Pub Date : 2025-12-11DOI: 10.1021/acscatal.5c07007
Henry P. Caldora, Elizabeth M. Dauncey, Daniele Leonori, Mateusz P. Plesniak, Oliver Turner, James J. Douglas
This Viewpoint examines the evolving landscape of academic-industrial partnerships, focusing on AstraZeneca’s collaborative framework within the U.K. research ecosystem. We highlight the 10-year partnership between AstraZeneca and the Leonori group at the University of Manchester (later RWTH Aachen University), which began in 2015 with Ph.D. studentship funding. This subsequently expanded to include a total of five Ph.D. students, a postdoctoral scientist, and multiple AstraZeneca collaborators. Unique aspects of this collaboration include the high quantity and diversity of supporting experimental work conducted by the industrial partner. Equally, the expansion of the collaboration to encompass multiple projects beyond those led by the funded students is noteworthy, alongside the frequency of face-to-face meetings. Through case studies and personal perspectives from participants, we demonstrate how strategic academic partnerships provide mutual benefits: advancing fundamental catalysis research while building industrial capabilities and talent pipelines essential for addressing future synthetic challenges in pharmaceutical development.
{"title":"Catalyzing Success: 10 Years of AstraZeneca and Leonori Group Collaboration","authors":"Henry P. Caldora, Elizabeth M. Dauncey, Daniele Leonori, Mateusz P. Plesniak, Oliver Turner, James J. Douglas","doi":"10.1021/acscatal.5c07007","DOIUrl":"https://doi.org/10.1021/acscatal.5c07007","url":null,"abstract":"This Viewpoint examines the evolving landscape of academic-industrial partnerships, focusing on AstraZeneca’s collaborative framework within the U.K. research ecosystem. We highlight the 10-year partnership between AstraZeneca and the Leonori group at the University of Manchester (later RWTH Aachen University), which began in 2015 with Ph.D. studentship funding. This subsequently expanded to include a total of five Ph.D. students, a postdoctoral scientist, and multiple AstraZeneca collaborators. Unique aspects of this collaboration include the high quantity and diversity of supporting experimental work conducted by the industrial partner. Equally, the expansion of the collaboration to encompass multiple projects beyond those led by the funded students is noteworthy, alongside the frequency of face-to-face meetings. Through case studies and personal perspectives from participants, we demonstrate how strategic academic partnerships provide mutual benefits: advancing fundamental catalysis research while building industrial capabilities and talent pipelines essential for addressing future synthetic challenges in pharmaceutical development.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718425","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}
Pub Date : 2025-12-11DOI: 10.1021/acscatal.5c06734
Shiyou Xing, Xiaochun Liu, Si Lu, Juan Fu, Wen Wang, Cuiyi Liang, Yong Liu, Ziyu Wang, Wei Qi
The hydrogenation of CO2 into methanol offers a promising approach to carbon sequestration and a potential approach to storing hydrogen derived from renewable energy. Herein, we report a facile surface engineering strategy by anchoring nickel oxide (NiO) clusters onto the surface of the commercial indium oxide (In2O3) to drive methanol synthesis. The anchored NiO clusters brought about the transfer of electrons from the NiO cluster to the In2O3 surface, which was revealed through a series of characterizations. This electronic interaction led to an increased level of oxidation of the anchored NiO clusters and facilitated the reduction of the In2O3 surface, thereby generating more active sites such as oxygen vacancies (OVs). More importantly, the anchored NiO clusters contributed to the dissociation activation of H2 compared to the OV site of pure In2O3. As a result, the CO2 conversion and methanol space-time yield were increased by approximately 2-fold and 1.4-fold, respectively. The high-pressure operando Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) measurements suggested that the methanol production was promoted by the formation of formate (HCOO*) and its subsequent conversion to methoxy species (CH3O*). The in situ X-ray adsorption experiments under working conditions indicated that the anchored NiO clusters remained in the oxidized state, with a slight partial reduction. This likely guaranteed the activation of H2, which not only contributed to the formation of more surface-active OVs during the reaction but also offered more active H species in the stepwise hydrogenation reactions for methanol synthesis.
{"title":"Surface Engineering of Indium Oxide by Nickel Oxide Clusters for Driving Methanol Production from CO2 Hydrogenation","authors":"Shiyou Xing, Xiaochun Liu, Si Lu, Juan Fu, Wen Wang, Cuiyi Liang, Yong Liu, Ziyu Wang, Wei Qi","doi":"10.1021/acscatal.5c06734","DOIUrl":"https://doi.org/10.1021/acscatal.5c06734","url":null,"abstract":"The hydrogenation of CO<sub>2</sub> into methanol offers a promising approach to carbon sequestration and a potential approach to storing hydrogen derived from renewable energy. Herein, we report a facile surface engineering strategy by anchoring nickel oxide (NiO) clusters onto the surface of the commercial indium oxide (In<sub>2</sub>O<sub>3</sub>) to drive methanol synthesis. The anchored NiO clusters brought about the transfer of electrons from the NiO cluster to the In<sub>2</sub>O<sub>3</sub> surface, which was revealed through a series of characterizations. This electronic interaction led to an increased level of oxidation of the anchored NiO clusters and facilitated the reduction of the In<sub>2</sub>O<sub>3</sub> surface, thereby generating more active sites such as oxygen vacancies (OVs). More importantly, the anchored NiO clusters contributed to the dissociation activation of H<sub>2</sub> compared to the OV site of pure In<sub>2</sub>O<sub>3</sub>. As a result, the CO<sub>2</sub> conversion and methanol space-time yield were increased by approximately 2-fold and 1.4-fold, respectively. The high-pressure <i>operando</i> Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) measurements suggested that the methanol production was promoted by the formation of formate (HCOO*) and its subsequent conversion to methoxy species (CH<sub>3</sub>O*). The <i>in situ</i> X-ray adsorption experiments under working conditions indicated that the anchored NiO clusters remained in the oxidized state, with a slight partial reduction. This likely guaranteed the activation of H<sub>2</sub>, which not only contributed to the formation of more surface-active OVs during the reaction but also offered more active H species in the stepwise hydrogenation reactions for methanol synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"144 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718424","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}
Pub Date : 2025-12-11DOI: 10.1021/acscatal.5c07508
Matteo Gasparetto, Attila Sveiczer, Andrea Fermi, Mounir Raji, Richard J. Fair, Timothy Noël, Paola Ceroni, Gellért Sipos
Herein, we report a general and scalable continuous flow metallaphotoredox amidine arylation protocol that efficiently couples diverse (hetero)aryl halides and amidines under mild open-air conditions. Mechanistic studies revealed the pivotal role of an in situ generated triazine cocatalyst, which acts as the quencher in the photocatalytic cycle via an underexplored oxidative quenching pathway. Its strategic use as a cocatalyst enabled faster kinetics, broader nucleophile scope, including sulfonamides and amines, and the use of alternative solvents. These insights unlock a previously challenging reactivity, enhancing both the synthetic utility and sustainability of our nickel/photoredox cross-coupling.
{"title":"In Situ Generated Triazine Co-Catalyst Unlocks Amidine Arylation under Dual Nickel/Photoredox Catalysis: A Platform for Mild C–N Bond Formation","authors":"Matteo Gasparetto, Attila Sveiczer, Andrea Fermi, Mounir Raji, Richard J. Fair, Timothy Noël, Paola Ceroni, Gellért Sipos","doi":"10.1021/acscatal.5c07508","DOIUrl":"https://doi.org/10.1021/acscatal.5c07508","url":null,"abstract":"Herein, we report a general and scalable continuous flow metallaphotoredox amidine arylation protocol that efficiently couples diverse (hetero)aryl halides and amidines under mild open-air conditions. Mechanistic studies revealed the pivotal role of an <i>in situ</i> generated triazine cocatalyst, which acts as the quencher in the photocatalytic cycle via an underexplored oxidative quenching pathway. Its strategic use as a cocatalyst enabled faster kinetics, broader nucleophile scope, including sulfonamides and amines, and the use of alternative solvents. These insights unlock a previously challenging reactivity, enhancing both the synthetic utility and sustainability of our nickel/photoredox cross-coupling.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"150 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718426","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}
Pub Date : 2025-12-10DOI: 10.1021/acscatal.5c06816
Fan Yuan, Hongshun Ran, Tingxi Chen, Yaxuan Jing
The growing accumulation of waste plastics has become a significant environmental challenge, posing significant risks to ecosystems and human health. Hydroconversion has emerged as a promising approach for efficiently converting waste plastics into value-added liquid fuels and wax products. This process typically occurs on supported metal catalysts, where the surface and interface properties of the active metal are critical in determining the catalytic performance. A comprehensive understanding of these metallic surface and interface properties is essential for advancing catalyst design. This Perspective systematically explores the effects of metallic surface properties (geometric and electronic effects) and interface properties (interface effects) on the hydroconversion of plastics containing C–C, C–O, and C–N bonds. Furthermore, it provides theoretical insights into the development of catalytic systems for the hydroconversion of waste plastics, drawing from lessons learned in catalyst design for biomass hydroconversion.
{"title":"Surface and Interface Properties of Metal Species for Waste Plastic Hydroconversion","authors":"Fan Yuan, Hongshun Ran, Tingxi Chen, Yaxuan Jing","doi":"10.1021/acscatal.5c06816","DOIUrl":"https://doi.org/10.1021/acscatal.5c06816","url":null,"abstract":"The growing accumulation of waste plastics has become a significant environmental challenge, posing significant risks to ecosystems and human health. Hydroconversion has emerged as a promising approach for efficiently converting waste plastics into value-added liquid fuels and wax products. This process typically occurs on supported metal catalysts, where the surface and interface properties of the active metal are critical in determining the catalytic performance. A comprehensive understanding of these metallic surface and interface properties is essential for advancing catalyst design. This Perspective systematically explores the effects of metallic surface properties (geometric and electronic effects) and interface properties (interface effects) on the hydroconversion of plastics containing C–C, C–O, and C–N bonds. Furthermore, it provides theoretical insights into the development of catalytic systems for the hydroconversion of waste plastics, drawing from lessons learned in catalyst design for biomass hydroconversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711478","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}
Pub Date : 2025-12-10DOI: 10.1021/acscatal.5c06453
Yongheng Jia, Kaihang Sun, Jianpeng Li, Longzhou Zhang, Shufang Zhao, Young Dok Kim, Jie Feng, Baojun Li, Zhongyi Liu, Zhikun Peng
The rational design of metal-acid bifunctional systems, which integrate (de)hydrogenation and acid-driven functionalities, holds great potential for steering tandem hydroconversion (HDC) processes. However, thermodynamic instability and unpredictable kinetic bifurcations of intermediates often compromise the target product selectivity. Herein, we reported a dual-confinement architecture that spatially encapsulates palladium nanoparticles and Keggin-type phosphotungstic acid (HPW) within a USY zeolite (denoted as Pd@HPW@USY), achieving geometrically optimized metal-acid proximity for regulation of the key intermediate in benzene hydroalkylation (HDA). Systematic investigations revealed that the spatial proximity of metal-acid sites facilitated the rapid migration of metal-generated cyclohexene to adjacent acid sites, where the enhanced protonation capability of confined W–OH acid sites of HPW (compared with conventional Al–OH acid sites in zeolites) promoted cyclohexene activation. The dual-confinement catalyst exhibited 73.8% selectivity and 47.3% yield toward cyclohexylbenzene, surpassing conventional catalysts with suboptimal spatial configurations: Pd/HPW/USY (40.9%, 25.5%), Pd/HPW@USY (51.6%, 30.5%), and Pd@HPW/USY (65.4%, 40.2%). In addition, Pd@HPW@USY exhibited superior cycling stability in the benzene HDA reaction. It is demonstrated that the synergistic interplay between spatial proximity and functional matching governs alkylation-dominated pathways for the key intermediate cyclohexene. This work establishes a paradigm for engineering metal-acid multifunctional systems, offering alternative opportunities for complex tandem reaction network manipulation.
{"title":"Synergistic Metal-Acid Unit for Boosting Tandem Catalysis via Efficient Transformation of the Key Intermediate","authors":"Yongheng Jia, Kaihang Sun, Jianpeng Li, Longzhou Zhang, Shufang Zhao, Young Dok Kim, Jie Feng, Baojun Li, Zhongyi Liu, Zhikun Peng","doi":"10.1021/acscatal.5c06453","DOIUrl":"https://doi.org/10.1021/acscatal.5c06453","url":null,"abstract":"The rational design of metal-acid bifunctional systems, which integrate (de)hydrogenation and acid-driven functionalities, holds great potential for steering tandem hydroconversion (HDC) processes. However, thermodynamic instability and unpredictable kinetic bifurcations of intermediates often compromise the target product selectivity. Herein, we reported a dual-confinement architecture that spatially encapsulates palladium nanoparticles and Keggin-type phosphotungstic acid (HPW) within a USY zeolite (denoted as Pd@HPW@USY), achieving geometrically optimized metal-acid proximity for regulation of the key intermediate in benzene hydroalkylation (HDA). Systematic investigations revealed that the spatial proximity of metal-acid sites facilitated the rapid migration of metal-generated cyclohexene to adjacent acid sites, where the enhanced protonation capability of confined W–OH acid sites of HPW (compared with conventional Al–OH acid sites in zeolites) promoted cyclohexene activation. The dual-confinement catalyst exhibited 73.8% selectivity and 47.3% yield toward cyclohexylbenzene, surpassing conventional catalysts with suboptimal spatial configurations: Pd/HPW/USY (40.9%, 25.5%), Pd/HPW@USY (51.6%, 30.5%), and Pd@HPW/USY (65.4%, 40.2%). In addition, Pd@HPW@USY exhibited superior cycling stability in the benzene HDA reaction. It is demonstrated that the synergistic interplay between spatial proximity and functional matching governs alkylation-dominated pathways for the key intermediate cyclohexene. This work establishes a paradigm for engineering metal-acid multifunctional systems, offering alternative opportunities for complex tandem reaction network manipulation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"38 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711480","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}
Pub Date : 2025-12-09DOI: 10.1021/acscatal.5c06638
Dongmei Chen, Ting Tu, Tianhui Liao, Donghan Liu, Shi-Chao Ren, Yonggui Robin Chi
Aryl migration-induced difunctionalization of alkenes is a fascinating strategy for increasing the molecular complexity via the simultaneous formation of two chemical bonds across the C–C double bond. Despite the significant advances in this area, the in situ functionalization of the migrating aryl ring remains elusive due to the incompatibility between the conventional arene C–H functionalization strategy and the aryl migration process. Herein, we disclose the photocatalytic in situ amination of the migrating aryl ring in which an aryl ring is aminated and migrated within a single step, providing rapid access to valuable 4-aminated benzenepropanamide scaffolds. Such transformations enable the formation of an additional chemical bond on the migrating aryl ring beyond those two formed on the alkene carbons, significantly increasing the flexibility of the aryl migration strategy and improving the migration efficiency for the aminated aryl ring. The energy transfer catalytic cycle between the photosensitizer and the bifunctional reagents plays a pivotal role in combining the aryl migration process with the emerging radical-based arene remote C–H amination step. Experimental mechanistic studies support the proposed reaction pathway. The power of this protocol was demonstrated by the functionalization of pharmaceutically relevant molecules, the efficient synthesis of bioactive molecule analogs, and antibacterial activity investigations.
{"title":"Photocatalytic In Situ Amination of the Migrating Aryl Group: Rapid Access to 4-Aminated Benzenepropanamides","authors":"Dongmei Chen, Ting Tu, Tianhui Liao, Donghan Liu, Shi-Chao Ren, Yonggui Robin Chi","doi":"10.1021/acscatal.5c06638","DOIUrl":"https://doi.org/10.1021/acscatal.5c06638","url":null,"abstract":"Aryl migration-induced difunctionalization of alkenes is a fascinating strategy for increasing the molecular complexity via the simultaneous formation of two chemical bonds across the C–C double bond. Despite the significant advances in this area, the <i>in situ</i> functionalization of the migrating aryl ring remains elusive due to the incompatibility between the conventional arene C–H functionalization strategy and the aryl migration process. Herein, we disclose the photocatalytic <i>in situ</i> amination of the migrating aryl ring in which an aryl ring is aminated and migrated within a single step, providing rapid access to valuable 4-aminated benzenepropanamide scaffolds. Such transformations enable the formation of an additional chemical bond on the migrating aryl ring beyond those two formed on the alkene carbons, significantly increasing the flexibility of the aryl migration strategy and improving the migration efficiency for the aminated aryl ring. The energy transfer catalytic cycle between the photosensitizer and the bifunctional reagents plays a pivotal role in combining the aryl migration process with the emerging radical-based arene remote C–H amination step. Experimental mechanistic studies support the proposed reaction pathway. The power of this protocol was demonstrated by the functionalization of pharmaceutically relevant molecules, the efficient synthesis of bioactive molecule analogs, and antibacterial activity investigations.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"138 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703902","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}
Transition metal-catalyzed asymmetric carbene Si–H insertion provides a straightforward and powerful protocol to access chiral organosilicon compounds. However, the silanes employed are largely limited to tertiary silanes, and the Si–H insertion of secondary silanes for the formation of Si-stereocenters is still underdeveloped. Herein, we report an enantioselective Si–H insertion of secondary silanes and α-alkyl-donor dirhodium-carbene generated from the cycloisomerization of diynes. This protocol delivers diverse silyl-substituted furan-fused dihydropyridine derivatives bearing C/Si-stereocenters with high efficiency (0.5 mol % catalyst loading, up to 93% yield) and good stereoselectivity (up to 99% ee, 96:4 dr). Critically, the chemoselectivity favoring intermolecular Si–H insertion over intramolecular β-hydride migration reaches up to 20:1. Notably, this protocol is successfully extended to primary silanes. The retained Si–H bonds in the products provide access for preparing chiral tetra-substituted silicon-stereogenic compounds, and the furan moiety allows further derivatization. Mechanistic studies indicated that the concerted [3 + 2] cycloaddition process is the rate-determining step. The furyl ring adjacent to dirhodium carbene was found to be essential for high chemoselectivity, as its favorable π–π stacking interactions and reduced steric hindrance stabilize the Si–H insertion transition state while outcompeting β-hydride migration
{"title":"Rh2(II)-Catalyzed Asymmetric Si–H Insertion of α-Alkyl-Donor Carbene from Diynes: Constructing C/Si-Stereocenters by Outcompeting β-H Migration","authors":"Rui Wu, Qi-Feng Wang, Haoran Zhang, Shunlong Liu, Kai Chen, Shifa Zhu","doi":"10.1021/acscatal.5c06981","DOIUrl":"https://doi.org/10.1021/acscatal.5c06981","url":null,"abstract":"Transition metal-catalyzed asymmetric carbene Si–H insertion provides a straightforward and powerful protocol to access chiral organosilicon compounds. However, the silanes employed are largely limited to tertiary silanes, and the Si–H insertion of secondary silanes for the formation of Si-stereocenters is still underdeveloped. Herein, we report an enantioselective Si–H insertion of secondary silanes and α-alkyl-donor dirhodium-carbene generated from the cycloisomerization of diynes. This protocol delivers diverse silyl-substituted furan-fused dihydropyridine derivatives bearing C/Si-stereocenters with high efficiency (0.5 mol % catalyst loading, up to 93% yield) and good stereoselectivity (up to 99% ee, 96:4 dr). Critically, the chemoselectivity favoring intermolecular Si–H insertion over intramolecular β-hydride migration reaches up to 20:1. Notably, this protocol is successfully extended to primary silanes. The retained Si–H bonds in the products provide access for preparing chiral tetra-substituted silicon-stereogenic compounds, and the furan moiety allows further derivatization. Mechanistic studies indicated that the concerted [3 + 2] cycloaddition process is the rate-determining step. The furyl ring adjacent to dirhodium carbene was found to be essential for high chemoselectivity, as its favorable π–π stacking interactions and reduced steric hindrance stabilize the Si–H insertion transition state while outcompeting β-hydride migration","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"7 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711388","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}
Pub Date : 2025-12-09DOI: 10.1021/acscatal.5c06537
Bereket Tassew Bekele, Rajamani Gounder
The secondary environment surrounding Brønsted acid (H+) sites in zeolites influences the stability of confined intermediates and transition states in acid catalysis. Extra-framework aluminum (Alex) moieties are commonly found within zeolitic voids, either formed intentionally via hydrothermal treatments that remove framework Al sites (Alf) or adventitiously during synthesis and subsequent treatments. Alex moieties have been documented to influence catalytic and adsorptive properties of zeolites via chemical interactions and mechanisms that remain debated. Although Alex species have been proposed to increase H+ site acid strength based on analogies to Lewis acid–base interactions in aqueous-phase superacid systems, we present experimental evidence demonstrating that the preeminent role of Alex species is instead to decrease effective void spaces in zeolitic micropores, which strengthens dispersive stabilization of both adsorbed neutral intermediates and their cationic transition states alike. We combine site-specific spectroscopic, kinetic, and adsorption studies to quantify entropy-enthalpy trade-offs for adsorbed charge-neutral alkanes and their carbocationic transition states mediating protolytic cracking and dehydrogenation, with increasing Alex content in model chabazite (CHA) zeolite materials containing isolated H+ sites. Entropy-enthalpy trade-offs with increasing Alex content are quantitatively identical to those describing changes in the size of confining micropore environments among zeolite topologies, a behavior characteristic of changes in the strength of dispersive forces. These findings enable catalyst design strategies that preferentially position extra-framework oxide moieties within confining voids containing H+ sites to alter dispersive interactions and influence catalytic reactivity, complementing strategies based on varying framework topology or the location of active sites among distinct voids of a given topology.
{"title":"Extra-Framework Aluminum Moieties Occluded within Zeolite Micropores Strengthen Dispersive Stabilization of Confined Alkanes and Carbocationic Transition States","authors":"Bereket Tassew Bekele, Rajamani Gounder","doi":"10.1021/acscatal.5c06537","DOIUrl":"https://doi.org/10.1021/acscatal.5c06537","url":null,"abstract":"The secondary environment surrounding Brønsted acid (H<sup>+</sup>) sites in zeolites influences the stability of confined intermediates and transition states in acid catalysis. Extra-framework aluminum (Al<sub>ex</sub>) moieties are commonly found within zeolitic voids, either formed intentionally via hydrothermal treatments that remove framework Al sites (Al<sub>f</sub>) or adventitiously during synthesis and subsequent treatments. Al<sub>ex</sub> moieties have been documented to influence catalytic and adsorptive properties of zeolites via chemical interactions and mechanisms that remain debated. Although Al<sub>ex</sub> species have been proposed to increase H<sup>+</sup> site acid strength based on analogies to Lewis acid–base interactions in aqueous-phase superacid systems, we present experimental evidence demonstrating that the preeminent role of Al<sub>ex</sub> species is instead to decrease effective void spaces in zeolitic micropores, which strengthens dispersive stabilization of both adsorbed neutral intermediates and their cationic transition states alike. We combine site-specific spectroscopic, kinetic, and adsorption studies to quantify entropy-enthalpy trade-offs for adsorbed charge-neutral alkanes and their carbocationic transition states mediating protolytic cracking and dehydrogenation, with increasing Al<sub>ex</sub> content in model chabazite (CHA) zeolite materials containing isolated H<sup>+</sup> sites. Entropy-enthalpy trade-offs with increasing Al<sub>ex</sub> content are quantitatively identical to those describing changes in the size of confining micropore environments among zeolite topologies, a behavior characteristic of changes in the strength of dispersive forces. These findings enable catalyst design strategies that preferentially position extra-framework oxide moieties within confining voids containing H<sup>+</sup> sites to alter dispersive interactions and influence catalytic reactivity, complementing strategies based on varying framework topology or the location of active sites among distinct voids of a given topology.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703818","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}
Pub Date : 2025-12-09DOI: 10.1021/acscatal.5c05612
Tapas R. Pradhan, Alina Dzhaparova, Gisela A. González-Montiel, Luis Borrego-Castaneda, Eunseok Park, Paul Ha-Yeon Cheong, Jin Kyoon Park
Difunctionalization of ynamides, whether through an intermolecular approach or in an atom-economical manner, continues to pose a significant challenge. This work presents a simpler method for such unprecedented functionalization through highly regio- and stereoselective bromoalkynylation. The developed strategy, which requires a Pd(II) catalyst and no additive, has a broad scope and high functional-group tolerance and provided access to 50 value-added β-bromo ynenamides. In addition to late-stage functionalization, the synthetic potential of this method was demonstrated through rapid access to previously challenging π-skeletons. A unique 1,3-alkynyl migration, which was enabled by Pd(IV)-bound keteniminium species, offers a platform for the development of atom-economical reactions. Experimental evidence, such as from Hammett plot analysis, X-ray photoelectron spectroscopy studies, and 13C kinetic isotope effect measurements, supported by density functional theory computations enabled a comprehensive understanding of the mechanism.
{"title":"Mechanistic Insights into Atom-Economical Bromoalkynylation of Ynamides: 1,3-Alkynyl Migration Explored through 13C Kinetic Isotope Effects, X-ray Photoelectron Spectroscopy, and Density Functional Theory Analysis","authors":"Tapas R. Pradhan, Alina Dzhaparova, Gisela A. González-Montiel, Luis Borrego-Castaneda, Eunseok Park, Paul Ha-Yeon Cheong, Jin Kyoon Park","doi":"10.1021/acscatal.5c05612","DOIUrl":"https://doi.org/10.1021/acscatal.5c05612","url":null,"abstract":"Difunctionalization of ynamides, whether through an intermolecular approach or in an atom-economical manner, continues to pose a significant challenge. This work presents a simpler method for such unprecedented functionalization through highly regio- and stereoselective bromoalkynylation. The developed strategy, which requires a Pd(II) catalyst and no additive, has a broad scope and high functional-group tolerance and provided access to 50 value-added β-bromo ynenamides. In addition to late-stage functionalization, the synthetic potential of this method was demonstrated through rapid access to previously challenging π-skeletons. A unique 1,3-alkynyl migration, which was enabled by Pd(IV)-bound keteniminium species, offers a platform for the development of atom-economical reactions. Experimental evidence, such as from Hammett plot analysis, X-ray photoelectron spectroscopy studies, and <sup>13</sup>C kinetic isotope effect measurements, supported by density functional theory computations enabled a comprehensive understanding of the mechanism.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704271","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}
Pub Date : 2025-12-09DOI: 10.1021/acscatal.5c04353
Daewon Oh, Miyeon Kim, Hojeong Lee, Jong-Seong Bae, Beomgyun Jeong, Changhun Hur, Jeong Woo Han, Kwangjin An
This study investigated the performances of Rh single-atom catalysts (SACs), cluster catalysts, and nanoparticle (NP) catalysts in olefin hydroformylation. Using in situ characterization techniques, we elucidated the distinct chemical and electronic properties of each catalyst type. Our findings revealed that Rh cluster catalysts exhibit distinctive characteristics between those of SACs and NPs, significantly influencing their catalytic performance. Notably, Rh cluster catalysts achieved a 5-fold increase in turnover frequency (∼25,589 h–1) compared to SACs (∼5,430 h–1) and a 9-fold increase relative to NP catalysts (∼2,838 h–1) in the propylene hydroformylation. Theoretical calculations revealed that the Rh cluster catalysts possess optimal CO adsorption energies, allowing them to efficiently overcome the energy barrier for CO insertion during the rate-determining step of propylene hydroformylation. Additionally, density of states and crystalline orbital Hamilton population analyses confirmed that the Rh cluster catalyst exhibited adjusted electronic properties, positioned between those of Rh SAC and NP catalysts. This study highlights the unique properties of the Rh cluster catalysts and offers valuable insights into the design of high-performance catalysts for hydroformylation and other catalytic processes.
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