Pub Date : 2026-02-03DOI: 10.1016/j.apcata.2026.120824
Hongping Fang , Wenjun Liang , Liangang Ma , Chenzi Teng , Dandan Tang , Yuling Nie
The poisoning effects of alkali metals (Na, K) and alkaline earth metals (Ca, Mg) on the catalytic performance of 25 % Fe-Al2O3 simulated red mud catalysts were systematically investigated. The impregnation method was used to prepare the catalysts and evaluate them in toluene oxidation reactions. The introduction of these metals resulted in a modest decline in catalytic activity, with the degree of poisoning generally following the order K > Na > Ca > Mg. Catalyst deactivation was attributed to the combined influence of physical and chemical effects. Physical deactivation was associated with metal-induced structural modifications, leading to reductions in surface area and pore volume. In contrast, chemical deactivation arose from changes in surface acidity, inhibition of the Fe2⁺/Fe3⁺ redox cycle, and a decrease in oxygen vacancy concentration. In particular, the presence of Na and Ca caused pronounced suppression of red mud activity. Consequently, for the effective utilisation of red mud as a catalyst, it is essential to minimise the contents of Na and Ca while appropriately adjusting surface acidity to optimise the catalytic performance of the active Fe2O3 component.
{"title":"Influence mechanism of alkali and alkaline earth metals on red mud catalysts for the catalytic oxidation of toluene","authors":"Hongping Fang , Wenjun Liang , Liangang Ma , Chenzi Teng , Dandan Tang , Yuling Nie","doi":"10.1016/j.apcata.2026.120824","DOIUrl":"10.1016/j.apcata.2026.120824","url":null,"abstract":"<div><div>The poisoning effects of alkali metals (Na, K) and alkaline earth metals (Ca, Mg) on the catalytic performance of 25 % Fe-Al<sub>2</sub>O<sub>3</sub> simulated red mud catalysts were systematically investigated. The impregnation method was used to prepare the catalysts and evaluate them in toluene oxidation reactions. The introduction of these metals resulted in a modest decline in catalytic activity, with the degree of poisoning generally following the order K > Na > Ca > Mg. Catalyst deactivation was attributed to the combined influence of physical and chemical effects. Physical deactivation was associated with metal-induced structural modifications, leading to reductions in surface area and pore volume. In contrast, chemical deactivation arose from changes in surface acidity, inhibition of the Fe<sup>2</sup>⁺/Fe<sup>3</sup>⁺ redox cycle, and a decrease in oxygen vacancy concentration. In particular, the presence of Na and Ca caused pronounced suppression of red mud activity. Consequently, for the effective utilisation of red mud as a catalyst, it is essential to minimise the contents of Na and Ca while appropriately adjusting surface acidity to optimise the catalytic performance of the active Fe<sub>2</sub>O<sub>3</sub> component.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"714 ","pages":"Article 120824"},"PeriodicalIF":4.8,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122603","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 direct condensation of acetic acid and formaldehyde is an important alternative route to the petroleum-based propylene two-step oxidation process for acrylic acid production. However, the poor activity and stability of traditional vanadium phosphorus oxide catalyst restrict its industrial application. This work precisely regulated the redox reactivity of VPO catalyst via Mo doping, achieving a highly efficient and stable aldol condensation process with a record-high acrylic acid yield (∼30 %) and outstanding productivity (∼50 μmol⋅gcat−1⋅min−1) in 40 h continuous reaction. The introduction of Mo additive induces the phase transformation of (VO)2P2O7 to VOPO4, successfully constituting a dual-phase redox and acid synergistic catalytic center. Meanwhile, the Mo doping increases the concentration of surface adsorbed oxygen species and the catalyst redox reactivity, efficiently participating in reactant activation and promoting acrylic acid production. Ultimately, the rapid surface oxygen redox process stabilizes the dual-phase synergistic sites and effectively eliminates coke deposit precursors, realizing a stable aldol condensation reaction.
{"title":"Precisely regulated redox behavior of Mo-doped VPO catalyst for efficient and stable condensation of acetic acid and formaldehyde to acrylic acid","authors":"Xueting Yu , Caixia Xu , Yijia Wang, Haoyu Wei, Guowei Wang, Chunyi Li, Chaohe Yang, Xiaolin Zhu","doi":"10.1016/j.apcata.2026.120819","DOIUrl":"10.1016/j.apcata.2026.120819","url":null,"abstract":"<div><div>The direct condensation of acetic acid and formaldehyde is an important alternative route to the petroleum-based propylene two-step oxidation process for acrylic acid production. However, the poor activity and stability of traditional vanadium phosphorus oxide catalyst restrict its industrial application. This work precisely regulated the redox reactivity of VPO catalyst via Mo doping, achieving a highly efficient and stable aldol condensation process with a record-high acrylic acid yield (∼30 %) and outstanding productivity (∼50 μmol⋅gcat<sup>−1</sup>⋅min<sup>−1</sup>) in 40 h continuous reaction. The introduction of Mo additive induces the phase transformation of (VO)<sub>2</sub>P<sub>2</sub>O<sub>7</sub> to VOPO<sub>4</sub>, successfully constituting a dual-phase redox and acid synergistic catalytic center. Meanwhile, the Mo doping increases the concentration of surface adsorbed oxygen species and the catalyst redox reactivity, efficiently participating in reactant activation and promoting acrylic acid production. Ultimately, the rapid surface oxygen redox process stabilizes the dual-phase synergistic sites and effectively eliminates coke deposit precursors, realizing a stable aldol condensation reaction.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120819"},"PeriodicalIF":4.8,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076015","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 : 2026-01-27DOI: 10.1016/j.apcata.2025.120675
Carl Fritsch , Andreas Serwe , Sven Jovanovic , Hariprasad Ranganathan , Marcus Hans , Andreas Hutzler , Jürgen Dornseiffer , Nikolay Kornienko
Zirconia (ZrO2)-, Ceria (CeO2)-, and Calcium (CaO) -promoted Copper oxide (CuO) Zinc oxide (ZnO) catalysts supported on -alumina spheres are synthesized via incipient wetness impregnation (IWI) and characterized using transmission electron microscopy (TEM), Raman spectroscopy, X-ray Photoelectron Spectroscopy (XPS), and CO2/H2-TPD. Catalytic performance is evaluated for carbon oxide hydrogenation to methanol (MeOH) in mixed carbon oxide synthesis gas, examining both CO and CO2-conversion pathways and MeOH space–time yields (STY). Temperature- and pressure-dependent reaction equilibria for MeOH formation from CO and CO2, as well as the reverse water-gas shift reaction (RWGS) are investigated to demonstrate promoter effects on surface reaction mechanisms and conversion efficiency towards MeOH and H2O. Reaction kinetics are optimized using a previously formulated re-parametrized two-site Langmuir–Hinshelwood–Hougen–Watson (LHHW) model for each catalyst system, providing comparative kinetic parameters for the binary, ternary, quaternary, and quinary catalyst formulations. The kinetic models demonstrate good numerical agreement with experimental data for both the promoted catalysts. Although CO-rich streams produce the highest MeOH production rates in all samples, the promotion through ZrO2 and CeO2 significantly improved both CO and CO2 conversion (XC) compared to the binary CuO/ZnO catalyst formulation.
{"title":"CO2- and CO-Conversion to Methanol over promoted CuO/ZnO-based infiltration composite catalyst spheres — Characterization, experimentals and comparative reaction kinetics","authors":"Carl Fritsch , Andreas Serwe , Sven Jovanovic , Hariprasad Ranganathan , Marcus Hans , Andreas Hutzler , Jürgen Dornseiffer , Nikolay Kornienko","doi":"10.1016/j.apcata.2025.120675","DOIUrl":"10.1016/j.apcata.2025.120675","url":null,"abstract":"<div><div>Zirconia (ZrO<sub>2</sub>)-, Ceria (CeO<sub>2</sub>)-, and Calcium (CaO) -promoted Copper oxide (CuO) Zinc oxide (ZnO) catalysts supported on <span><math><mi>γ</mi></math></span>-alumina spheres are synthesized via incipient wetness impregnation (IWI) and characterized using transmission electron microscopy (TEM), Raman spectroscopy, X-ray Photoelectron Spectroscopy (XPS), and CO<sub>2</sub>/H<sub>2</sub>-TPD. Catalytic performance is evaluated for carbon oxide hydrogenation to methanol (MeOH) in mixed carbon oxide synthesis gas, examining both CO and CO<sub>2</sub>-conversion pathways and MeOH space–time yields (STY). Temperature- and pressure-dependent reaction equilibria for MeOH formation from CO and CO<sub>2</sub>, as well as the reverse water-gas shift reaction (RWGS) are investigated to demonstrate promoter effects on surface reaction mechanisms and conversion efficiency towards MeOH and H<sub>2</sub>O. Reaction kinetics are optimized using a previously formulated re-parametrized two-site Langmuir–Hinshelwood–Hougen–Watson (LHHW) model for each catalyst system, providing comparative kinetic parameters for the binary, ternary, quaternary, and quinary catalyst formulations. The kinetic models demonstrate good numerical agreement with experimental data for both the promoted catalysts. Although CO-rich streams produce the highest MeOH production rates in all samples, the promotion through ZrO<sub>2</sub> and CeO<sub>2</sub> significantly improved both CO and CO<sub>2</sub> conversion (X<sub>C</sub>) compared to the binary CuO/ZnO catalyst formulation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120675"},"PeriodicalIF":4.8,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076021","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}
Radical-dependent advanced oxidation processes (AOPs) have emerged as promising technologies for water decontamination, yet remain constrained by critical limitations, including susceptibility to matrix quenching and the formation of toxic byproducts, which hinder their broad application. To address these challenges, this study engineers a ligand-stabilized permanganate/sulfite (Mn(VII)/S(IV)) system using nitrilotriacetic acid (NTA) for efficient degradation of recalcitrant organic pollutants across a wide pH range. The NTA coordination critically stabilizes reactive Mn intermediates (Mn(III) and Mn(V)), generated via two-electron reduction of Mn(VII) by S(IV), effectively mitigating their deactivation through hydrolysis or disproportionation at near-neutral pH. This stabilization enables sustained catalytic activity from pH 4–7.5, overcoming the strict acidic pH requirement of conventional Mn(VII)/S(IV) systems. Mechanistic investigations reveal dual oxidation pathways: Mn(III)–NTA species mediate radical-based oxidation through SO4•− generation, while Mn(V)−NTA species dominate non-radical two-electron oxidation process. Crucially, the Mn(VII)/S(IV) molar ratio serves as a tunable lever governing oxidation pathway selection: higher ratios favor non-radical Mn(V)−NTA oxidation, whereas lower ratios promote SO4•−-based pathways that are subject to self-quenching by excess S(IV). Dissolved oxygen further sustains the catalytic cycles by preventing premature Mn(V) reduction and facilitating oxysulfur radical chain propagation. Moreover, the NTA coordination confers exceptional resilience against common water matrix interferents (e.g., anions and natural organic maters), while maintaining high degradation efficacy in diverse natural waters. This work demonstrates that ligand-stabilized high-valent Mn(V) catalysis enables tunable and robust oxidation pathways, providing new mechanistic insights for precision oxidation technologies.
{"title":"Tunable oxidation pathways via ligand-assisted stabilization of Mn(III)/Mn(V) in a permanganate/sulfite process for robust water treatment","authors":"Junren Zhu , Zhenzhen Jiang , Chaohan Jiang , Hongxiang Zeng , Wei Ding , Xintao Tan , Xinyi Li , Faxiang Zhang","doi":"10.1016/j.apcata.2026.120811","DOIUrl":"10.1016/j.apcata.2026.120811","url":null,"abstract":"<div><div>Radical-dependent advanced oxidation processes (AOPs) have emerged as promising technologies for water decontamination, yet remain constrained by critical limitations, including susceptibility to matrix quenching and the formation of toxic byproducts, which hinder their broad application. To address these challenges, this study engineers a ligand-stabilized permanganate/sulfite (Mn(VII)/S(IV)) system using nitrilotriacetic acid (NTA) for efficient degradation of recalcitrant organic pollutants across a wide pH range. The NTA coordination critically stabilizes reactive Mn intermediates (Mn(III) and Mn(V)), generated via two-electron reduction of Mn(VII) by S(IV), effectively mitigating their deactivation through hydrolysis or disproportionation at near-neutral pH. This stabilization enables sustained catalytic activity from pH 4–7.5, overcoming the strict acidic pH requirement of conventional Mn(VII)/S(IV) systems. Mechanistic investigations reveal dual oxidation pathways: Mn(III)–NTA species mediate radical-based oxidation through SO<sub>4</sub><sup>•−</sup> generation, while Mn(V)−NTA species dominate non-radical two-electron oxidation process. Crucially, the Mn(VII)/S(IV) molar ratio serves as a tunable lever governing oxidation pathway selection: higher ratios favor non-radical Mn(V)−NTA oxidation, whereas lower ratios promote SO<sub>4</sub><sup>•−</sup>-based pathways that are subject to self-quenching by excess S(IV). Dissolved oxygen further sustains the catalytic cycles by preventing premature Mn(V) reduction and facilitating oxysulfur radical chain propagation. Moreover, the NTA coordination confers exceptional resilience against common water matrix interferents (e.g., anions and natural organic maters), while maintaining high degradation efficacy in diverse natural waters. This work demonstrates that ligand-stabilized high-valent Mn(V) catalysis enables tunable and robust oxidation pathways, providing new mechanistic insights for precision oxidation technologies.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120811"},"PeriodicalIF":4.8,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076018","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 : 2026-01-27DOI: 10.1016/j.apcata.2026.120810
Wei-Fan Shao , Bing-Hao Wang , Xiong Wang , Sheng Tian , Hui-Juan Wang , Xing-Sheng Hu , Chao Peng , Jin-Xin Li , Yang Li , Lang Chen , Shuang-Feng Yin
Efficient separation and migration of photogenerated carriers remains pivotal yet challenging for advancing photocatalytic performance. To address this bottleneck, we construct an intimately coupled hydrogen-bonded organic framework (HOF)-perovskite (MA3Bi2Br9, MABB) heterojunction, where augmented built-in electric field (IEF) intensity enables directed accelerated carrier transfer. Benefiting from the interfacial compressive strain induced by lattice distortion, reinforced interfacial coupling interactions achieved in the optimized HOF-MABB-100. This system demonstrates exceptional performance in selective toluene photooxidation, with benzaldehyde production rate reaching 11,350 μmol g−1 h−1 and selectivity up 84 %. Simultaneously, HOF passivates the surface defects of MABB and thereby enhancing its stability by retaining 93 % of its catalytic activity after 4 successive cycles. This work validates the immense potential of HOF as a coupling module for designing high-performance lead-free perovskite photocatalysts.
{"title":"Simultaneous charge separation and defect passivation of perovskite by hydrogen-bonded organic framework for selective toluene photooxidation","authors":"Wei-Fan Shao , Bing-Hao Wang , Xiong Wang , Sheng Tian , Hui-Juan Wang , Xing-Sheng Hu , Chao Peng , Jin-Xin Li , Yang Li , Lang Chen , Shuang-Feng Yin","doi":"10.1016/j.apcata.2026.120810","DOIUrl":"10.1016/j.apcata.2026.120810","url":null,"abstract":"<div><div>Efficient separation and migration of photogenerated carriers remains pivotal yet challenging for advancing photocatalytic performance. To address this bottleneck, we construct an intimately coupled hydrogen-bonded organic framework (HOF)-perovskite (MA<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub>, MABB) heterojunction, where augmented built-in electric field (IEF) intensity enables directed accelerated carrier transfer. Benefiting from the interfacial compressive strain induced by lattice distortion, reinforced interfacial coupling interactions achieved in the optimized HOF-MABB-100. This system demonstrates exceptional performance in selective toluene photooxidation, with benzaldehyde production rate reaching 11,350 μmol g<sup>−1</sup> h<sup>−1</sup> and selectivity up 84 %. Simultaneously, HOF passivates the surface defects of MABB and thereby enhancing its stability by retaining 93 % of its catalytic activity after 4 successive cycles. This work validates the immense potential of HOF as a coupling module for designing high-performance lead-free perovskite photocatalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120810"},"PeriodicalIF":4.8,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076022","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 : 2026-01-26DOI: 10.1016/j.apcata.2026.120802
Lucia Mengel , Pieter van den Berg , Clara Aletsee , Pieter Neethling , Gurthwin Bosman , Benjamin Agyei-Tuffour , Joshua Tuah Asante , Emmanuel Nyankson , David Dodoo-Arhin , Zwonaka Mapholi , Martin Tschurl , Neill Goosen , Ueli Heiz
TiO2 is one of the most studied photocatalysts for hydrogen evolution. As decoration with a metal co-catalyst is essential for catalytic formation of hydrogen, there is an ongoing search for low-cost alternatives to the currently predominant noble metals. In this work, we directly compare Cu and Pt co-catalysts on anatase TiO2 in liquid ethanol photoreforming in the absence of water and oxygen. Under these conditions, high product selectivities are achievable on the carbonaceous side of the reaction. The activity of Cu is in the same order of magnitude as Pt, which makes Cu a prospective candidate. Our results also indicate that low metal loadings might be favorable to achieve high co-catalyst efficiencies. Additional insights into the photocatalyst behavior under reaction conditions complement the photocatalytic investigation. Namely, color changes and absorbance features in the visible indicate a reduction of both TiO2 and the Cu co-catalyst when excluding water and oxygen from the reaction solution. The surface hydroxyls formed during the photooxidation of the alcohol likely take part in these processes, which can be comprehensively explained when considering previous insights from UHV experiments. Consequently, this work not only suggests Cu to be a suitable and cost-efficient replacement for Pt as a co-catalyst for hydrogen evolution but also indicates that surface hydroxyls might play a decisive role in complex photocatalytic reactions on TiO2 in a liquid environment.
{"title":"Cu/TiO2 as a low-cost alternative to Pt/TiO2 for hydrogen production via photocatalytic ethanol reforming: a direct comparison and mechanistic analysis","authors":"Lucia Mengel , Pieter van den Berg , Clara Aletsee , Pieter Neethling , Gurthwin Bosman , Benjamin Agyei-Tuffour , Joshua Tuah Asante , Emmanuel Nyankson , David Dodoo-Arhin , Zwonaka Mapholi , Martin Tschurl , Neill Goosen , Ueli Heiz","doi":"10.1016/j.apcata.2026.120802","DOIUrl":"10.1016/j.apcata.2026.120802","url":null,"abstract":"<div><div>TiO<sub>2</sub> is one of the most studied photocatalysts for hydrogen evolution. As decoration with a metal co-catalyst is essential for catalytic formation of hydrogen, there is an ongoing search for low-cost alternatives to the currently predominant noble metals. In this work, we directly compare Cu and Pt co-catalysts on anatase TiO<sub>2</sub> in liquid ethanol photoreforming in the absence of water and oxygen. Under these conditions, high product selectivities are achievable on the carbonaceous side of the reaction. The activity of Cu is in the same order of magnitude as Pt, which makes Cu a prospective candidate. Our results also indicate that low metal loadings might be favorable to achieve high co-catalyst efficiencies. Additional insights into the photocatalyst behavior under reaction conditions complement the photocatalytic investigation. Namely, color changes and absorbance features in the visible indicate a reduction of both TiO<sub>2</sub> and the Cu co-catalyst when excluding water and oxygen from the reaction solution. The surface hydroxyls formed during the photooxidation of the alcohol likely take part in these processes, which can be comprehensively explained when considering previous insights from UHV experiments. Consequently, this work not only suggests Cu to be a suitable and cost-efficient replacement for Pt as a co-catalyst for hydrogen evolution but also indicates that surface hydroxyls might play a decisive role in complex photocatalytic reactions on TiO<sub>2</sub> in a liquid environment.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120802"},"PeriodicalIF":4.8,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076017","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 : 2026-01-26DOI: 10.1016/j.apcata.2026.120803
Peng-Ge Li , Yi-Fan Yao , Hui Wu, Long-Ren OuYang, Ai-Ping Jia, Yu Wang, Ji-Qing Lu
Bimetallic Fe-Cu modified SSZ-13 catalyst (FeCu-SSZ-13) was prepared by a sequential ion-exchange method and tested for catalytic oxidation of dichloromethane. It was found that the FeCu-SSZ-13 catalyst was more active than the Cu- and Fe-SSZ-13 catalysts, giving a very high reaction rate of 5.04 mmolCH2Cl2 gcat−1 h−1 at 250 °C. The catalyst was highly resistant to water vapor during the reaction, thus showing potential in practical application. The improved performance was attributed to the strong Fe-Cu interaction, not only enhancing the surface acidity and redox capability of the catalyst for higher activity, but stabilizing isolated Cu cations for better catalyst stability particularly under wet condition. Moreover, the in situ spectroscopic investigation on the reaction route revealed that C-Cl cleavage on the surface acid site while the oxidation of reactive intermediates is related to metal cations, which thus showed a clear synergy and accounted for higher mineralization rate.
{"title":"Fe-Cu interaction in SSZ-13 enhanced reactivity and H2O tolerance during catalytic combustion of dichloromethane","authors":"Peng-Ge Li , Yi-Fan Yao , Hui Wu, Long-Ren OuYang, Ai-Ping Jia, Yu Wang, Ji-Qing Lu","doi":"10.1016/j.apcata.2026.120803","DOIUrl":"10.1016/j.apcata.2026.120803","url":null,"abstract":"<div><div>Bimetallic Fe-Cu modified SSZ-13 catalyst (FeCu-SSZ-13) was prepared by a sequential ion-exchange method and tested for catalytic oxidation of dichloromethane. It was found that the FeCu-SSZ-13 catalyst was more active than the Cu- and Fe-SSZ-13 catalysts, giving a very high reaction rate of 5.04 mmol<sub>CH2Cl2</sub> g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup> at 250 °C. The catalyst was highly resistant to water vapor during the reaction, thus showing potential in practical application. The improved performance was attributed to the strong Fe-Cu interaction, not only enhancing the surface acidity and redox capability of the catalyst for higher activity, but stabilizing isolated Cu cations for better catalyst stability particularly under wet condition. Moreover, the in situ spectroscopic investigation on the reaction route revealed that C-Cl cleavage on the surface acid site while the oxidation of reactive intermediates is related to metal cations, which thus showed a clear synergy and accounted for higher mineralization rate.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120803"},"PeriodicalIF":4.8,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076016","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 : 2026-01-22DOI: 10.1016/j.apcata.2026.120800
Zhengxiang Ma , Yanhua Zhang , Qian Zhao , Liya Gao , Dongsheng Zhang , Xinqiang Zhao , Yanji Wang
Adipamide (ADM) is an important intermediate for various polyamides and nitrogen-containing fine chemicals. However, the selective dehydroxylation of α-hydroxyamides remains a significant challenge in catalytic deoxygenation, due to the high bond dissociation energy of aliphatic C–OH bonds and the pronounced electron-withdrawing and intramolecular hydrogen-bonding effects of the amide groups. These structural features greatly stabilize the molecular framework, making C–OH activation difficult under conventional hydrodeoxygenation (HDO) conditions and often leading to undesired C–N or C–C cleavage. In this work, a series of N-modified β-Mo2C catalysts were designed to promote the hydrodehydroxylation (HDH) of 2-hydroxyadipamide (2-HADM) to bio-based ADM. Structural characterizations reveal that nitrogen incorporation forms interstitial Mo–N–Mo environments within the Mo2C lattice, thereby tuning the electronic structure and acid–base properties of Mo sites. The optimized β-Mo2C-N-650 catalyst achieves a 33.2 % conversion and 92.0 % selectivity to ADM at 150 °C and 4 MPa H2. Density functional theory (DFT) calculations further suggest that nitrogen doping may lower the transition-state barrier for C–OH bond scission and stabilize the key intermediates, thus enhancing dehydroxylation selectivity. This study demonstrates that tailoring the local electronic structure of Mo2C provides mechanistic insights and a potential design principle for achieving mild and selective deoxygenation of multifunctional α-hydroxyamide substrates.
己二酰胺（ADM）是各种聚酰胺和含氮精细化学品的重要中间体。然而，α-羟酰胺的选择性去羟基化仍然是催化脱氧中的一个重大挑战，因为脂肪族C-OH键的键解离能很高，并且酰胺基团具有明显的吸电子和分子内氢键作用。这些结构特征极大地稳定了分子框架，使得C-OH在常规氢脱氧（HDO）条件下难以活化，并经常导致不希望的C-N或C-C裂解。在这项工作中，设计了一系列n修饰的β-Mo2C催化剂，以促进2-羟基己二胺（2-HADM）的氢化去羟基化（HDH）为生物基adm。结构表征表明，氮的掺入在Mo2C晶格内形成间隙Mo - n -Mo环境，从而调节Mo位点的电子结构和酸碱性质。优化后的β-Mo2C-N-650催化剂在150℃、4 MPa H2条件下对ADM的转化率为33.2% %，选择性为92.0 %。密度泛函理论（DFT）计算进一步表明，氮掺杂可以降低C-OH键断裂的过渡态势垒，稳定关键中间体，从而提高脱羟基的选择性。该研究表明，定制Mo2C的局部电子结构为实现多功能α-羟酰胺底物的轻度选择性脱氧提供了机制见解和潜在的设计原则。
{"title":"Highly selective hydrodehydroxylation of 2-hydroxyadipamide to bio-based adipamide over N-doped Mo2C catalysts","authors":"Zhengxiang Ma , Yanhua Zhang , Qian Zhao , Liya Gao , Dongsheng Zhang , Xinqiang Zhao , Yanji Wang","doi":"10.1016/j.apcata.2026.120800","DOIUrl":"10.1016/j.apcata.2026.120800","url":null,"abstract":"<div><div>Adipamide (ADM) is an important intermediate for various polyamides and nitrogen-containing fine chemicals. However, the selective dehydroxylation of α-hydroxyamides remains a significant challenge in catalytic deoxygenation, due to the high bond dissociation energy of aliphatic C–OH bonds and the pronounced electron-withdrawing and intramolecular hydrogen-bonding effects of the amide groups. These structural features greatly stabilize the molecular framework, making C–OH activation difficult under conventional hydrodeoxygenation (HDO) conditions and often leading to undesired C–N or C–C cleavage. In this work, a series of N-modified β-Mo<sub>2</sub>C catalysts were designed to promote the hydrodehydroxylation (HDH) of 2-hydroxyadipamide (2-HADM) to bio-based ADM. Structural characterizations reveal that nitrogen incorporation forms interstitial Mo–N–Mo environments within the Mo<sub>2</sub>C lattice, thereby tuning the electronic structure and acid–base properties of Mo sites. The optimized β-Mo<sub>2</sub>C-N-650 catalyst achieves a 33.2 % conversion and 92.0 % selectivity to ADM at 150 °C and 4 MPa H<sub>2</sub>. Density functional theory (DFT) calculations further suggest that nitrogen doping may lower the transition-state barrier for C–OH bond scission and stabilize the key intermediates, thus enhancing dehydroxylation selectivity. This study demonstrates that tailoring the local electronic structure of Mo<sub>2</sub>C provides mechanistic insights and a potential design principle for achieving mild and selective deoxygenation of multifunctional α-hydroxyamide substrates.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120800"},"PeriodicalIF":4.8,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076019","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 : 2026-01-22DOI: 10.1016/j.apcata.2026.120801
Grigory B. Veselov, Ekaterina V. Ilyina, Vladimir O. Stoyanovskii, Aleksey A. Vedyagin
Sol-gel-prepared Ni-Mg-O oxide systems are considered promising catalysts for dry reforming of methane. The addition of CeO2 to the catalyst composition enhances its performance under reaction conditions. Another factor affecting the activity and thermal stability of such catalysts is the strength of the NiO-MgO interaction. In this research, the effects of calcination temperature on the textural characteristics, strength of NiO-MgO interaction, and catalytic performance of Ni-Mg-O and Ni-Ce-Mg-O in the dry reforming of methane are studied. As found, the sintering resistance of MgO is noticeably enhanced in the presence of CeO2. Moreover, CeO2 hinders the formation of NixMg1-xO solid solutions, thus improving the reducibility of Ni. The strength of the NiO-MgO interaction increased with the temperature for both the Ni-Mg-O and Ni-Ce-Mg-O samples, while the NiO-CeO2 interaction was optimal after calcination at 600 °C. The increased stability of the CeO2-containing catalyst under dry reforming conditions is due to the suppressed formation of carbon deposits. Among the Ce-containing catalysts, the samples calcined at 500 and 600 °С exhibited an optimal catalytic performance. Thus, the former demonstrated a higher conversion of the reagents, while the latter showed a higher stability. At a higher calcination temperature (700 °С), the weaker NiO-CeO2 and NiO-MgO interactions worsened both the stability and catalytic activity. The Ni-Ce-Mg-O sample calcined at 600 °C was tested at 30 L/(g·h) and 750 °C for 140 h and demonstrated the values of CH4 and CO2 conversions of 89.6 and 90.2 %, respectively. As revealed by high-resolution transmission electron microscopy, regardless of calcination temperature, reduction of CeO2 in hydrogen at 750 °C has led to the formation of highly dispersed clusters along with layers at the intra-crystallite boundaries. The interaction of these CeO2 species with Ni is supposed to be responsible for the enhanced catalytic performance.
{"title":"Dry reforming of methane over Ni-Mg-O and Ni-Ce-Mg-O oxide catalysts: Effect of the calcination temperature on the catalytic performance and thermal stability","authors":"Grigory B. Veselov, Ekaterina V. Ilyina, Vladimir O. Stoyanovskii, Aleksey A. Vedyagin","doi":"10.1016/j.apcata.2026.120801","DOIUrl":"10.1016/j.apcata.2026.120801","url":null,"abstract":"<div><div>Sol-gel-prepared Ni-Mg-O oxide systems are considered promising catalysts for dry reforming of methane. The addition of CeO<sub>2</sub> to the catalyst composition enhances its performance under reaction conditions. Another factor affecting the activity and thermal stability of such catalysts is the strength of the NiO-MgO interaction. In this research, the effects of calcination temperature on the textural characteristics, strength of NiO-MgO interaction, and catalytic performance of Ni-Mg-O and Ni-Ce-Mg-O in the dry reforming of methane are studied. As found, the sintering resistance of MgO is noticeably enhanced in the presence of CeO<sub>2</sub>. Moreover, CeO<sub>2</sub> hinders the formation of Ni<sub>x</sub>Mg<sub>1-x</sub>O solid solutions, thus improving the reducibility of Ni. The strength of the NiO-MgO interaction increased with the temperature for both the Ni-Mg-O and Ni-Ce-Mg-O samples, while the NiO-CeO<sub>2</sub> interaction was optimal after calcination at 600 °C. The increased stability of the CeO<sub>2</sub>-containing catalyst under dry reforming conditions is due to the suppressed formation of carbon deposits. Among the Ce-containing catalysts, the samples calcined at 500 and 600 °С exhibited an optimal catalytic performance. Thus, the former demonstrated a higher conversion of the reagents, while the latter showed a higher stability. At a higher calcination temperature (700 °С), the weaker NiO-CeO<sub>2</sub> and NiO-MgO interactions worsened both the stability and catalytic activity. The Ni-Ce-Mg-O sample calcined at 600 °C was tested at 30 L/(g·h) and 750 °C for 140 h and demonstrated the values of CH<sub>4</sub> and CO<sub>2</sub> conversions of 89.6 and 90.2 %, respectively. As revealed by high-resolution transmission electron microscopy, regardless of calcination temperature, reduction of CeO<sub>2</sub> in hydrogen at 750 °C has led to the formation of highly dispersed clusters along with layers at the intra-crystallite boundaries. The interaction of these CeO<sub>2</sub> species with Ni is supposed to be responsible for the enhanced catalytic performance.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120801"},"PeriodicalIF":4.8,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076023","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 : 2026-01-21DOI: 10.1016/j.apcata.2026.120798
Yanke Huang , Pengzhen Yin , Xingtao Zhao , Fengqi Zhang , Huibing Shi , Zhaozhan Wang , Chen Li , Xufeng Lin , Yong Yang
Developing ligand-free heterogeneous catalysts capable of efficient and selective hydroformylation of sterically hindered alkenes remains a challenge. In this work, we report a stable and highly efficient ligand-free heterogeneous catalyst comprising atomically dispersed Rh sites anchored on N-doped SiO2. The N-doped SiO2 support was synthesized through a sol-gel method followed by high-temperature calcination under an inert atmosphere, endowing it with a large surface area, hierarchical pores, and tunable nitrogen content. This support facilitates the atomic dispersion and stabilization of Rh sites via strong Rh-N bond coordination. The morphological structure and local environment of single-Rh sites was comprehensively characterization by means of X-ray diffraction (XRD), N2 sorption isotherm, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), high-angle angular dark field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), CO in-situ diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS), and X-ray absorption spectroscopy (XAS). The resulting catalyst exhibits outstanding catalytic performance and excellent selectivity in the hydroformylation of diisobutylene and also shows broad applicability to various other alkenes, including α-olefins, internal alkenes, and aromatic alkenes. Furthermore, it exhibits remarkable stability and recyclability, maintaining its catalytic performance without degradation upon successive cycles. Comparative studies further confirm the essential role of N-doping in achieving high activity and stability.
{"title":"An atomically dispersed Rh catalyst on nitrogen-doped silica for hydroformylation of sterically hindered diisobutylene","authors":"Yanke Huang , Pengzhen Yin , Xingtao Zhao , Fengqi Zhang , Huibing Shi , Zhaozhan Wang , Chen Li , Xufeng Lin , Yong Yang","doi":"10.1016/j.apcata.2026.120798","DOIUrl":"10.1016/j.apcata.2026.120798","url":null,"abstract":"<div><div>Developing ligand-free heterogeneous catalysts capable of efficient and selective hydroformylation of sterically hindered alkenes remains a challenge. In this work, we report a stable and highly efficient ligand-free heterogeneous catalyst comprising atomically dispersed Rh sites anchored on N-doped SiO<sub>2</sub>. The N-doped SiO<sub>2</sub> support was synthesized through a sol-gel method followed by high-temperature calcination under an inert atmosphere, endowing it with a large surface area, hierarchical pores, and tunable nitrogen content. This support facilitates the atomic dispersion and stabilization of Rh sites via strong Rh-N bond coordination. The morphological structure and local environment of single-Rh sites was comprehensively characterization by means of X-ray diffraction (XRD), N<sub>2</sub> sorption isotherm, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), high-angle angular dark field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), CO in-situ diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS), and X-ray absorption spectroscopy (XAS). The resulting catalyst exhibits outstanding catalytic performance and excellent selectivity in the hydroformylation of diisobutylene and also shows broad applicability to various other alkenes, including α-olefins, internal alkenes, and aromatic alkenes. Furthermore, it exhibits remarkable stability and recyclability, maintaining its catalytic performance without degradation upon successive cycles. Comparative studies further confirm the essential role of N-doping in achieving high activity and stability.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120798"},"PeriodicalIF":4.8,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146037363","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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