Journal of Catalysis最新文献_第9页

Composites of Fe2O3 quantum dots/2D g-C3N4 for heterogeneous photocatalytic oxidative trifluoromethylation of alkenes Fe2O3量子点/2D g-C3N4复合材料在烯烃非均相光催化氧化三氟甲基化中的应用

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-21 DOI: 10.1016/j.jcat.2025.116385

Yuyang Wang, Chun Cai

{"title":"Composites of Fe2O3 quantum dots/2D g-C3N4 for heterogeneous photocatalytic oxidative trifluoromethylation of alkenes","authors":"Yuyang Wang, Chun Cai","doi":"10.1016/j.jcat.2025.116385","DOIUrl":"10.1016/j.jcat.2025.116385","url":null,"abstract":"<div><div>It is a promising choice to explore the oxidative trifluoromethylation of alkenes for α-trifluoromethylated ketone compounds with CF<sub>3</sub>SO<sub>2</sub>Na in heterogeneous catalytic systems. However, the single electron transfer (SET) process that occurred with production of reactive oxygen species (ROS), is rarely reported in the field of heterogeneous photocatalysis. In this study, we report composites of Fe<sub>2</sub>O<sub>3</sub> quantum dots (QDs)/graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) layered nanosheets constructed by calcination method for the photocatalytic process. Excitingly, the Fe<sub>2</sub>O<sub>3</sub> QDs/g-C<sub>3</sub>N<sub>4</sub>-1200 catalyst exhibits highest activity and broad substrate flexibility under mild conditions. Moreover, we reveal that Fe<sub>2</sub>O<sub>3</sub> QDs could offer efficient charge separation to facilitate the production of ROS, which is beneficial to activation of CF<sub>3</sub>SO<sub>2</sub>Na for CF<sub>3</sub> radical. Meanwhile, sufficiently exposed metal active sites have been proven indispensable. This study provides an eco-friendly approach to design heterogeneous QDs photocatalysts, promoting the advancement of fluorine chemistry.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116385"},"PeriodicalIF":6.5,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Carbene enzyme-inspired confined catalysis in metal-organic framework for enhanced selectivity 金属-有机骨架中卡宾酶激发的限制性催化增强选择性

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-21 DOI: 10.1016/j.jcat.2025.116359

Jianing Li , Xiongwen Li , Pinyi Ma , Tiexin Zhang , Chunying Duan

{"title":"Carbene enzyme-inspired confined catalysis in metal-organic framework for enhanced selectivity","authors":"Jianing Li , Xiongwen Li , Pinyi Ma , Tiexin Zhang , Chunying Duan","doi":"10.1016/j.jcat.2025.116359","DOIUrl":"10.1016/j.jcat.2025.116359","url":null,"abstract":"<div><div>Developing catalysts with precise micro-environments to regulate catalytic performance has been a continuous endeavor. A carbene enzyme-inspired crystalline porous metal–organic framework (MOF) material incorporating dense and ordered imidazolium cations was synthesized and named <strong>IMI-1</strong>. In a proper alkaline environment, <strong>IMI-1</strong> was found to have dynamic N-heterocyclic carbene (NHC) on its inner pore walls. This catalytic material exhibits potential for various NHC-catalyzed reactions. After applied to annulation reactions between chalcone and 3-aryl acrolein, <strong>IMI-1</strong> has shown a notable selectivity with a high diastereomeric ratio up to 139:1 (<em>trans</em>/<em>cis</em>) for <em>p</em>-alkoxylphenyl acrolein, a top-level performance compared to existing literature. Critical transition states that determine reaction selectivity were assessed with semi-empirical computations, and initial findings suggested that a unique micro-environment near the NHC catalytic center is the primary determinant of this enhancement. Similar to natural enzymes, in <strong>IMI-1</strong> pores, the Breslow intermediate, a key molecule attached to the pore wall, was uniquely constrained to a conformation that significantly differentiated the energies required for generating different geometric isomers. This regulative capability of <strong>IMI-1</strong> has similarities to natural enzymes and could shed some light on the future design of catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116359"},"PeriodicalIF":6.5,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

The use of highly polar additives to reduce the degradation of Cu/ZnO/Al2O3 catalysts during the gas phase hydrogenation of CO2 to methanol and CO 采用高极性添加剂减少Cu/ZnO/Al2O3催化剂在CO2气相加氢制甲醇和CO过程中的降解

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-20 DOI: 10.1016/j.jcat.2025.116384

Dominic Walter , Pit Völs , Andreas Lißner , Bianca Störr , Nikola Kostková , Petr Sazama , Florian Mertens

{"title":"The use of highly polar additives to reduce the degradation of Cu/ZnO/Al2O3 catalysts during the gas phase hydrogenation of CO2 to methanol and CO","authors":"Dominic Walter , Pit Völs , Andreas Lißner , Bianca Störr , Nikola Kostková , Petr Sazama , Florian Mertens","doi":"10.1016/j.jcat.2025.116384","DOIUrl":"10.1016/j.jcat.2025.116384","url":null,"abstract":"<div><div>The impact of catalyst deactivation due to sintering on the activity and properties of the Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> system in CO<sub>2</sub> hydrogenation to methanol was systematically investigated. Additionally, the effects of various additives on methanol yield and catalyst stability during CO<sub>2</sub>/H<sub>2</sub> hydrogenation were evaluated. Additives such as methanol were confirmed to enhance catalytic activity, while components with high dipole moments exhibited a poisoning effect. Interestingly, despite their deactivating influence on activity, these polar additives significantly improved catalyst stability. It is presumed that highly polar species adsorb onto the catalyst surface, displacing water that would otherwise promote crystal growth of copper and zinc oxides, leading to deactivation. A combined additive strategy using methanol (to boost activity) and propylene carbonate (to enhance stability) offers a novel approach to significantly slow down Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> catalyst deactivation during gas-phase CO<sub>2</sub> hydrogenation, without compromising initial activity compared to conventional additive-free systems. Thus, catalyst stability can be effectively improved through the addition of appropriate components to the feed, without sacrificing reaction rate.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116384"},"PeriodicalIF":6.5,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144903532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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-catalyst system without supported metals toward polyethylene waste upcycling 无负载金属双催化剂体系对聚乙烯废弃物升级回收的研究

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-20 DOI: 10.1016/j.jcat.2025.116383

Shuai Wang , Rongyao Wang , Yifan Jiang, Huabin Lian, Yipin Lv, Bin Wang, Huaiqing Zhao, Gengxiu Zheng, Guozhu Chen, Daowei Gao

{"title":"Dual-catalyst system without supported metals toward polyethylene waste upcycling","authors":"Shuai Wang , Rongyao Wang , Yifan Jiang, Huabin Lian, Yipin Lv, Bin Wang, Huaiqing Zhao, Gengxiu Zheng, Guozhu Chen, Daowei Gao","doi":"10.1016/j.jcat.2025.116383","DOIUrl":"10.1016/j.jcat.2025.116383","url":null,"abstract":"<div><div>The accumulation of polyolefin plastic wastes has emerged as a pressing global environmental challenge, driven by its inherent resistance to degradation and the limited efficiency of current recycling technologies. Hydroconversion methods, such as hydrocracking, offer a promising route for transforming polyolefins into high-value liquid alkanes under mild conditions. However, most current catalytic systems are heavily dependent on expensive noble metals, resulting in high management costs. Here, we report a cost-effective and scalable free of supported metals dual-catalyst system combining β zeolite and metal oxides (Nb<sub>2</sub>O<sub>5</sub>, CeO<sub>2</sub>, TiO<sub>2</sub>, or ZrO<sub>2</sub>) for the tandem cracking-hydrogenation of polyolefins under mild conditions. The system exploits a strong synergistic effect between β zeolite and oxide, achieving a polyethylene (PE) conversion of up to 98.2 % and liquid alkane yields of 87.1 %, with a product distribution centered in the C<sub>4</sub>–C<sub>15</sub> range. Mechanistic investigations, supported by in situ spectroscopy and DFT calculations, revealed that polymer chains are initially cracked at the Brønsted acid sites of β zeolite to form olefins, which are subsequently hydrogenated on oxides via heterolytic H<sub>2</sub> activation. Notably, the system demonstrated stability and versatility in processing PE-rich waste plastics. This study presents a practical and economically viable approach to converting plastic waste into valuable fuels, which is expected to advance sustainable chemical recycling strategies.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116383"},"PeriodicalIF":6.5,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144903538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

On the deactivation and regeneration mechanisms of Pd/θ-Al2O3 catalysts for propane oxidation Pd/θ-Al2O3丙烷氧化催化剂的失活与再生机理研究

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-18 DOI: 10.1016/j.jcat.2025.116380

Tieyao Xu , Meiqing Shen , Gurong Shen , Xinhua Li , Liwei Jia , Feng Gao , Wei Li

{"title":"On the deactivation and regeneration mechanisms of Pd/θ-Al2O3 catalysts for propane oxidation","authors":"Tieyao Xu , Meiqing Shen , Gurong Shen , Xinhua Li , Liwei Jia , Feng Gao , Wei Li","doi":"10.1016/j.jcat.2025.116380","DOIUrl":"10.1016/j.jcat.2025.116380","url":null,"abstract":"<div><div>Pd/Al<sub>2</sub>O<sub>3</sub> is widely used to eliminate hydrocarbon volatile organic compounds (VOCs) via catalytic oxidation under lean conditions. However, a long-standing issue with this catalytic system is the rapid deactivation of the catalyst due to H<sub>2</sub>O poisoning. In this study, we employed a variety of regeneration methods to treat deactivated Pd/θ-Al<sub>2</sub>O<sub>3</sub>, and then conducted detailed characterizations using X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and <em>in situ</em> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to explore the underlying mechanisms of catalyst deactivation and regeneration. Our findings indicate that only surface hydroxyls that form on PdO or at the PdO-Al<sub>2</sub>O<sub>3</sub> boundary exhibit poisoning effects. Among the regeneration methods tested, a reduction treatment with H<sub>2</sub>, followed by <em>in situ</em> or <em>ex situ</em> reoxidation, proved to be the most effective in eliminating these poisoning surface hydroxyls and restoring the highly active form of PdO. In contrast, treatment in O<sub>2</sub> at elevated temperatures, although highly efficient in eliminating surface hydroxyls, does not restore the highly active PdO form. This is likely due to adverse high-temperature morphological transformation of PdO that lowers the reactant activation capacity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116380"},"PeriodicalIF":6.5,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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 efficient epoxide carbonylation to β-lactones using a monophosphine cobalt acetyl complex 利用单膦钴乙酰配合物，高效地将环氧化物羰基化成β-内酯

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-18 DOI: 10.1016/j.jcat.2025.116381

Vinothkumar Ganesan, Senkuttuvan Rajendiran, Jianwei Jiang, Sungho Yoon

引用次数: 0

Oxygen vacancy-rich metal oxides and Co-Cu alloy bifunctional sites for selective conversion of furfural to 1,2-pentanediol and 1,5-pentanediol 富氧空的金属氧化物和Co-Cu合金的双功能位点选择性转化糠醛为1,2-戊二醇和1,5-戊二醇

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-14 DOI: 10.1016/j.jcat.2025.116378

Zonghao Zhang , Lei Huang , Pingle Liu

{"title":"Oxygen vacancy-rich metal oxides and Co-Cu alloy bifunctional sites for selective conversion of furfural to 1,2-pentanediol and 1,5-pentanediol","authors":"Zonghao Zhang , Lei Huang , Pingle Liu","doi":"10.1016/j.jcat.2025.116378","DOIUrl":"10.1016/j.jcat.2025.116378","url":null,"abstract":"<div><div>One-step conversion of biomass-derived furfural (FA) to 1,2-pentanediol (1,2-PeD) and 1,5-pentanediol (1,5-PeD) by selective cleavage of C<img>O<img>C is of great significance. However, the lack of knowledge of the active sites in this reaction leads to poor catalytic performance over the currently used non-noble metal hydrogenation catalysts. In this work, xCoyCu/MgAlO<sub>x</sub>-T catalysts with Co-Cu alloy as well as O<sub>v</sub>-rich CuO and CoO bifunctional active sites were constructed by modulating the metal ratio and reduction temperature. During the reaction, the Co-Cu alloy enhanced the H<sub>2</sub> dissociation efficiency and hydrogenation of FA to furfuryl alcohol (FOL). In addition, the C<img>O<img>C is inclined to adsorb on the O<sub>v</sub>-rich CuO and CoO, while the active H* dissociates from the Co-Cu alloy and spills out onto the surfaces of CuO and CoO to participate in the hydrogenation reaction. Moreover, DFT calculation shows that O<sub>v</sub>-rich CuO and CoO significantly reduce the cleavage energy barrier of C<img>O<img>C bond, leading to 22.57 % yield of 1,2-PeD and 49.78 % yield of 1,5-PeD over 3Co1Cu/MgAlO<sub>x</sub>-600. This study provides an in-depth understanding of the reaction mechanism of FA conversion to 1,2-PeD and 1,5-PeD, as well as offers a viable approach for the construction of bifunctional catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116378"},"PeriodicalIF":6.5,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144851472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Harnessing methanol as a C1 source for tunable C–H functionalization over CdS-based photocatalysts 利用甲醇作为C1源在cds光催化剂上实现可调碳氢功能化

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-14 DOI: 10.1016/j.jcat.2025.116363

Huinan Sun , Yufeng Wu , Jingnan Zhao , Cunfei Ma , Jianing Li , Liyuan Duan , Guofeng Zhao , Rui Cai , Qilei Liu , Qingwei Meng

{"title":"Harnessing methanol as a C1 source for tunable C–H functionalization over CdS-based photocatalysts","authors":"Huinan Sun , Yufeng Wu , Jingnan Zhao , Cunfei Ma , Jianing Li , Liyuan Duan , Guofeng Zhao , Rui Cai , Qilei Liu , Qingwei Meng","doi":"10.1016/j.jcat.2025.116363","DOIUrl":"10.1016/j.jcat.2025.116363","url":null,"abstract":"<div><div>Achieving divergent synthesis of multiple molecular scaffolds from identical starting materials via a single catalytic system represents a fascinating yet challenging frontier in organic transformation. Herein, we present a heterogeneous photocatalytic strategy that leverages methanol as a green and renewable C1 feedstock to unlock tunable α-C(sp<sup>3</sup>)-H functionalization of ketones, including α-hydroxymethylation, α-methoxymethylation, and α-methylation. By simply modulting reaction temperature and NiCo-LDH co-catalyst loading, precise control over product selectivity is achieved, with yields up to 98% across three pathways. A gas–liquid-solid segmented flow (PGSF) system enables effective process intensification alongside demonstrated gram-scale scalability with a remarkable turnover number (TON) of 31591. Mechanistic investigations integrating in-situ characterization and DFT calculations revealed that NiCo-LDH incorporation tailors CdS electronic properties to suppress methanol overoxidation, enhancing α-hydroxymethylation efficiency, while modulating the desorption kinetics of reactive intermediates, thereby directing the reaction selectivity between α-methoxymethylation and α-methylation reaction. This strategy establishes a robust platform for methanol-enabled divergent C–H functionalization, expecting to open up new prospects for semiconductor-catalyzed organic synthesis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116363"},"PeriodicalIF":6.5,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144851471","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Efficient catalytic upcycling of polyester and polycarbonate plastics using an NNN-based iron catalyst 用nnn基铁催化剂催化聚酯和聚碳酸酯塑料的高效升级回收

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-13 DOI: 10.1016/j.jcat.2025.116358

Xiaoxiao Chu , Guoren Zhou , Chongyan Ren , Xiaoshi Zhang , Maofu Pang , Nuoyan Zhao , Hongwu Zhang

引用次数: 0

Design and synthesis of nickel-containing covalent organic frameworks for visible light induced directed ortho-trifluoromethylation of aromatic amides 可见光诱导芳酰胺定向邻三氟甲基化的含镍共价有机骨架的设计与合成

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-08-12 DOI: 10.1016/j.jcat.2025.116367

Mengqi Zou, Houhai Fan, Feiyang Xie, Jing Xu, Hongbo Zhao, Wenyi Chu

{"title":"Design and synthesis of nickel-containing covalent organic frameworks for visible light induced directed ortho-trifluoromethylation of aromatic amides","authors":"Mengqi Zou, Houhai Fan, Feiyang Xie, Jing Xu, Hongbo Zhao, Wenyi Chu","doi":"10.1016/j.jcat.2025.116367","DOIUrl":"10.1016/j.jcat.2025.116367","url":null,"abstract":"<div><div>A nickel based covalent organic framework (Ni(II)@TFPA-COF) was designed and synthesized by bonding the double bonds of olefins and imines formed through orthogonal Schiff base reaction and Knoevenagel condensation using 4-aminobenzyl cyanide and tris-(4-formylphenyl) amine as starting materials, and its structure and optical properties were characterized. Ni(II)@TFPA-COF was used as a recyclable catalyst to develop a visible-light-induced reaction strategy for the directed <em>ortho</em>-trifluoromethylation of aromatic amide, and a series of <em>ortho</em>-trifluoromethylated aromatic amides were synthesized with good yields under mild and green conditions. Ni(II)@TFPA-COF exhibited good dual-functionality in photocatalysis and transition metal catalysis in the reaction. Based on the control experiments and literatures, a possible reaction mechanism for visible-light-induced directed C–H activation was proposed. This provides a novel, green, sustainable and efficient solution for the <em>ortho</em>-trifluoromethylation reaction of aromatic amides.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116367"},"PeriodicalIF":6.5,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144826036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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