity of 87 %, whereas the Zn-NC material with a Zn-N<sub>3</sub> coordination structure exhibited a acetaldehyde selectivity of 70 % under identical reaction conditions. XPS and XAFS analyses revealed that pyrolysis induced a transformation in the coordination environment of ZIF-8 from Zn-N<sub>4</sub> to Zn-N<sub>3</sub>. DFT calculations further clarified the structure-selectivity relationship between coordination geometry and product distribution. Specifically, for ZIF-8 with Zn-N<sub>4</sub> sites, β-ketobutyraldehyde decarbonylation served as the rate-determining step, featuring a lower energy barrier that favors acetone formation. In contrast, for Zn-NC with Zn-N<sub>3</sub> sites, acetylene activation becomes the rate-determining step, and its lower energy barrier promotes acetaldehyde production. This work underscores the critical role of local coordination structures in acetylene hydration and offers a novel strategy for enhancing catalytic selectivity through precise modulation of the metal active center coordination environment.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120762"},"PeriodicalIF":4.8,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880357","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}
Pub Date : 2025-12-25DOI: 10.1016/j.apcata.2025.120760
Juan J. Giraldo , Juliana Perez Espinoza , Cristian Díaz , Diana López , Sébastien Royer , Camila A. Teles , Frédéric Richard , Ruben Palacio
In this work, a series of bimetallic NiFe catalysts supported on SBA-15 silica and ZrO2/SBA-15 were synthesized for the hydrodeoxygenation of guaiacol with the aim of evaluating the chemical composition, Ni:Fe ratio, electronic properties of NiFe and solvent nature impact on conversion and selectivity. In hexadecane solvent at 300 ºC, catalysts containing ZrO2, Ni8.2Fe1.6-ZrO2/SBA-15 and Ni8.3Fe0.7-ZrO2/SBA-15, achieved high guaiacol conversion of 99.0 ± 0.5 % after 5 h of reaction and were selective toward cyclohexane, 23.2 % and 50.6 % respectively, but suffer from low carbon balance. For catalysts without ZrO2, Ni13.3Fe1.3/SBA-15 and Ni4.7Fe0.5/SBA-15, the conversion of guaiacol reached 84.8 ± 0.5 %, but the main product was cyclohexanol, reaching 91.5 % selectivity with Ni4.7Fe0.5/SBA-15 catalyst, and with high carbon balance of 96.5 % indicating low by-product/coke formation. At 250 ºC, the Ni4.7Fe0.5/SBA-15 catalyst reached a guaiacol conversion of 73.7 % and cyclohexanol selectivity of 57.3 %. This material exhibits nanoparticles (5.2 nm) with Ni and Fe in close contact, confined inside the mesopores of the SBA-15, and is the one showing the highest surface concentration of reduced nickel (Ni0). Results also showed that Fe3+ species modified the electronic structure of Ni0, that resulted in improved conversion and product selectivity compared to monometallic Ni-containing catalysts which exhibited lower catalytic activity. Using water as a solvent at 250 ºC resulted in a lower guaiacol conversion (36.5 % after 8 h under H2) but favored selectivity toward aromatics: catechol and phenol while retaining satisfying carbon balance (67.5 %).
{"title":"Bimetallic NiFe confined in SBA-15 for efficient guaiacol hydrodeoxygenation","authors":"Juan J. Giraldo , Juliana Perez Espinoza , Cristian Díaz , Diana López , Sébastien Royer , Camila A. Teles , Frédéric Richard , Ruben Palacio","doi":"10.1016/j.apcata.2025.120760","DOIUrl":"10.1016/j.apcata.2025.120760","url":null,"abstract":"<div><div>In this work, a series of bimetallic NiFe catalysts supported on SBA-15 silica and ZrO<sub>2</sub>/SBA-15 were synthesized for the hydrodeoxygenation of guaiacol with the aim of evaluating the chemical composition, Ni:Fe ratio, electronic properties of NiFe and solvent nature impact on conversion and selectivity. In hexadecane solvent at 300 ºC, catalysts containing ZrO<sub>2</sub>, Ni<sub>8.2</sub>Fe<sub>1.6</sub>-ZrO<sub>2</sub>/SBA-15 and Ni<sub>8.3</sub>Fe<sub>0.7</sub>-ZrO<sub>2</sub>/SBA-15, achieved high guaiacol conversion of 99.0 ± 0.5 % after 5 h of reaction and were selective toward cyclohexane, 23.2 % and 50.6 % respectively, but suffer from low carbon balance. For catalysts without ZrO<sub>2</sub>, Ni<sub>13.3</sub>Fe<sub>1.3</sub>/SBA-15 and Ni<sub>4.7</sub>Fe<sub>0.5</sub>/SBA-15, the conversion of guaiacol reached 84.8 ± 0.5 %, but the main product was cyclohexanol, reaching 91.5 % selectivity with Ni<sub>4.7</sub>Fe<sub>0.5</sub>/SBA-15 catalyst, and with high carbon balance of 96.5 % indicating low by-product/coke formation. At 250 ºC, the Ni<sub>4.7</sub>Fe<sub>0.5</sub>/SBA-15 catalyst reached a guaiacol conversion of 73.7 % and cyclohexanol selectivity of 57.3 %. This material exhibits nanoparticles (5.2 nm) with Ni and Fe in close contact, confined inside the mesopores of the SBA-15, and is the one showing the highest surface concentration of reduced nickel (Ni<sup>0</sup>). Results also showed that Fe<sup>3+</sup> species modified the electronic structure of Ni<sup>0</sup>, that resulted in improved conversion and product selectivity compared to monometallic Ni-containing catalysts which exhibited lower catalytic activity. Using water as a solvent at 250 ºC resulted in a lower guaiacol conversion (36.5 % after 8 h under H<sub>2</sub>) but favored selectivity toward aromatics: catechol and phenol while retaining satisfying carbon balance (67.5 %).</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120760"},"PeriodicalIF":4.8,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836470","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}
Pub Date : 2025-12-25DOI: 10.1016/j.apcata.2025.120761
Ziqiang Wang , Youxi Dong , Xin Zhang , Qi Wang , Yinmin Zhang , Yongfeng Zhang , Zhifei Hao
Modulating the electronic metal-support interaction (EMSI) has been widely recognized as an effective strategy for significantly enhancing the performance of noble metal catalysts in heterogeneous catalysis. However, studies aimed at further enhancing EMSI through the creation of metal vacancies on the support surface has been rarely reported in the field of volatile organic compounds (VOCs) oxidation. Herein, we develop a TiO2 support with abundant titanium vacancies (TiO2-VM) for the stable anchoring of well-dispersed platinum (Pt) nanoparticles. The as-prepared Pt/TiO2-VM catalyst is evaluated in the catalytic oxidation of toluene, demonstrating superior catalytic performance, including a low temperature (164 °C) for 90 % toluene conversion (T90), high CO2 selectivity, excellent long-term stability and water resistance. These performance improvements are mainly attributed to the strong electronic metal-support interaction (EMSI) at the Pt–support interface, which arises from the interaction between Pt species and titanium vacancies. Electron transfer from the TiO2-VM support to Pt through Pt-O-Ti bonding results in the formation of electron-enriched Pt⁰ species. Furthermore, the EMSI between the metal vacancies in the support and the Pt species imposes a confinement effect on the Pt nanoparticles, effectively suppressing their agglomeration and enhancing their dispersion. This study proposes a novel strategy for designing highly efficient supported catalysts through the regulation of EMSI to enhance the catalytic performance in VOCs abatement.
调节电子金属-载体相互作用（EMSI）已被广泛认为是提高贵金属催化剂多相催化性能的有效策略。然而，在挥发性有机化合物（VOCs）氧化领域，旨在通过在支撑表面产生金属空位来进一步提高EMSI的研究很少有报道。在此，我们开发了一种具有丰富钛空位的TiO2载体（TiO2- vm），用于稳定锚定分散良好的铂（Pt）纳米颗粒。制备的Pt/TiO2-VM催化剂在甲苯的催化氧化中进行了评价，表现出优异的催化性能，包括低温（164°C）达到90% %的甲苯转化率（T90），高CO2选择性，优异的长期稳定性和耐水性。这些性能的提高主要归因于Pt -支撑界面上的强电子金属-支撑相互作用（EMSI），这是由Pt和钛空位之间的相互作用产生的。通过Pt- o - ti键，电子从TiO2-VM载体转移到Pt，形成富电子Pt⁰。此外，载体中金属空位与Pt之间的EMSI对Pt纳米粒子施加了约束效应，有效地抑制了它们的团聚，增强了它们的分散。本研究提出了一种通过调节EMSI来设计高效负载型催化剂的新策略，以提高其在VOCs减排中的催化性能。
{"title":"Enhancing Pt-TiO₂ interaction via titanium defect-mediated electronic modulation for efficient toluene combustion","authors":"Ziqiang Wang , Youxi Dong , Xin Zhang , Qi Wang , Yinmin Zhang , Yongfeng Zhang , Zhifei Hao","doi":"10.1016/j.apcata.2025.120761","DOIUrl":"10.1016/j.apcata.2025.120761","url":null,"abstract":"<div><div>Modulating the electronic metal-support interaction (EMSI) has been widely recognized as an effective strategy for significantly enhancing the performance of noble metal catalysts in heterogeneous catalysis. However, studies aimed at further enhancing EMSI through the creation of metal vacancies on the support surface has been rarely reported in the field of volatile organic compounds (VOCs) oxidation. Herein, we develop a TiO<sub>2</sub> support with abundant titanium vacancies (TiO<sub>2</sub>-V<sub>M</sub>) for the stable anchoring of well-dispersed platinum (Pt) nanoparticles. The as-prepared Pt/TiO<sub>2</sub>-V<sub>M</sub> catalyst is evaluated in the catalytic oxidation of toluene, demonstrating superior catalytic performance, including a low temperature (164 °C) for 90 % toluene conversion (<em>T</em><sub><em>90</em></sub>), high CO<sub>2</sub> selectivity, excellent long-term stability and water resistance. These performance improvements are mainly attributed to the strong electronic metal-support interaction (EMSI) at the Pt–support interface, which arises from the interaction between Pt species and titanium vacancies. Electron transfer from the TiO<sub>2</sub>-V<sub>M</sub> support to Pt through Pt-O-Ti bonding results in the formation of electron-enriched Pt⁰ species. Furthermore, the EMSI between the metal vacancies in the support and the Pt species imposes a confinement effect on the Pt nanoparticles, effectively suppressing their agglomeration and enhancing their dispersion. This study proposes a novel strategy for designing highly efficient supported catalysts through the regulation of EMSI to enhance the catalytic performance in VOCs abatement.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120761"},"PeriodicalIF":4.8,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836533","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}
Pub Date : 2025-12-24DOI: 10.1016/j.apcata.2025.120759
Wenjuan Zhang , Panpan Zhang , Yezhi Ding , Zhongliang Li , Youliang Wang , Henan Jia , Zhiqi Feng , Peiqing La
As the global industry advances rapidly, organic pollutants in water have been posing threats to human health and ecosystems. Photo-Fenton oxidation has emerged as a promising way to degrade organic pollutants. Herein, we constructed MXene-derived bimetallic composites (3D TiO2/Ti3C2Tx@MCuFe-MOF) for the photo-Fenton degradation of methylene blue (MB) by self-assembly and in situ derivation strategy. The 3D porous structure of the composite can significantly reduce the molecular transfer resistance, achieve adsorption of pollutants and efficient transfer of active substances. The tight Schottky junction between TiO2 and Ti3C2Tx plays a synergetic role in improving charge separation and accelerating the transfer of photogenerated carriers. Meanwhile, TiO2 was used as an electron donor to promote the metal valence cycle in MCuFe-MOF. The optimal MXene-derived bimetallic composite exhibited 91.8 % degradation rate for MB (2.5 g/L) within 60 min. The composite has extremely high degradation efficiency for high-concentration pollutants. Overall, by introducing two-dimensional cocatalysts into metal organic framework materials, followed by in-situ derivatization to construct highly active photo-Fenton catalyst, offers a forward-looking strategy for designing catalyst materials with excellent photo-Fenton performance and industrial applications.
{"title":"MXene-derived bimetallic composites: A heterogeneous catalyst for enhanced photo-Fenton degradation activities","authors":"Wenjuan Zhang , Panpan Zhang , Yezhi Ding , Zhongliang Li , Youliang Wang , Henan Jia , Zhiqi Feng , Peiqing La","doi":"10.1016/j.apcata.2025.120759","DOIUrl":"10.1016/j.apcata.2025.120759","url":null,"abstract":"<div><div>As the global industry advances rapidly, organic pollutants in water have been posing threats to human health and ecosystems. Photo-Fenton oxidation has emerged as a promising way to degrade organic pollutants. Herein, we constructed MXene-derived bimetallic composites (3D TiO<sub>2</sub>/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>@MCuFe-MOF) for the photo-Fenton degradation of methylene blue (MB) by self-assembly and in situ derivation strategy. The 3D porous structure of the composite can significantly reduce the molecular transfer resistance, achieve adsorption of pollutants and efficient transfer of active substances. The tight Schottky junction between TiO<sub>2</sub> and Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> plays a synergetic role in improving charge separation and accelerating the transfer of photogenerated carriers. Meanwhile, TiO<sub>2</sub> was used as an electron donor to promote the metal valence cycle in MCuFe-MOF. The optimal MXene-derived bimetallic composite exhibited 91.8 % degradation rate for MB (2.5 g/L) within 60 min. The composite has extremely high degradation efficiency for high-concentration pollutants. Overall, by introducing two-dimensional cocatalysts into metal organic framework materials, followed by in-situ derivatization to construct highly active photo-Fenton catalyst, offers a forward-looking strategy for designing catalyst materials with excellent photo-Fenton performance and industrial applications.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120759"},"PeriodicalIF":4.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880355","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}
Pub Date : 2025-12-22DOI: 10.1016/j.apcata.2025.120758
Guillermo Penche , María P. González-Marcos , Juan R. González-Velasco , Cyler W. Vos , Christopher M. Kozak
The use of CO2 as building block in organic chemistry is compelling due to its availability, cost-effectiveness, and potential to mitigate emissions while generating valuable, sustainable materials. Ring-opening copolymerization (ROCOP) of CO2 and epoxides is a prime example of this. The viability of this technology, however, is highly dependent on the performance of the catalyst, and the Co-Ni DMC complex has recently demonstrated significant potential for industrial application. Thus, this article delves into the physicochemical characterization of this complex and offers a detailed examination of the kinetics and mechanism of CO2/PO ROCOP using in situ infrared spectroscopy. The behaviour of the catalyst is investigated under various operating conditions, including four different reaction temperatures, yielding an apparent activation energy of 59.8 kJ/mol. Zero-order kinetics with respect to CO2 pressure and first-order kinetics with respect to PO concentration are observed, with minimal formation of cyclic by-products across all conditions. The influence of chloride ions and the role of chain-transfer agents on the complex are corroborated. Based on the characterization, kinetic, and mechanistic studies, an insertion-coordination copolymerization mechanism is proposed for the studied complex.
{"title":"Kinetics and mechanism of the ring-opening copolymerization of CO2 and propylene oxide on a two-dimensional Co-Ni double metal cyanide complex","authors":"Guillermo Penche , María P. González-Marcos , Juan R. González-Velasco , Cyler W. Vos , Christopher M. Kozak","doi":"10.1016/j.apcata.2025.120758","DOIUrl":"10.1016/j.apcata.2025.120758","url":null,"abstract":"<div><div>The use of CO<sub>2</sub> as building block in organic chemistry is compelling due to its availability, cost-effectiveness, and potential to mitigate emissions while generating valuable, sustainable materials. Ring-opening copolymerization (ROCOP) of CO<sub>2</sub> and epoxides is a prime example of this. The viability of this technology, however, is highly dependent on the performance of the catalyst, and the Co-Ni DMC complex has recently demonstrated significant potential for industrial application. Thus, this article delves into the physicochemical characterization of this complex and offers a detailed examination of the kinetics and mechanism of CO<sub>2</sub>/PO ROCOP using <em>in situ</em> infrared spectroscopy. The behaviour of the catalyst is investigated under various operating conditions, including four different reaction temperatures, yielding an apparent activation energy of 59.8 kJ/mol. Zero-order kinetics with respect to CO<sub>2</sub> pressure and first-order kinetics with respect to PO concentration are observed, with minimal formation of cyclic by-products across all conditions. The influence of chloride ions and the role of chain-transfer agents on the complex are corroborated. Based on the characterization, kinetic, and mechanistic studies, an insertion-coordination copolymerization mechanism is proposed for the studied complex.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120758"},"PeriodicalIF":4.8,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880350","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}
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