Pub Date : 2026-01-08DOI: 10.1016/j.apcata.2026.120783
Changshun Deng , Chaoxiang Li , Haoyu Lu , Bingqing Ge , Weiping Ding
MoVTeNbO is a famous oxide of multi-component and effective for gaseous toluene oxidation to benzaldehyde, but exhibits catalytic properties highly sensitive to composition and surface properties. Here, we report the regulation of catalytic properties of MoVTeNbO by Te defects tuned in hydrothermal synthesis, even in the same bulk crystal structure of M1 phase, leading to significant difference in catalytic performance for selective oxidation of toluene using air as oxidant. The catalyst MoVTeNbO-1 in nano brick shape exhibits weaker redox capacity and acidity as well as lower contents of surface V5 + and electrophilic oxygen species, giving rise to a conversion of toluene exceeding 8 % with a selectivity of 73 % to benzaldehyde at 350 °C. Nevertheless, the stronger oxidation capacity of MoVTeNbO-2 in nano firewood shape shows an outstanding activity for toluene oxidation at a conversion of ∼84 % and a selectivity more than 60 % to maleic anhydride at the same temperature. Further study indicates that much more Te defects in MoVTeNbO-2 play a key role for the regulation of its surface properties and direct the catalyst for toluene oxidation following totally different pathways of conversion. Results of characterizations including kinetics in-situ spectroscopy also indicate that the toluene oxidation over nano brick MoVTeNbO-1 follows an Eley-Rideal mechanism, but the toluene oxidation over nano firewood shaped MoVTeNbO-2 complies with a Langmuir-Hinshelwood mechanism.
{"title":"Reaction pathways of MoVTeNbO directed by Te defects for selective oxidation of toluene","authors":"Changshun Deng , Chaoxiang Li , Haoyu Lu , Bingqing Ge , Weiping Ding","doi":"10.1016/j.apcata.2026.120783","DOIUrl":"10.1016/j.apcata.2026.120783","url":null,"abstract":"<div><div>MoVTeNbO is a famous oxide of multi-component and effective for gaseous toluene oxidation to benzaldehyde, but exhibits catalytic properties highly sensitive to composition and surface properties. Here, we report the regulation of catalytic properties of MoVTeNbO by Te defects tuned in hydrothermal synthesis, even in the same bulk crystal structure of M1 phase, leading to significant difference in catalytic performance for selective oxidation of toluene using air as oxidant. The catalyst MoVTeNbO-1 in nano brick shape exhibits weaker redox capacity and acidity as well as lower contents of surface V<sup>5 +</sup> and electrophilic oxygen species, giving rise to a conversion of toluene exceeding 8 % with a selectivity of 73 % to benzaldehyde at 350 °C. Nevertheless, the stronger oxidation capacity of MoVTeNbO-2 in nano firewood shape shows an outstanding activity for toluene oxidation at a conversion of ∼84 % and a selectivity more than 60 % to maleic anhydride at the same temperature. Further study indicates that much more Te defects in MoVTeNbO-2 play a key role for the regulation of its surface properties and direct the catalyst for toluene oxidation following totally different pathways of conversion. Results of characterizations including kinetics <em>in-situ</em> spectroscopy also indicate that the toluene oxidation over nano brick MoVTeNbO-1 follows an Eley-Rideal mechanism, but the toluene oxidation over nano firewood shaped MoVTeNbO-2 complies with a Langmuir-Hinshelwood mechanism.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120783"},"PeriodicalIF":4.8,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974700","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}
Cobalt-doped zeolite catalysts have been identified as a potentially viable non-precious metal alternative for toluene oxidation, exhibiting characteristics reminiscent of noble metals, such as the ability to activate C-H bonds, abundance, and minimal adverse environmental impact. However, the catalytic activity is greatly reliant on the diversity of cobalt species embedded within the zeolite framework. To address this, a ligand-engineering strategy was utilized to precisely control the coordination environment of the cobalt precursor, thereby regulating the resulting cobalt species and accordingly the catalytic activity of cobalt-doped zeolite catalysts. Four distinct Co@S-1 zeolites were synthesized with disparate ligands including ethylenediamine, water, ammonia water and acetylacetone, and meanwhile applied as heterogeneous catalysts for the selective oxidation of toluene with molecular oxygen as oxidant. Among them, the Co@S-1(EDA) zeolite catalyst synthesized with ethylenediamine demonstrated superior catalytic reaction performance, achieving a toluene conversion of 63.8 % with a benzaldehyde selectivity of 68.5 % within 6 h of reaction. This eminent catalytic oxidation ability for Co@S-1(EDA) zeolite catalyst is mainly ascribed to its largest Co2+/Co3+ ratio, its most oxygen vacancy amount and its largest external surface area. Furthermore, the Co@S-1(EDA) zeolite catalyst exhibited excellent re-usability, maintaining its activity over five consecutive catalytic cycles. This study emphasizes ligand engineering as an effective approach to create highly efficient and stable cobalt-based zeolite catalysts for selective hydrocarbon oxidation reactions.
{"title":"Ligand-engineered cobalt precursors toward enhanced catalytic activity of Co@S-1 zeolite in toluene oxidation","authors":"Shengnan Xu, Yu Yu, Fuxin Wang, Jiande Hu, Zixiang Li, Guojun Lv","doi":"10.1016/j.apcata.2026.120784","DOIUrl":"10.1016/j.apcata.2026.120784","url":null,"abstract":"<div><div>Cobalt-doped zeolite catalysts have been identified as a potentially viable non-precious metal alternative for toluene oxidation, exhibiting characteristics reminiscent of noble metals, such as the ability to activate C-H bonds, abundance, and minimal adverse environmental impact. However, the catalytic activity is greatly reliant on the diversity of cobalt species embedded within the zeolite framework. To address this, a ligand-engineering strategy was utilized to precisely control the coordination environment of the cobalt precursor, thereby regulating the resulting cobalt species and accordingly the catalytic activity of cobalt-doped zeolite catalysts. Four distinct Co@S-1 zeolites were synthesized with disparate ligands including ethylenediamine, water, ammonia water and acetylacetone, and meanwhile applied as heterogeneous catalysts for the selective oxidation of toluene with molecular oxygen as oxidant. Among them, the Co@S-1(EDA) zeolite catalyst synthesized with ethylenediamine demonstrated superior catalytic reaction performance, achieving a toluene conversion of 63.8 % with a benzaldehyde selectivity of 68.5 % within 6 h of reaction. This eminent catalytic oxidation ability for Co@S-1(EDA) zeolite catalyst is mainly ascribed to its largest Co<sup>2+</sup>/Co<sup>3+</sup> ratio, its most oxygen vacancy amount and its largest external surface area. Furthermore, the Co@S-1(EDA) zeolite catalyst exhibited excellent re-usability, maintaining its activity over five consecutive catalytic cycles. This study emphasizes ligand engineering as an effective approach to create highly efficient and stable cobalt-based zeolite catalysts for selective hydrocarbon oxidation reactions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120784"},"PeriodicalIF":4.8,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974697","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 : 2026-01-08DOI: 10.1016/j.apcata.2025.120765
Lei Shi , Jinyu Sun , Xiguang Wang , Xinyi Cao , Jiankai Cheng , Yong Gao , Luyang Qiao , Zhangfeng Zhou , Yuangen Yao
Semi-hydrogenation of dimethyl oxalate (DMO) is an attractive route for methyl glycolate (MG) synthesis. However, constructing efficient catalyst remains a great challenge. Herein, a series of Ag-xZr/SiO2 catalysts were prepared via the ammonia evaporation method and the effects of Zr doping over Ag/SiO2 catalysts are investigated. Characterization results indicated that Zr doping promotes the formation of Ag10Si4O13 species, which played a key role in regulating the Ag0 / Ag⁺ ratio and promoting the Ag dispersion. Moreover, Zr doped SiO2 generated strengthened Lewis acids (LA) for DMO activation and more Brønsted acids (BA) for H transfer. In comparison, over-doping may promote the growth of Ag particles due to changed coordination environment of Ag-O. With an optimal Zr content, the Ag-3Zr/SiO2 catalyst achieves 99 % DMO conversion with over 90 % MG yield under a WHSV of 1.0 mL·g⁻¹ ·h⁻¹ . This work offered valuable insights about the balances of Ag0 and Ag+, as well as LA and BA for designing efficient catalysts for DMO semi-hydrogenation.
{"title":"Synthesis of methyl glycolate via dimethyl oxalate hydrogenation over Zr‑modified Ag/SiO2 catalysts","authors":"Lei Shi , Jinyu Sun , Xiguang Wang , Xinyi Cao , Jiankai Cheng , Yong Gao , Luyang Qiao , Zhangfeng Zhou , Yuangen Yao","doi":"10.1016/j.apcata.2025.120765","DOIUrl":"10.1016/j.apcata.2025.120765","url":null,"abstract":"<div><div>Semi-hydrogenation of dimethyl oxalate (DMO) is an attractive route for methyl glycolate (MG) synthesis. However, constructing efficient catalyst remains a great challenge. Herein, a series of Ag-xZr/SiO<sub>2</sub> catalysts were prepared via the ammonia evaporation method and the effects of Zr doping over Ag/SiO<sub>2</sub> catalysts are investigated. Characterization results indicated that Zr doping promotes the formation of Ag<sub>10</sub>Si<sub>4</sub>O<sub>13</sub> species, which played a key role in regulating the Ag<sup>0</sup> / Ag⁺ ratio and promoting the Ag dispersion. Moreover, Zr doped SiO<sub>2</sub> generated strengthened Lewis acids (LA) for DMO activation and more Brønsted acids (BA) for H transfer. In comparison, over-doping may promote the growth of Ag particles due to changed coordination environment of Ag-O. With an optimal Zr content, the Ag-3Zr/SiO<sub>2</sub> catalyst achieves 99 % DMO conversion with over 90 % MG yield under a WHSV of 1.0 mL·g⁻¹ ·h⁻¹ . This work offered valuable insights about the balances of Ag<sup>0</sup> and Ag<sup>+</sup>, as well as LA and BA for designing efficient catalysts for DMO semi-hydrogenation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120765"},"PeriodicalIF":4.8,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076020","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 : 2026-01-08DOI: 10.1016/j.apcata.2025.120767
Konrad Koschnick , Alison M. Ferris , Marcel Stark , Danny Stark , Jan Welzenbach , Nico Winkler , Andreas Weinmann , Christian Hess , Bastian J.M. Etzold , Alfons Drochner , Tanja Franken , Dirk Geyer , Andreas Dreizler
A novel optically accessible catalysis flow channel is introduced that enables quantitative, contiguous, two-dimensional in situ measurements of gas-phase temperature and species concentrations during heterogeneous catalytic reactions. Spatially resolved gas-phase Raman spectroscopy, integral Fourier-transform infrared spectroscopy, and catalyst-resolved infrared thermography establish a well-defined platform for studying coupled reaction–transport phenomena. Applied to the oxidative dehydrogenation of ethanol over iron–molybdenum oxide catalysts, spontaneous Raman measurements yielded two-dimensional profiles of nine gas-phase species – with limits of detection in the tens-to-hundreds-of-ppm range – and gas-phase temperature within 500 µm of the catalyst surface. Transport analysis in the boundary layer yielded a Lewis number of approximately 1.65, indicating dominant thermal diffusion near the surface, while axial Péclet numbers revealed diffusion-controlled heat transport but advection-dominated product transport in a laminar regime. Varying the bulk flow velocity did not significantly alter conversion or product distributions, indicating kinetic and diffusive control under the present conditions. An iron-rich catalyst formulation exhibited higher activity than stoichiometric , whereas temperatures above 511 K reduced selectivity due to increased formation of total-oxidation products. Catalyst-free experiments, supported by kinetic simulations, confirmed partial gas-phase oxidation of acetaldehyde to CO, CO2, acetic acid, methanol, formaldehyde, and peracetic acid. These results highlight the importance of local gas-phase contributions and demonstrate that spatially resolving the gas-phase thermochemistry enables the gas phase to act as a reporter of surface reactions and facilitates the decoupling of chemical processes from transport phenomena.
{"title":"Gas-phase Raman spectroscopy for two-dimensional temperature and concentration profiling in the catalytic oxidative dehydrogenation of ethanol","authors":"Konrad Koschnick , Alison M. Ferris , Marcel Stark , Danny Stark , Jan Welzenbach , Nico Winkler , Andreas Weinmann , Christian Hess , Bastian J.M. Etzold , Alfons Drochner , Tanja Franken , Dirk Geyer , Andreas Dreizler","doi":"10.1016/j.apcata.2025.120767","DOIUrl":"10.1016/j.apcata.2025.120767","url":null,"abstract":"<div><div>A novel optically accessible catalysis flow channel is introduced that enables quantitative, contiguous, two-dimensional in situ measurements of gas-phase temperature and species concentrations during heterogeneous catalytic reactions. Spatially resolved gas-phase Raman spectroscopy, integral Fourier-transform infrared spectroscopy, and catalyst-resolved infrared thermography establish a well-defined platform for studying coupled reaction–transport phenomena. Applied to the oxidative dehydrogenation of ethanol over iron–molybdenum oxide catalysts, spontaneous Raman measurements yielded two-dimensional profiles of nine gas-phase species – with limits of detection in the tens-to-hundreds-of-ppm range – and gas-phase temperature within 500<!--> <!-->µm of the catalyst surface. Transport analysis in the boundary layer yielded a Lewis number of approximately 1.65, indicating dominant thermal diffusion near the surface, while axial Péclet numbers revealed diffusion-controlled heat transport but advection-dominated product transport in a laminar regime. Varying the bulk flow velocity did not significantly alter conversion or product distributions, indicating kinetic and diffusive control under the present conditions. An iron-rich catalyst formulation exhibited higher activity than stoichiometric <figure><img></figure> , whereas temperatures above 511<!--> <!-->K reduced selectivity due to increased formation of total-oxidation products. Catalyst-free experiments, supported by kinetic simulations, confirmed partial gas-phase oxidation of acetaldehyde to CO, CO<sub>2</sub>, acetic acid, methanol, formaldehyde, and peracetic acid. These results highlight the importance of local gas-phase contributions and demonstrate that spatially resolving the gas-phase thermochemistry enables the gas phase to act as a reporter of surface reactions and facilitates the decoupling of chemical processes from transport phenomena.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120767"},"PeriodicalIF":4.8,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145940923","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 : 2026-01-07DOI: 10.1016/j.apcata.2026.120773
Jiangnan Zhang, Zhou Wang, Jiaxin Hu, Jinyan Tan, Na Zhang, Jun Wang
To clarify the role of bridging groups in the catalytic process, a series of chromium-based precursor catalysts without bridging groups and with two monodentate phosphine ligands were designed. The absence of bridging groups enhanced the structural flexibility, enabling the catalyst to better adapt to the polymerization thermodynamics. Three commercially available substituted diphenylphosphine ligands were used to prepare P-Cr-P type chromium complexes without bridging groups. Among them, the triphenylphosphine system exhibited the best performance, achieving a catalytic activity of 1.06 × 106 g/mol Cr·h at 60 °C and 4 MPa ethylene pressure. The catalyst showed a total selectivity of 82.7 wt% for 1-hexene (17.6 wt%) and 1-octene (65.1 wt%). Density functional theory (DFT) calculations indicated that complex Cr3 thermodynamically favored the tetramerization of ethylene over trimerization, which was consistent with the oligomerization results in the experiment. Continuous space embedding rate analysis of the transition state model showed that the coordination and insertion of ethylene into the nine-membered ring imposed spatial pressure on the ligands, expanding their degrees of freedom. The removal of the bridging group made this process easier to occur.
{"title":"Non-bridged bisphosphine chromium catalysts for ethylene tetramerization: The influence of bridging groups in dynamic catalytic processes","authors":"Jiangnan Zhang, Zhou Wang, Jiaxin Hu, Jinyan Tan, Na Zhang, Jun Wang","doi":"10.1016/j.apcata.2026.120773","DOIUrl":"10.1016/j.apcata.2026.120773","url":null,"abstract":"<div><div>To clarify the role of bridging groups in the catalytic process, a series of chromium-based precursor catalysts without bridging groups and with two monodentate phosphine ligands were designed. The absence of bridging groups enhanced the structural flexibility, enabling the catalyst to better adapt to the polymerization thermodynamics. Three commercially available substituted diphenylphosphine ligands were used to prepare P-Cr-P type chromium complexes without bridging groups. Among them, the triphenylphosphine system exhibited the best performance, achieving a catalytic activity of 1.06 × 10<sup>6</sup> g/mol Cr·h at 60 °C and 4 MPa ethylene pressure. The catalyst showed a total selectivity of 82.7 wt% for 1-hexene (17.6 wt%) and 1-octene (65.1 wt%). Density functional theory (DFT) calculations indicated that complex Cr3 thermodynamically favored the tetramerization of ethylene over trimerization, which was consistent with the oligomerization results in the experiment. Continuous space embedding rate analysis of the transition state model showed that the coordination and insertion of ethylene into the nine-membered ring imposed spatial pressure on the ligands, expanding their degrees of freedom. The removal of the bridging group made this process easier to occur.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120773"},"PeriodicalIF":4.8,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076013","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 : 2026-01-07DOI: 10.1016/j.apcata.2026.120775
Yan Wang , Yuxi Si , Feiyue Zhang , Zhanqi Yang , Libin Liu , Yanming Hou , Hairui Lin , Zhuohan Li , Hu Li , Lele Zhang , Pengfei Xie , Youwei Cheng
Complete oxidation of propane has attracted widespread attention in the treatment of volatile organic compounds (VOCs) from Fischer-Tropsch synthesis tail gas. Pt-based catalysts have been considered highly promising catalysts for the catalytic oxidation of propane due to their high-activity. However, despite the recognized importance of the synergistic effect between Pt nanoparticles (NPs) and support materials, the detailed reaction mechanism investigation remains limited. In this work, we demonstrate that the Pt/Al2O3 catalyst exhibits improved propane catalytic performance, which is attributed to the synergistic interaction between Pt NPs and surface hydroxyl groups on the support. The improved Pt dispersion in Pt/Al2O3 catalysts with smaller Pt NPs facilitates the spillover of gaseous oxygen species and the stabilization of active sites for propane oxidation. Furthermore, in-situ DRIFTS characterization and density functional theory (DFT) calculation confirm that surface hydroxyl groups on Al2O3 effectively reduce the activation barrier for C-H bond cleavage, thereby improving the reactivity of propane molecules. This work provides a novel insight into metal-support synergy for propane oxidation, which offers strategic guidance for the rational design of efficient catalysts in hydrocarbon conversion processes.
{"title":"Size-dependent Pt dispersion and hydroxyl-assisted synergistic mechanism for propane complete oxidation over Pt/Al2O3 catalyst","authors":"Yan Wang , Yuxi Si , Feiyue Zhang , Zhanqi Yang , Libin Liu , Yanming Hou , Hairui Lin , Zhuohan Li , Hu Li , Lele Zhang , Pengfei Xie , Youwei Cheng","doi":"10.1016/j.apcata.2026.120775","DOIUrl":"10.1016/j.apcata.2026.120775","url":null,"abstract":"<div><div>Complete oxidation of propane has attracted widespread attention in the treatment of volatile organic compounds (VOCs) from Fischer-Tropsch synthesis tail gas. Pt-based catalysts have been considered highly promising catalysts for the catalytic oxidation of propane due to their high-activity. However, despite the recognized importance of the synergistic effect between Pt nanoparticles (NPs) and support materials, the detailed reaction mechanism investigation remains limited. In this work, we demonstrate that the Pt/Al<sub>2</sub>O<sub>3</sub> catalyst exhibits improved propane catalytic performance, which is attributed to the synergistic interaction between Pt NPs and surface hydroxyl groups on the support. The improved Pt dispersion in Pt/Al<sub>2</sub>O<sub>3</sub> catalysts with smaller Pt NPs facilitates the spillover of gaseous oxygen species and the stabilization of active sites for propane oxidation. Furthermore, in-<em>situ</em> DRIFTS characterization and density functional theory (DFT) calculation confirm that surface hydroxyl groups on Al<sub>2</sub>O<sub>3</sub> effectively reduce the activation barrier for C-H bond cleavage, thereby improving the reactivity of propane molecules. This work provides a novel insight into metal-support synergy for propane oxidation, which offers strategic guidance for the rational design of efficient catalysts in hydrocarbon conversion processes.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120775"},"PeriodicalIF":4.8,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974698","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 : 2026-01-06DOI: 10.1016/j.apcata.2026.120774
Elsayed G. Blall , Rafah Mohammed Thyab , Ahmed H. Abdel-Salam , Ahmed Morsy , Leonara de Oliveira Moura , Asmaa Mohamed , Ashraf Morsy
Heavy-metal contamination remains one of the most persistent global environmental challenges due to its toxicity, non-biodegradability, and accumulation in ecosystems. Conventional remediation techniques often struggle to achieve sustainable, selective, and efficient removal under realistic conditions. Chalcones, a subclass of flavonoids characterized by an α,β-unsaturated carbonyl framework, have recently attracted attention as multifunctional ligands capable of chelation, redox mediation, and surface interactions with transition metals. Recent studies have elucidated the mechanistic role of chalcone-based accelerators in cementation processes, particularly in enhancing catalytic activity and electron-transfer pathways for metal recovery. In parallel, chalcone-functionalized nanoparticles and hybrid nanocomposites have been reported to integrate adsorption, complexation, and redox mechanisms, enabling efficient removal of heavy metals such as Pb(II), Cd(II), and Cr(VI). Comparative analyses of adsorption kinetics, thermodynamic behavior, and regeneration performance reveal distinct advantages of chalcone-derived systems over conventional adsorbents, supported by molecular-level insights from density functional theory (DFT) and spectroscopic investigations. Current research trends indicate growing potential for incorporating chalcone-based nanomaterials into scalable water-treatment and resource-recovery applications, particularly through green synthesis approaches, stability enhancement, and cost-effective implementation.
{"title":"Chalcone-based catalysts and functional nanomaterials for heavy-metal remediation: Mechanistic insights and environmental applications","authors":"Elsayed G. Blall , Rafah Mohammed Thyab , Ahmed H. Abdel-Salam , Ahmed Morsy , Leonara de Oliveira Moura , Asmaa Mohamed , Ashraf Morsy","doi":"10.1016/j.apcata.2026.120774","DOIUrl":"10.1016/j.apcata.2026.120774","url":null,"abstract":"<div><div>Heavy-metal contamination remains one of the most persistent global environmental challenges due to its toxicity, non-biodegradability, and accumulation in ecosystems. Conventional remediation techniques often struggle to achieve sustainable, selective, and efficient removal under realistic conditions. Chalcones, a subclass of flavonoids characterized by an α,β-unsaturated carbonyl framework, have recently attracted attention as multifunctional ligands capable of chelation, redox mediation, and surface interactions with transition metals. Recent studies have elucidated the mechanistic role of chalcone-based accelerators in cementation processes, particularly in enhancing catalytic activity and electron-transfer pathways for metal recovery. In parallel, chalcone-functionalized nanoparticles and hybrid nanocomposites have been reported to integrate adsorption, complexation, and redox mechanisms, enabling efficient removal of heavy metals such as Pb(II), Cd(II), and Cr(VI). Comparative analyses of adsorption kinetics, thermodynamic behavior, and regeneration performance reveal distinct advantages of chalcone-derived systems over conventional adsorbents, supported by molecular-level insights from density functional theory (DFT) and spectroscopic investigations. Current research trends indicate growing potential for incorporating chalcone-based nanomaterials into scalable water-treatment and resource-recovery applications, particularly through green synthesis approaches, stability enhancement, and cost-effective implementation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120774"},"PeriodicalIF":4.8,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903923","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 : 2026-01-06DOI: 10.1016/j.apcata.2026.120772
Liuqingqing Yang , An Bao , Tingting Wang, Chenju Chen, Chunlei Zhang
The direct hydrogenation of succinic anhydride (SA) represents an efficient and industrially promising route for γ-butyrolactone (GBL) production. However, systematic studies on this reaction remain scarce in literature. The present work investigates various SiO2 supported Ni catalysts prepared via different silica sources (silica sol, silica aerogel, and sodium silicate). Results reveal that the silica source could profoundly influence the catalytic performance through modulation of nickel phases over the catalyst surface. Particularly, the silica aerogel synthesized catalyst (Ni/SiO2-SA) demonstrates balanced phyllosilicate and NiO phases, which collectively provide optimal acidity and hydrogen dissociation capability, leading to superior catalytic performance at mild conditions. During a 72 h stability test, this catalyst maintained SA conversion and GBL selectivity at 90 % and 88 %, respectively. This study elucidates the critical role of precursor selection in active phase composition and provides valuable insights for industrial catalyst design for GBL production.
{"title":"Unveiling the importance of nickel phases for selective hydrogenation of succinic anhydride to γ-butyrolactone over Ni/SiO2 catalysts: The impact of silica sources","authors":"Liuqingqing Yang , An Bao , Tingting Wang, Chenju Chen, Chunlei Zhang","doi":"10.1016/j.apcata.2026.120772","DOIUrl":"10.1016/j.apcata.2026.120772","url":null,"abstract":"<div><div>The direct hydrogenation of succinic anhydride (SA) represents an efficient and industrially promising route for γ-butyrolactone (GBL) production. However, systematic studies on this reaction remain scarce in literature. The present work investigates various SiO<sub>2</sub> supported Ni catalysts prepared via different silica sources (silica sol, silica aerogel, and sodium silicate). Results reveal that the silica source could profoundly influence the catalytic performance through modulation of nickel phases over the catalyst surface. Particularly, the silica aerogel synthesized catalyst (Ni/SiO<sub>2</sub>-SA) demonstrates balanced phyllosilicate and NiO phases, which collectively provide optimal acidity and hydrogen dissociation capability, leading to superior catalytic performance at mild conditions. During a 72 h stability test, this catalyst maintained SA conversion and GBL selectivity at 90 % and 88 %, respectively. This study elucidates the critical role of precursor selection in active phase composition and provides valuable insights for industrial catalyst design for GBL production.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120772"},"PeriodicalIF":4.8,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145940921","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 : 2026-01-05DOI: 10.1016/j.apcata.2026.120771
Fang Fang, Dongping Sun, Xinhua Peng
Selective catalytic aerobic oxidation of alcohols into aldehydes and ketones using water as solvent and layered double hydroxides as alkaline catalyst exemplifies both atom economy and environmental benignity. In this work, we initially synthesized oxygen vacancy-rich monolayer m-CoAl-LDH nanosheets through a facile direct synthesis method. Then, by reassembling the CMCD anions with m-CoAl-LDH layers to form an oxygen vacancy-rich heterogeneous CMCD-CoAl-LDH intercalation hybrid. We investigated the application of CMCD-CoAl-LDH in the aerobic oxidation of alcohol in water, and examined the structure-activity relationship. The oxygen vacancy defect sites on the LDH layers activate both oxygen and alcohol molecules. Concurrently, CMCD with LDH layers collaboratively form a confined environment, exerting the confinement effect to achieve highly efficient and selective aerobic oxidation. The adsorption and surface reaction of benzyl alcohol on the catalyst in an O2 atmosphere were investigated by in situ DRIFT spectroscopy. DFT calculation of adsorption energy reveals that oxygen vacancies serve as the primary sites for the adsorption of benzyl alcohol and oxygen molecules. This catalyst system demonstrates excellent compatibility with green aqueous media and significantly promotes the aerobic oxidation of alcohol. It provides a feasible paradigm of integrating supramolecular chemistry with materials chemistry to address challenges in catalysis.
{"title":"Synergy of confinement effect and oxygen vacancy in carboxymethyl-β-cyclodextrin-intercalated CoAl-LDH for boosting selective aerobic oxidation of alcohols in water","authors":"Fang Fang, Dongping Sun, Xinhua Peng","doi":"10.1016/j.apcata.2026.120771","DOIUrl":"10.1016/j.apcata.2026.120771","url":null,"abstract":"<div><div>Selective catalytic aerobic oxidation of alcohols into aldehydes and ketones using water as solvent and layered double hydroxides as alkaline catalyst exemplifies both atom economy and environmental benignity. In this work, we initially synthesized oxygen vacancy-rich monolayer m-CoAl-LDH nanosheets through a facile direct synthesis method. Then, by reassembling the CMCD anions with m-CoAl-LDH layers to form an oxygen vacancy-rich heterogeneous CMCD-CoAl-LDH intercalation hybrid. We investigated the application of CMCD-CoAl-LDH in the aerobic oxidation of alcohol in water, and examined the structure-activity relationship. The oxygen vacancy defect sites on the LDH layers activate both oxygen and alcohol molecules. Concurrently, CMCD with LDH layers collaboratively form a confined environment, exerting the confinement effect to achieve highly efficient and selective aerobic oxidation. The adsorption and surface reaction of benzyl alcohol on the catalyst in an O<sub>2</sub> atmosphere were investigated by in situ DRIFT spectroscopy. DFT calculation of adsorption energy reveals that oxygen vacancies serve as the primary sites for the adsorption of benzyl alcohol and oxygen molecules. This catalyst system demonstrates excellent compatibility with green aqueous media and significantly promotes the aerobic oxidation of alcohol. It provides a feasible paradigm of integrating supramolecular chemistry with materials chemistry to address challenges in catalysis.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120771"},"PeriodicalIF":4.8,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941062","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 : 2026-01-03DOI: 10.1016/j.apcata.2026.120770
Yufei Gu , Yanning Pan , Qi Wei , Ting Zhao , Wei Wang , Yunshuang Hu , Lei Miao , Hongfei Lin , Zhongmin Wang , Zhixia Li
A novel freeze-drying steam-assisted crystallization protocol fabricates multistage porous ZSM-5 zeolites, incorporating multiscale channel architectures (0.5 nm-10 μm) to alleviate mass-transfer constraints inherent in conventional microporous zeolites. This eco-friendly, scalable methodology pioneers catalytic polyethylene pyrolysis by augmenting catalytic activity, achieving exceptional monocyclic aromatic hydrocarbons selectivity of 97.3 % and BTEX (benzene/toluene/ethylbenzene/xylene) selectivity of 94.9 %, surpassing commercial and nanosized counterparts. Demonstrating operational stability, the catalyst maintains 23.7–30.0 wt% oil yields and 71.3–74.9 % BTEX selectivity, attributed to enhanced intracrystalline diffusivity that mitigates coke deposition. Computational simulations reveal that multistage porous structures facilitate reactant diffusion and regulate C-C bond cleavage via steric confinement, synergizing with acid sites to promote cracking-aromatization cascades. Life-cycle analysis confirms the technology’s economic superiority over conventional pyrolysis through improved product value and reduced separation costs. This advancement establishes a sustainable paradigm for zeolite synthesis and plastic-to-aromatics conversion, aligning with circular economy goals.
{"title":"Ice template steam-assisted synthesis of multistage porous ZSM-5 boosts catalytic reforming of plastics to produce aromatics","authors":"Yufei Gu , Yanning Pan , Qi Wei , Ting Zhao , Wei Wang , Yunshuang Hu , Lei Miao , Hongfei Lin , Zhongmin Wang , Zhixia Li","doi":"10.1016/j.apcata.2026.120770","DOIUrl":"10.1016/j.apcata.2026.120770","url":null,"abstract":"<div><div>A novel freeze-drying steam-assisted crystallization protocol fabricates multistage porous ZSM-5 zeolites, incorporating multiscale channel architectures (0.5 nm-10 μm) to alleviate mass-transfer constraints inherent in conventional microporous zeolites. This eco-friendly, scalable methodology pioneers catalytic polyethylene pyrolysis by augmenting catalytic activity, achieving exceptional monocyclic aromatic hydrocarbons selectivity of 97.3 % and BTEX (benzene/toluene/ethylbenzene/xylene) selectivity of 94.9 %, surpassing commercial and nanosized counterparts. Demonstrating operational stability, the catalyst maintains 23.7–30.0 wt% oil yields and 71.3–74.9 % BTEX selectivity, attributed to enhanced intracrystalline diffusivity that mitigates coke deposition. Computational simulations reveal that multistage porous structures facilitate reactant diffusion and regulate C-C bond cleavage via steric confinement, synergizing with acid sites to promote cracking-aromatization cascades. Life-cycle analysis confirms the technology’s economic superiority over conventional pyrolysis through improved product value and reduced separation costs. This advancement establishes a sustainable paradigm for zeolite synthesis and plastic-to-aromatics conversion, aligning with circular economy goals.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120770"},"PeriodicalIF":4.8,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920790","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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