Pub Date : 2025-11-16DOI: 10.1007/s10562-025-05196-1
Eric I. Altman, Hans-Joachim Freund, Detlef W. Bahnemann, Bruno Chaudret, Alison R. Fout, Andrew J. Gellman, Thomas R. Ward, Francisco Zaera, Paul Cremer, Peidong Yang, Ji Su
{"title":"In Memory of Gabor Somorjai (1935–2025)","authors":"Eric I. Altman, Hans-Joachim Freund, Detlef W. Bahnemann, Bruno Chaudret, Alison R. Fout, Andrew J. Gellman, Thomas R. Ward, Francisco Zaera, Paul Cremer, Peidong Yang, Ji Su","doi":"10.1007/s10562-025-05196-1","DOIUrl":"10.1007/s10562-025-05196-1","url":null,"abstract":"","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145561412","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}
Cathode catalysts are vital for proton exchange membrane fuel cells (PEMFCs). However, the sluggish Oxygen reduction reaction (ORR) kinetics and the high cost of platinum-based catalysts collectively pose significant barriers to the large-scale commercialization of PEMFCs. To address these issues, a Pt–Pd–Cu ultrathin nanosheet was prepared with a thickness of about 1.626 nm through chemical synthesis and the substitution method. The synthesis, which involves chemical reduction of Pt precursors followed by directional deposition on the Pd–Cu layer, produces Pt3Pd33Cu64 catalysts with a composite structure that exhibits structural stability and enhanced catalytic performance. Electrochemical tests reveal that the as-synthesized Pt3Pd33Cu64 ultrathin nanosheets show the mass activity (MA) of 1.59 A mg−1Pt+Pd, and the specific activity (SA) of 0.422 mA cm−2. These performances show 4.42-fold and 1.66-fold enhancements over commercial Pt/C catalysts (MA: 0.36 A mg−1Pt+Pd, SA:0.255 mA cm−2), respectively. The results demonstrate that the ultrathin nanosheet-structured catalyst enhances catalytic activity, offering a strategy for the design of advanced cathode catalysts.
Graphical Abstract
阴极催化剂是质子交换膜燃料电池（pemfc）的重要组成部分。然而，缓慢的氧还原反应（ORR）动力学和铂基催化剂的高成本共同构成了pemfc大规模商业化的重大障碍。为了解决这些问题，通过化学合成和取代法制备了厚度约为1.626 nm的Pt-Pd-Cu超薄纳米片。该合成方法通过化学还原Pt前驱体，然后在Pd-Cu层上定向沉积，制备出具有复合结构的Pt3Pd33Cu64催化剂，该催化剂具有结构稳定和催化性能增强的特点。电化学测试表明，合成的Pt3Pd33Cu64超薄纳米片的质量活性（MA）为1.59 A mg - 1Pt+Pd，比活性（SA）为0.422 MA cm - 2。这些性能分别比商用Pt/C催化剂（MA: 0.36 A mg - 1Pt+Pd, SA:0.255 MA cm - 2）提高了4.42倍和1.66倍。结果表明，超薄纳米片结构的催化剂提高了催化活性，为先进阴极催化剂的设计提供了策略。图形抽象
{"title":"Ultrathin Porous PtPdCu Nanosheets as Efficient Electrocatalysts for Oxygen Reduction Reaction","authors":"Yaru Li, Jianglong Cheng, Quan Wang, Hongbin Wang, Haipeng Hou, Yumeng Zhu, Jiamin Sun, Miaoling Shi, Xue Zhang","doi":"10.1007/s10562-025-05232-0","DOIUrl":"10.1007/s10562-025-05232-0","url":null,"abstract":"<div><p>Cathode catalysts are vital for proton exchange membrane fuel cells (PEMFCs). However, the sluggish Oxygen reduction reaction (ORR) kinetics and the high cost of platinum-based catalysts collectively pose significant barriers to the large-scale commercialization of PEMFCs. To address these issues, a Pt–Pd–Cu ultrathin nanosheet was prepared with a thickness of about 1.626 nm through chemical synthesis and the substitution method. The synthesis, which involves chemical reduction of Pt precursors followed by directional deposition on the Pd–Cu layer, produces Pt<sub>3</sub>Pd<sub>33</sub>Cu<sub>64</sub> catalysts with a composite structure that exhibits structural stability and enhanced catalytic performance. Electrochemical tests reveal that the as-synthesized Pt<sub>3</sub>Pd<sub>33</sub>Cu<sub>64</sub> ultrathin nanosheets show the mass activity (MA) of 1.59 A mg<sup>−1</sup><sub>Pt+Pd</sub>, and the specific activity (SA) of 0.422 mA cm<sup>−2</sup>. These performances show 4.42-fold and 1.66-fold enhancements over commercial Pt/C catalysts (MA: 0.36 A mg<sup>−1</sup><sub>Pt+Pd</sub>, SA:0.255 mA cm<sup>−2</sup>), respectively. The results demonstrate that the ultrathin nanosheet-structured catalyst enhances catalytic activity, offering a strategy for the design of advanced cathode catalysts.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145561415","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}
Pub Date : 2025-11-16DOI: 10.1007/s10562-025-05236-w
Ali Rahmatpour, Abolfazl Jahani
We report the efficient synthesis of a novel acrylic fiber-supported monovalent copper catalyst (PAFPr-IA-Cu(I)) via a straightforward three-step procedure: fiber amination, ligand grafting using isatoic anhydride (IA), and subsequent chelation with Cu(I) ions. Comprehensive characterization using Fourier Transform Infrared Spectroscopy (FT-IR), Thermogravimetric Analysis (TGA/DTG), X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Energy-Dispersive X-ray Spectroscopy (EDX), and Inductively Coupled Plasma (ICP) analysis confirmed the successful immobilization of the catalyst and its structural stability. The catalyst demonstrated excellent activity in aqueous 1,3-dipolar cycloaddition (“click”) reactions between terminal alkynes, sodium azide, and alkyl halides, yielding 1,2,3-triazoles in high yields (86–95%) under mild conditions. Notably, the fibrous catalyst could be easily recovered using simple mechanical removal (e.g., tweezers), retained high catalytic performance over multiple cycles with minimal copper leaching, and maintained structural integrity as confirmed by hot filtration and leaching tests. This work highlights the potential of functionalized acrylic fibers as sustainable, cost-effective, and recyclable supports for heterogeneous Cu(I) catalysts in environmentally friendly organic synthesis.
{"title":"Cu(I) Anchored on IA-bound Acrylic Fiber: A Recyclable Catalyst for Aqueous Click Reactions","authors":"Ali Rahmatpour, Abolfazl Jahani","doi":"10.1007/s10562-025-05236-w","DOIUrl":"10.1007/s10562-025-05236-w","url":null,"abstract":"<div><p>We report the efficient synthesis of a novel acrylic fiber-supported monovalent copper catalyst (PAF<sub>Pr</sub>-<sub>IA</sub>-Cu(I)) via a straightforward three-step procedure: fiber amination, ligand grafting using isatoic anhydride (IA), and subsequent chelation with Cu(I) ions. Comprehensive characterization using Fourier Transform Infrared Spectroscopy (FT-IR), Thermogravimetric Analysis (TGA/DTG), X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Energy-Dispersive X-ray Spectroscopy (EDX), and Inductively Coupled Plasma (ICP) analysis confirmed the successful immobilization of the catalyst and its structural stability. The catalyst demonstrated excellent activity in aqueous 1,3-dipolar cycloaddition (“click”) reactions between terminal alkynes, sodium azide, and alkyl halides, yielding 1,2,3-triazoles in high yields (86–95%) under mild conditions. Notably, the fibrous catalyst could be easily recovered using simple mechanical removal (e.g., tweezers), retained high catalytic performance over multiple cycles with minimal copper leaching, and maintained structural integrity as confirmed by hot filtration and leaching tests. This work highlights the potential of functionalized acrylic fibers as sustainable, cost-effective, and recyclable supports for heterogeneous Cu(I) catalysts in environmentally friendly organic synthesis.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145561417","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}
Pub Date : 2025-11-16DOI: 10.1007/s10562-025-05240-0
Arthur O. Preto, Willian S. M. Reis, Paulo W. Tardioli, Daniela B. Hirata, Ernandes B. Pereira
Waste cooking oils (WCO) are residues capable of causing severe environmental harm if disposed of incorrectly. Nonetheless, they can be easily reused as lipid feedstock for producing biodiesel through the hydroesterification route, therefore being the chief objective herein. In this route, there is an initial hydrolysis reaction of WCO into free fatty acids (FFA) and glycerol, followed by esterification of FFA into esters (biodiesel) using alcohol and free lipases in both reactions. The hydrolysis step was carried out using lipase from Candida rugosa (CRL) and the central composite rotatable design (CCRD) selecting WCO and enzyme contents as variables, and 100% hydrolysis of WCOs into FFA was observed after 150 min of reaction at 40ºC and 10% content for both variables. In the esterification step, reactions were catalyzed using Eversa® Transform 2.0 (ET 2.0) and the FFA:ethanol molar ratio, enzyme content and reaction time were evaluated, thus achieving maximum conversion of 91.94% of FFA into biodiesel in a FFA:ethanol molar ratio of 1:2 and enzyme content of 5.0% after 4 h of reaction. The produced biodiesel presented high unsaturation content in its composition, which is advantageous since it favors fluidity at low temperatures and assists in avoiding the obstruction of engine injection systems.
{"title":"Sustainable Biodiesel Production Through Waste Cooking Oil Hydrosterification","authors":"Arthur O. Preto, Willian S. M. Reis, Paulo W. Tardioli, Daniela B. Hirata, Ernandes B. Pereira","doi":"10.1007/s10562-025-05240-0","DOIUrl":"10.1007/s10562-025-05240-0","url":null,"abstract":"<div><p>Waste cooking oils (WCO) are residues capable of causing severe environmental harm if disposed of incorrectly. Nonetheless, they can be easily reused as lipid feedstock for producing biodiesel through the hydroesterification route, therefore being the chief objective herein. In this route, there is an initial hydrolysis reaction of WCO into free fatty acids (FFA) and glycerol, followed by esterification of FFA into esters (biodiesel) using alcohol and free lipases in both reactions. The hydrolysis step was carried out using lipase from <i>Candida rugosa</i> (CRL) and the central composite rotatable design (CCRD) selecting WCO and enzyme contents as variables, and 100% hydrolysis of WCOs into FFA was observed after 150 min of reaction at 40ºC and 10% content for both variables. In the esterification step, reactions were catalyzed using Eversa® Transform 2.0 (ET 2.0) and the FFA:ethanol molar ratio, enzyme content and reaction time were evaluated, thus achieving maximum conversion of 91.94% of FFA into biodiesel in a FFA:ethanol molar ratio of 1:2 and enzyme content of 5.0% after 4 h of reaction. The produced biodiesel presented high unsaturation content in its composition, which is advantageous since it favors fluidity at low temperatures and assists in avoiding the obstruction of engine injection systems.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145561416","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}
Pub Date : 2025-11-16DOI: 10.1007/s10562-025-05239-7
Gai Shen, Shuangming Li, Nan Wang, Yiwen Wang, Yaxin Xing, Mingxian Jiang, Ying Sun, Sansan Yu
A series of MoVTeNbOx catalysts with different Sr doping amounts were prepared by spray-drying method and used in the one-step oxidation of propane to acrylic acid. The results showed that Sr doping does not cause significant damage to the M1 phase structure, and moderate Sr doping increases the relative content of the M1 phase by inhibiting the transformation to the MoO2 phase. Concurrently, the introduction of Sr alters the pore size distribution of the catalyst, leading to a trend toward a transition from mesoporous to microporous catalysts. The introduction of Sr reduces the surface acidity of MoVTeNbOx, inhibits the peroxidation of acrylic acid, and improves the distribution of surface elements. Moderate Sr doping promotes an increase in the Te4+ content on the surface of MoVTeNbOx, which is beneficial for the formation of acrylic acid. Compared with the undoped MoVTeNbOx sample, the sample with the Sr/Mo atomic ratio of 0.015 possessed the highest M1 phase content (97%) and the best catalytic performance, with an increase from 46 to 77% for the selectivity to acrylic acid and an increase from 30 to 49% in for the acrylic acid yield.
{"title":"Effect of Sr Doping on the Structure-Activity Relationship of MoVTeNbO for Catalyzing the Direct Conversion of Propane to Acrylic Acid","authors":"Gai Shen, Shuangming Li, Nan Wang, Yiwen Wang, Yaxin Xing, Mingxian Jiang, Ying Sun, Sansan Yu","doi":"10.1007/s10562-025-05239-7","DOIUrl":"10.1007/s10562-025-05239-7","url":null,"abstract":"<div><p>A series of MoVTeNbOx catalysts with different Sr doping amounts were prepared by spray-drying method and used in the one-step oxidation of propane to acrylic acid. The results showed that Sr doping does not cause significant damage to the M1 phase structure, and moderate Sr doping increases the relative content of the M1 phase by inhibiting the transformation to the MoO<sub>2</sub> phase. Concurrently, the introduction of Sr alters the pore size distribution of the catalyst, leading to a trend toward a transition from mesoporous to microporous catalysts. The introduction of Sr reduces the surface acidity of MoVTeNbOx, inhibits the peroxidation of acrylic acid, and improves the distribution of surface elements. Moderate Sr doping promotes an increase in the Te<sup>4+</sup> content on the surface of MoVTeNbOx, which is beneficial for the formation of acrylic acid. Compared with the undoped MoVTeNbOx sample, the sample with the Sr/Mo atomic ratio of 0.015 possessed the highest M1 phase content (97%) and the best catalytic performance, with an increase from 46 to 77% for the selectivity to acrylic acid and an increase from 30 to 49% in for the acrylic acid yield.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145561414","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}
Pub Date : 2025-11-16DOI: 10.1007/s10562-025-05223-1
Liya Wang, Xuejun Cui, Fengqi Wang, Yuming Qi
TiO2 catalytically active coating on TC4 titanium alloy was prepared through plasma electrolytic oxidation (PEO) utilizing aqueous electrolytes. The elemental and phase composition, microstructure, and catalytic performance of the coating was characterized by EDS, XRD, SEM, UV-Vis, TOC, and COD methods, respectively. The coating, with a surface porosity of 20%, primarily consists of rutile-type TiO2 and amorphous vanadium compounds. The catalysis originates from the synergistic interaction between the porous TiO2 coating and ozone activation, where the plasma-electrolytic porous architecture enhances surface adsorption and radical-mediated from ozone decomposition reaction pathways. Combined with ozone oxidation, the coating exhibits excellent catalytic performance in degrading methyl orange (MO), and the degradation rate has been increased. Notably, the catalyst showed the most significant effect in catalytic ozonation of a 10 mg/L MO, achieving a degradation rate of up to 95.6% in 60 min, representing 71.8% enhancement compared to ozone oxidation. What’s more, the result of TOC and COD jointly confirms that the PEO catalytic coating exhibits high efficiency for the catalytic degradation of low-concentration MO solution. This study establishes a potential application in advanced oxidation processes for the degradation of organic pollutants.
{"title":"Plasma Electrolytic Oxidation Coating as an Alternative Support for TiO2 Catalysts in Catalytic Ozonation","authors":"Liya Wang, Xuejun Cui, Fengqi Wang, Yuming Qi","doi":"10.1007/s10562-025-05223-1","DOIUrl":"10.1007/s10562-025-05223-1","url":null,"abstract":"<div><p>TiO<sub>2</sub> catalytically active coating on TC4 titanium alloy was prepared through plasma electrolytic oxidation (PEO) utilizing aqueous electrolytes. The elemental and phase composition, microstructure, and catalytic performance of the coating was characterized by EDS, XRD, SEM, UV-Vis, TOC, and COD methods, respectively. The coating, with a surface porosity of 20%, primarily consists of rutile-type TiO<sub>2</sub> and amorphous vanadium compounds. The catalysis originates from the synergistic interaction between the porous TiO<sub>2</sub> coating and ozone activation, where the plasma-electrolytic porous architecture enhances surface adsorption and radical-mediated from ozone decomposition reaction pathways. Combined with ozone oxidation, the coating exhibits excellent catalytic performance in degrading methyl orange (MO), and the degradation rate has been increased. Notably, the catalyst showed the most significant effect in catalytic ozonation of a 10 mg/L MO, achieving a degradation rate of up to 95.6% in 60 min, representing 71.8% enhancement compared to ozone oxidation. What’s more, the result of TOC and COD jointly confirms that the PEO catalytic coating exhibits high efficiency for the catalytic degradation of low-concentration MO solution. This study establishes a potential application in advanced oxidation processes for the degradation of organic pollutants.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145561413","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}
Pub Date : 2025-11-14DOI: 10.1007/s10562-025-05231-1
Xiao-Yan Wang, Ya-Jing Wang, Fei Wang, Jie Xu, Bing Xue
The liquid-phase selective oxidation of benzyl alcohol (BZA) by atmospheric oxygen is a more sustainable and cleaner strategy for the synthesis of benzaldehyde (BZL) compared with the traditional hydrolysis of chlorobenzene. Herein, a series of C3N4–CeO2 composites were prepared and then utilized as catalyst supports to load Pd nanoparticles. The effects of the amount of carbon nitride (C3N4) and the calcination conditions on the physicochemical properties of C3N4–CeO2 materials were investigated. In the solvent-free selective oxidation of BZA, the Pd/C3N4–CeO2 materials demonstrated higher catalytic activity than Pd/C3N4 and Pd/CeO2. Under the reaction temperature of 90 °C and 4 mL of BZA, the BZA conversion could reach 84.6%, whereas the selectivity of benzaldehyde was 98.7%. In addition, the solid catalyst could be reused six times while the conversion did not significantly decrease. Based on the characterization results, the possible catalytically active sites of 2Pd/C3N4–CeO2-1 for the selective oxidation of BZA were Ce3+ and oxygen vacancies, and the introduction of C3N4 effectively increased the content of these two species.
{"title":"Preparation of Pd Nanocatalysts Supported on C3N4–CeO2 Composites for Solvent-Free and Atmospheric Selective Oxidation of Benzyl Alcohol","authors":"Xiao-Yan Wang, Ya-Jing Wang, Fei Wang, Jie Xu, Bing Xue","doi":"10.1007/s10562-025-05231-1","DOIUrl":"10.1007/s10562-025-05231-1","url":null,"abstract":"<div><p>The liquid-phase selective oxidation of benzyl alcohol (BZA) by atmospheric oxygen is a more sustainable and cleaner strategy for the synthesis of benzaldehyde (BZL) compared with the traditional hydrolysis of chlorobenzene. Herein, a series of C<sub>3</sub>N<sub>4</sub>–CeO<sub>2</sub> composites were prepared and then utilized as catalyst supports to load Pd nanoparticles. The effects of the amount of carbon nitride (C<sub>3</sub>N<sub>4</sub>) and the calcination conditions on the physicochemical properties of C<sub>3</sub>N<sub>4</sub>–CeO<sub>2</sub> materials were investigated. In the solvent-free selective oxidation of BZA, the Pd/C<sub>3</sub>N<sub>4</sub>–CeO<sub>2</sub> materials demonstrated higher catalytic activity than Pd/C<sub>3</sub>N<sub>4</sub> and Pd/CeO<sub>2</sub>. Under the reaction temperature of 90 °C and 4 mL of BZA, the BZA conversion could reach 84.6%, whereas the selectivity of benzaldehyde was 98.7%. In addition, the solid catalyst could be reused six times while the conversion did not significantly decrease. Based on the characterization results, the possible catalytically active sites of 2Pd/C<sub>3</sub>N<sub>4</sub>–CeO<sub>2</sub>-1 for the selective oxidation of BZA were Ce<sup>3+</sup> and oxygen vacancies, and the introduction of C<sub>3</sub>N<sub>4</sub> effectively increased the content of these two species.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145511074","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}
This study addresses the key issues of low activity and slow reaction rates in supported nickel-based catalysts for the hydrogenation of m-dinitrobenzene (DNB). Density Functional Theory (DFT) calculations revealed that the Ni(111) crystal plane exhibits the highest adsorption energy for the reactant, indicating its potential advantage in DNB hydrogenation. Based on this, using KBr as a structure-directing agent, a supported catalyst with a high proportion of exposed Ni(111) planes was prepared by regulating the crystal plane orientation of nickel nanoparticles. Characterization techniques including XRD, TEM, N2 physical adsorption-desorption, NH3-TPD, and XPS were used to systematically elucidate the mechanism of KBr’s regulation on crystal planes: KBr optimizes the exposure ratio of crystal planes by influencing the agglomeration-dispersion balance of particles. When the molar ratio of KBr to Ni is 50, the exposure proportion of the Ni(111) plane reached 80.81%. The prepared Ni-KBr-50/ZSM-5-Al catalyst exhibited optimal catalytic performance: DNB conversion reached 99.99% within 5 min, and m-phenylenediamine (MPD) selectivity reached 99.99%, consistent with the DFT-predicted trend of “high adsorption energy crystal plane promotes reaction activity.” Additionally, catalyst stability tests showed excellent stability: Ni-KBr-50/ZSM-5-Al maintained a DNB conversion of 99.99% over 10 recycling experiments, with MPD selectivity still reaching 98.71% in the 10th cycle.
{"title":"Study on Ni Catalyst Crystal Plane Orientation and Its Effect on Hydrogenation Performance of m-Dinitrobenzene","authors":"Hongwei Li, Pengju Lei, Zhibin Liu, Jichong Xia, Shoudeng Wang, Guixian Li, Xinhong Zhao, Dong Ji","doi":"10.1007/s10562-025-05210-6","DOIUrl":"10.1007/s10562-025-05210-6","url":null,"abstract":"<p>This study addresses the key issues of low activity and slow reaction rates in supported nickel-based catalysts for the hydrogenation of <i>m</i>-dinitrobenzene (DNB). Density Functional Theory (DFT) calculations revealed that the Ni(111) crystal plane exhibits the highest adsorption energy for the reactant, indicating its potential advantage in DNB hydrogenation. Based on this, using KBr as a structure-directing agent, a supported catalyst with a high proportion of exposed Ni(111) planes was prepared by regulating the crystal plane orientation of nickel nanoparticles. Characterization techniques including XRD, TEM, N<sub>2</sub> physical adsorption-desorption, NH<sub>3</sub>-TPD, and XPS were used to systematically elucidate the mechanism of KBr’s regulation on crystal planes: KBr optimizes the exposure ratio of crystal planes by influencing the agglomeration-dispersion balance of particles. When the molar ratio of KBr to Ni is 50, the exposure proportion of the Ni(111) plane reached 80.81%. The prepared Ni-KBr-50/ZSM-5-Al catalyst exhibited optimal catalytic performance: DNB conversion reached 99.99% within 5 min, and <i>m</i>-phenylenediamine (MPD) selectivity reached 99.99%, consistent with the DFT-predicted trend of “high adsorption energy crystal plane promotes reaction activity.” Additionally, catalyst stability tests showed excellent stability: Ni-KBr-50/ZSM-5-Al maintained a DNB conversion of 99.99% over 10 recycling experiments, with MPD selectivity still reaching 98.71% in the 10th cycle.</p>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145456237","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}
A highly efficient Fe-Sn-Cu ternary oxide catalyst was developed for the Baeyer-Villiger oxidation of cyclohexanone using O₂/benzaldehyde to synthesize ε-caprolactone (ε-CL), a key precursor for biodegradable polycaprolactone. Catalysts with varying Cu ratios were synthesized via co-precipitation and characterized. Moderate Cu doping (n(Fe): n(Sn): n(Cu) = 1:1:0.1) optimized mesoporous structure and mass transfer, with SnO₂ as the skeleton and highly dispersed Fe₂O₃/CuO creating synergistic active sites. BET analysis showed that this specific composition achieved an optimized mesoporous architecture with the largest average pore diameter (37.27 nm), enhancing mass transport and active site accessibility compared to the un-doped (28.55 nm) and over-doped (30.52 nm) variants. XPS analysis confirmed the coexistence of active species Fe³⁺, Sn⁴⁺, and Cu²⁺, where the incorporation of Cu²⁺ is crucial for accelerating the oxidation of benzaldehyde, the rate-determining step. Under optimal conditions (55 °C, 5 h, cyclohexanone/benzaldehyde = 1:3, O₂ flow = 25 mL·min⁻¹), Fe-Sn-0.1Cu achieved 99.9% cyclohexanone conversion, 99.9% ε-CL selectivity, and 98.5% benzaldehyde conversion. The catalyst retained activity over 9 cycles, demonstrating retained activity. Its low-cost preparation and potential for industrial application were highlighted. Notably, phenyl formate, a benzaldehyde oxidation byproduct requiring chromatographic separation, was identified to prevent analytical inaccuracies.
{"title":"Potent Fe-Sn-Cu Trioxide Catalysts for the Highly Efficient Green Synthesis of ε-Caprolactone by the Baeyer-Villiger Oxidation Reaction","authors":"Jia Sun, Qingyang Gu, Haibo Jin, Suohe Yang, Rui Qin","doi":"10.1007/s10562-025-05212-4","DOIUrl":"10.1007/s10562-025-05212-4","url":null,"abstract":"<div><p>A highly efficient Fe-Sn-Cu ternary oxide catalyst was developed for the Baeyer-Villiger oxidation of cyclohexanone using O₂/benzaldehyde to synthesize ε-caprolactone (ε-CL), a key precursor for biodegradable polycaprolactone. Catalysts with varying Cu ratios were synthesized via co-precipitation and characterized. Moderate Cu doping (n(Fe): n(Sn): n(Cu) = 1:1:0.1) optimized mesoporous structure and mass transfer, with SnO₂ as the skeleton and highly dispersed Fe₂O₃/CuO creating synergistic active sites. BET analysis showed that this specific composition achieved an optimized mesoporous architecture with the largest average pore diameter (37.27 nm), enhancing mass transport and active site accessibility compared to the un-doped (28.55 nm) and over-doped (30.52 nm) variants. XPS analysis confirmed the coexistence of active species Fe³⁺, Sn⁴⁺, and Cu²⁺, where the incorporation of Cu²⁺ is crucial for accelerating the oxidation of benzaldehyde, the rate-determining step. Under optimal conditions (55 °C, 5 h, cyclohexanone/benzaldehyde = 1:3, O₂ flow = 25 mL·min⁻¹), Fe-Sn-0.1Cu achieved 99.9% cyclohexanone conversion, 99.9% ε-CL selectivity, and 98.5% benzaldehyde conversion. The catalyst retained activity over 9 cycles, demonstrating retained activity. Its low-cost preparation and potential for industrial application were highlighted. Notably, phenyl formate, a benzaldehyde oxidation byproduct requiring chromatographic separation, was identified to prevent analytical inaccuracies.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145456262","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}
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