Applied Catalysis A: General最新文献

Influence mechanism of alkali and alkaline earth metals on red mud catalysts for the catalytic oxidation of toluene 碱和碱土金属对赤泥催化剂催化氧化甲苯的影响机理

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-25 Epub Date: 2026-02-03 DOI: 10.1016/j.apcata.2026.120824

Hongping Fang , Wenjun Liang , Liangang Ma , Chenzi Teng , Dandan Tang , Yuling Nie

{"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":"2026-03-25","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}

引用次数: 0

CO2- and CO-Conversion to Methanol over promoted CuO/ZnO-based infiltration composite catalyst spheres — Characterization, experimentals and comparative reaction kinetics CuO/ zno基渗透复合催化剂球上的CO2和co转化为甲醇——表征、实验和比较反应动力学

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-05 Epub Date: 2026-01-27 DOI: 10.1016/j.apcata.2025.120675

Carl Fritsch , Andreas Serwe , Sven Jovanovic , Hariprasad Ranganathan , Marcus Hans , Andreas Hutzler , Jürgen Dornseiffer , Nikolay Kornienko

{"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":"2026-03-05","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}

引用次数: 0

Dual design strategy in Zr–MOFs: Enlarged channels and electron-withdrawing linkers boost oxygen evolution zr - mof的双重设计策略：扩大通道和吸电子连接体促进氧析出

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-05 Epub Date: 2026-01-21 DOI: 10.1016/j.apcata.2026.120799

Ayyavu Thirunarayanan , Sivalingam Gopi , Arasappan Hemamalini , Monica Soler , Francisco Gracia

{"title":"Dual design strategy in Zr–MOFs: Enlarged channels and electron-withdrawing linkers boost oxygen evolution","authors":"Ayyavu Thirunarayanan , Sivalingam Gopi , Arasappan Hemamalini , Monica Soler , Francisco Gracia","doi":"10.1016/j.apcata.2026.120799","DOIUrl":"10.1016/j.apcata.2026.120799","url":null,"abstract":"<div><div>Electrocatalytic water splitting is limited by the sluggish oxygen evolution reaction (OER). This study investigates how structural and electronic modifications in UiO-type zirconium metal–organic frameworks (MOFs) influence their catalytic activity toward the oxygen evolution reaction. UiO-67, constructed from biphenyl-4,4′-dicarboxylate linkers, provides enlarged pore channels that enhance electrolyte accessibility and mass transport, whereas UiO-66-NO<sub>2</sub>, based on nitro-functionalized terephthalate linkers, incorporates strong electron-withdrawing groups that modulate the local Zr–O–C coordination environment. FE-SEM, FTIR, and N<sub>2</sub> sorption analyses confirmed the characteristic <em>fcu</em> topology and high surface areas expected for successful linker incorporation. In 0.1 M KOH, UiO-67 exhibited an overpotential (η<sub>10</sub>) of 290 mV at 10 mA cm<sup>−2</sup>, and a Tafel slope of 70 mV dec<sup>−1</sup>. UiO-66-NO<sub>2</sub> required 340 mV to reach 10 mA cm<sup>−2</sup>, while commercial RuO<sub>2</sub> showed an overpotential (η<sub>10</sub>) of 470 mV under identical conditions. Both MOFs sustained stable activity over 27 h of continuous electrolysis. These results demonstrate that integrating enlarged pore architectures with electron-withdrawing linker functionality can effectively reduce OER overpotentials and enhance charge-transfer characteristics in alkaline media.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120799"},"PeriodicalIF":4.8,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147421442","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}

引用次数: 0

Synergistic vanadium-cerium bimetallic oxide catalyst and solvent effect for efficient oxidation of ethylbenzene to acetophenone 协同钒铈双金属氧化物催化剂及溶剂效应对乙苯高效氧化制苯乙酮的影响

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-05 Epub Date: 2026-02-02 DOI: 10.1016/j.apcata.2026.120820

Xin Guo , Weitao Wang , Huan Wang , Jiaqi Zhu , Yang Liu , Zhen-Hong He , Yang Yang , Kuan Wang , Zhao-Tie Liu

{"title":"Synergistic vanadium-cerium bimetallic oxide catalyst and solvent effect for efficient oxidation of ethylbenzene to acetophenone","authors":"Xin Guo , Weitao Wang , Huan Wang , Jiaqi Zhu , Yang Liu , Zhen-Hong He , Yang Yang , Kuan Wang , Zhao-Tie Liu","doi":"10.1016/j.apcata.2026.120820","DOIUrl":"10.1016/j.apcata.2026.120820","url":null,"abstract":"<div><div>Given the widespread application of acetophenone, the development of a green synthetic process for selective oxidation from ethylbenzene to acetophenone has garnered significant attention in recent years. This study synthesized a vanadium-cerium bimetallic catalyst (CeVO<sub><em>x</em></sub>), which achieved an 87.2 % conversion rate and 90.2 % selectivity under reaction conditions of 80 °C for 8 h. Solvent effect studies revealed that solvent influence on catalytic performance primarily stems from substrate adsorption and product desorption. Apparent activation energies for the reaction under different solvents were also investigated. Kinetic studies revealed a two-step sequential first-order reaction mechanism, where both high ethylbenzene conversion and high acetophenone selectivity are kinetically controlled. Comprehensive characterization confirmed a synergistic effect between vanadium and cerium, effectively lowering the activation energy barrier. Radical trapping experiments demonstrated the involvement of peroxy radicals and hydroxyl radicals in the reaction process. In addition, the present catalytic system exhibits excellent expansion for ethylbenzene derivatives.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120820"},"PeriodicalIF":4.8,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147421444","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}

引用次数: 0

Cu/TiO2 as a low-cost alternative to Pt/TiO2 for hydrogen production via photocatalytic ethanol reforming: a direct comparison and mechanistic analysis Cu/TiO2作为Pt/TiO2光催化乙醇重整制氢的低成本替代品：直接比较和机理分析

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-05 Epub Date: 2026-01-26 DOI: 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

{"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":"2026-03-05","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}

引用次数: 0

Understanding the synergistic role of ZnO-ZnGa2O4 in Cu-based catalysts for CO2 hydrogenation to methanol ZnO-ZnGa2O4在cu基CO2加氢制甲醇催化剂中的协同作用

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-05 Epub Date: 2026-01-29 DOI: 10.1016/j.apcata.2026.120817

Xiaohang Sun , Shuairen Qian , Hongwei Li , Binhang Yan

{"title":"Understanding the synergistic role of ZnO-ZnGa2O4 in Cu-based catalysts for CO2 hydrogenation to methanol","authors":"Xiaohang Sun , Shuairen Qian , Hongwei Li , Binhang Yan","doi":"10.1016/j.apcata.2026.120817","DOIUrl":"10.1016/j.apcata.2026.120817","url":null,"abstract":"<div><div>The catalytic hydrogenation of CO<sub>2</sub> to methanol represents a promising approach for carbon recycling and renewable fuel synthesis. Although Cu/ZnO-based catalysts are well-established for this process, the structure-activity relationship in ZnGa<sub>2</sub>O<sub>4</sub> spinel-promoted catalysts remains poorly understood. In particular, the electronic and defect-related roles of ZnGa<sub>2</sub>O<sub>4</sub> and its interaction with ZnO require further clarification. This work aims to address this gap by designing a series of Cu/ZnO-ZnGa<sub>2</sub>O<sub>4</sub> catalysts with varying Zn/Ga ratios to harness the synergistic effects at their interfaces. The results demonstrated that the ZnO and ZnGa<sub>2</sub>O<sub>4</sub> composite support significantly improves Cu dispersion by creating a higher-surface-area, porous support and ZnO-ZnGa<sub>2</sub>O<sub>4</sub> interface, thereby suppressing Cu agglomeration. And the ZnO dispersion has also been improved by spatially segregating ZnO through spinel formation. Meanwhile, optimizing the Zn/Ga molar ratio to 1:1 markedly enhances both CO<sub>2</sub> activation capacity, methanol yield and reaction stability. Quasi in-situ XPS, EPR, CO<sub>2</sub>-N<sub>2</sub>O titration, CO<sub>2</sub>-TPSR and CO<sub>2</sub>-TPD studies revealed the formation of oxygen vacancies and partially reduced Zn species, which are closely associated with enhanced CO<sub>2</sub> adsorption and activation. In-situ DRIFTS provided dynamic evidence of the formation and hydrogenation behavior of key intermediates, highlighting the synergistic role of Cu, ZnO and ZnGa<sub>2</sub>O<sub>4</sub> in facilitating CO<sub>2</sub> adsorption and hydrogenation. Based on these insights into the spinel-enhanced activation process, this work provides a foundation for designing structurally optimized Cu-based catalysts for efficient CO<sub>2</sub>-to-methanol conversion.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"713 ","pages":"Article 120817"},"PeriodicalIF":4.8,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147421443","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}

引用次数: 0

Non-bridged bisphosphine chromium catalysts for ethylene tetramerization: The influence of bridging groups in dynamic catalytic processes 乙烯四聚化非桥接双膦铬催化剂：桥接基团在动态催化过程中的影响

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-05 Epub Date: 2026-01-07 DOI: 10.1016/j.apcata.2026.120773

Jiangnan Zhang, Zhou Wang, Jiaxin Hu, Jinyan Tan, Na Zhang, Jun Wang

{"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":"2026-03-05","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}

引用次数: 0

Precisely regulated redox behavior of Mo-doped VPO catalyst for efficient and stable condensation of acetic acid and formaldehyde to acrylic acid 精确调控mo掺杂VPO催化剂氧化还原行为，实现醋酸和甲醛高效稳定缩合成丙烯酸

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-05 Epub Date: 2026-01-30 DOI: 10.1016/j.apcata.2026.120819

Xueting Yu , Caixia Xu , Yijia Wang, Haoyu Wei, Guowei Wang, Chunyi Li, Chaohe Yang, Xiaolin Zhu

{"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":"2026-03-05","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}

引用次数: 0

Highly selective hydrodehydroxylation of 2-hydroxyadipamide to bio-based adipamide over N-doped Mo2C catalysts n掺杂Mo2C催化剂上2-羟基己二胺的高选择性氢脱羟基化制备生物基己二胺

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-05 Epub Date: 2026-01-22 DOI: 10.1016/j.apcata.2026.120800

Zhengxiang Ma , Yanhua Zhang , Qian Zhao , Liya Gao , Dongsheng Zhang , Xinqiang Zhao , Yanji Wang

{"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":"2026-03-05","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}

引用次数: 0

An atomically dispersed Rh catalyst on nitrogen-doped silica for hydroformylation of sterically hindered diisobutylene 氮掺杂二氧化硅上原子分散的Rh催化剂用于位阻二异丁烯的氢甲酰化

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2026-03-05 Epub Date: 2026-01-21 DOI: 10.1016/j.apcata.2026.120798

Yanke Huang , Pengzhen Yin , Xingtao Zhao , Fengqi Zhang , Huibing Shi , Zhaozhan Wang , Chen Li , Xufeng Lin , Yong Yang

{"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":"2026-03-05","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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