Pub Date : 2026-02-04DOI: 10.1021/acscatal.5c07220
Kinga Gołabek, Svetlana Kurucová, Juan Francisco Miñambres, Klára Veselá, Talat Zakeri, Jan Přech
Lewis acid zeolites, primarily Al-free Zr and Sn silicates, catalyze the chemoselective reduction of ketones and aldehydes to the corresponding alcohols through hydrogen transfer (Meerwein–Ponndorf–Verley (MPV) reduction). Sn silicates are more active in the MPV reduction of ketones, whereas Zr silicates are more active in the MPV reduction of aldehydes. However, the catalytic activity of these zeolites has not been accurately ascribed to “open” vs. “closed” Zr sites even though this correlation is crucial for systems whose substrate structure allows competing reaction pathways. For example, MPV reduction of citronellal competes with carbonyl-ene cyclization to isopulegol and acetalization in the citronellal reaction with 2-propanol. Therefore, we aimed to correlate thoroughly characterized Lewis acid sites in Zr-substituted beta and MFI zeolites with their selectivity. For this purpose, we analyzed Zr-zeolite acidity by fourier transform infrared spectroscopy (FTIR) spectroscopy of adsorbed deuterated acetonitrile and acetone because deuterated acetonitrile probes “open” Zr sites without interacting with “closed” sites, but acetone identifies both “open” and “closed” sites. Our results showed that Zr-beta rich in Zr “closed” sites favored MPV reduction. Conversely, Zr-beta rich in “open” sites and reference catalysts yielded isopulegol as the main product. Ion exchange of the Zr-beta “open” sites with Na+ cations deactivated these sites, thereby switching the selectivity to citronellol. In turn, the silanol groups of the catalyst promoted acetalization, regardless of substituting the heteroelement (Zr or Sn). These findings demonstrate that Zr-site Lewis acidity determines terpenoid reduction selectivity, as the relatively weaker Zr-beta “closed” sites catalyze citronellal MPV reduction to citronellol, while the relatively stronger Zr-beta “open” sites catalyze intramolecular carbonyl-ene cyclization to isopulegol. Moreover, this correlation between selectivity and Zr-site Lewis acidity may enable us to design specific catalysts, even for systems with competing reactions, based on quantitative data acquired using our experimental paradigm.
{"title":"Zr-Site Lewis Acidity Determines Terpenoid Reduction Selectivity","authors":"Kinga Gołabek, Svetlana Kurucová, Juan Francisco Miñambres, Klára Veselá, Talat Zakeri, Jan Přech","doi":"10.1021/acscatal.5c07220","DOIUrl":"https://doi.org/10.1021/acscatal.5c07220","url":null,"abstract":"Lewis acid zeolites, primarily Al-free Zr and Sn silicates, catalyze the chemoselective reduction of ketones and aldehydes to the corresponding alcohols through hydrogen transfer (Meerwein–Ponndorf–Verley (MPV) reduction). Sn silicates are more active in the MPV reduction of ketones, whereas Zr silicates are more active in the MPV reduction of aldehydes. However, the catalytic activity of these zeolites has not been accurately ascribed to “open” vs. “closed” Zr sites even though this correlation is crucial for systems whose substrate structure allows competing reaction pathways. For example, MPV reduction of citronellal competes with carbonyl-ene cyclization to isopulegol and acetalization in the citronellal reaction with 2-propanol. Therefore, we aimed to correlate thoroughly characterized Lewis acid sites in Zr-substituted beta and MFI zeolites with their selectivity. For this purpose, we analyzed Zr-zeolite acidity by fourier transform infrared spectroscopy (FTIR) spectroscopy of adsorbed deuterated acetonitrile and acetone because deuterated acetonitrile probes “open” Zr sites without interacting with “closed” sites, but acetone identifies both “open” and “closed” sites. Our results showed that Zr-beta rich in Zr “closed” sites favored MPV reduction. Conversely, Zr-beta rich in “open” sites and reference catalysts yielded isopulegol as the main product. Ion exchange of the Zr-beta “open” sites with Na<sup>+</sup> cations deactivated these sites, thereby switching the selectivity to citronellol. In turn, the silanol groups of the catalyst promoted acetalization, regardless of substituting the heteroelement (Zr or Sn). These findings demonstrate that Zr-site Lewis acidity determines terpenoid reduction selectivity, as the relatively weaker Zr-beta “closed” sites catalyze citronellal MPV reduction to citronellol, while the relatively stronger Zr-beta “open” sites catalyze intramolecular carbonyl-ene cyclization to isopulegol. Moreover, this correlation between selectivity and Zr-site Lewis acidity may enable us to design specific catalysts, even for systems with competing reactions, based on quantitative data acquired using our experimental paradigm.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116056","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 : 2026-02-04DOI: 10.1021/acscatal.5c07128
Xiaoru Wang,Zhanwu Lei,Jicong Yan,Penglong Wang,Ruifeng Chong,Fuping Tian,Tao Hu,Ruiguo Cao,Xiang Wang
Developing non-noble metal catalysts for hydrocracking polyolefins is a promising yet formidable challenge for upcycling waste plastics in practice. Herein, we report a NiW/WOx (2 < x < 3) catalyst, which accomplishes polyolefin hydrocracking at 250 °C, yielding a liquid product of about 73 wt % and a gaseous product of about 22 wt %. The liquid fraction primarily consists of hydrocarbons in the C4–C25 range, with more than 77% falling within the jet-fuel-range components (C8–C16). The gas product is dominated by branched C3–C6 hydrocarbons, characteristic of liquefied petroleum gas (LPG), with negligible carbon loss, such as methane and ethane.A sequence change from inactive to active, and back to inactive in polyolefin hydrocracking was found accompanying the reconstruction of the surface structure of the catalyst from Ni-doped WO3 to NiW alloy nanoparticles supported on WOx (NiW/WOx), and then to WO2-encapsulated NiW (NiW@WO2). The coexposure of NiW alloy nanoparticles and WOx is further demonstrated to be necessary for fulfilling the bifunctionality of the catalyst in hydrogen dissociation and C–C bond cleavage in polyolefin hydrocracking, and the absence of either will deactivate the catalyst.
{"title":"Hydrocracking Polyolefins to Jet Fuel over a NiW/WOx Catalyst","authors":"Xiaoru Wang,Zhanwu Lei,Jicong Yan,Penglong Wang,Ruifeng Chong,Fuping Tian,Tao Hu,Ruiguo Cao,Xiang Wang","doi":"10.1021/acscatal.5c07128","DOIUrl":"https://doi.org/10.1021/acscatal.5c07128","url":null,"abstract":"Developing non-noble metal catalysts for hydrocracking polyolefins is a promising yet formidable challenge for upcycling waste plastics in practice. Herein, we report a NiW/WOx (2 < x < 3) catalyst, which accomplishes polyolefin hydrocracking at 250 °C, yielding a liquid product of about 73 wt % and a gaseous product of about 22 wt %. The liquid fraction primarily consists of hydrocarbons in the C4–C25 range, with more than 77% falling within the jet-fuel-range components (C8–C16). The gas product is dominated by branched C3–C6 hydrocarbons, characteristic of liquefied petroleum gas (LPG), with negligible carbon loss, such as methane and ethane.A sequence change from inactive to active, and back to inactive in polyolefin hydrocracking was found accompanying the reconstruction of the surface structure of the catalyst from Ni-doped WO3 to NiW alloy nanoparticles supported on WOx (NiW/WOx), and then to WO2-encapsulated NiW (NiW@WO2). The coexposure of NiW alloy nanoparticles and WOx is further demonstrated to be necessary for fulfilling the bifunctionality of the catalyst in hydrogen dissociation and C–C bond cleavage in polyolefin hydrocracking, and the absence of either will deactivate the catalyst.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"108 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111135","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 : 2026-02-04DOI: 10.1021/acscatal.5c08001
Yingxiang Zhao,Yingjie Zhao,Xinyue Zhou,Haiwei Guo,Qiqi Yin,Yutao Jiang,Haiyan He,Na Liu,Gengbo Ren,Christopher M. A. Parlett,Changzhi Li
M–N–C single-atom catalysts (SACs) represent promising candidates owing to their atomically dispersed active sites and tunable catalytic properties and have shown broad potential in various catalysis reactions. However, the mechanisms and true active sites involved in lignin conversion, particularly oxidative depolymerization, remain unclear. Herein, a Ru–N–C SAC with a well-defined configuration, including coordination environment and coordination number, was synthesized via a straightforward ball-milling method for lignin oxidation. The Ru–N–C SAC prepared with 12 h of ball milling demonstrated high catalytic performance in the oxidative depolymerization of various β-O-4 model compounds and diverse lignin feedstocks. Structural analysis via X-ray absorption spectroscopy demonstrated that the Ru–N4 motif constitutes the predominant coordination environment in Ru–N–C, which is regarded as the primary active site in activating O2 into superoxide radicals, as confirmed by free-radical quenching experiments and electron paramagnetic resonance analysis; meanwhile, it also served as a basic site in polarizing Cβ–H bonds in β-O-4 that favored C–O/C–C bond cleavage, which was disclosed by CO2 temperature-programmed desorption and electron localization function analysis. The critical role of Ru–N4 in the activation of O2 and C–O/C–C bond cleavage was further confirmed by density functional theory calculation, which indicated that the Ru–N4 center exhibits strong adsorption toward both the O2 and β-O-4 linkages. This work provides a deep understanding on the active sites within Ru–N–C SACs for lignin oxidative cleavage and offers great potential on the rational design of next-generation SACs in biomass valorization.
{"title":"Unveiling the Role of Ru–N4 on Ru–N–C Single-Atom Catalyst in C–O/C–C Bonds’ Oxidative Cleavage in Lignin","authors":"Yingxiang Zhao,Yingjie Zhao,Xinyue Zhou,Haiwei Guo,Qiqi Yin,Yutao Jiang,Haiyan He,Na Liu,Gengbo Ren,Christopher M. A. Parlett,Changzhi Li","doi":"10.1021/acscatal.5c08001","DOIUrl":"https://doi.org/10.1021/acscatal.5c08001","url":null,"abstract":"M–N–C single-atom catalysts (SACs) represent promising candidates owing to their atomically dispersed active sites and tunable catalytic properties and have shown broad potential in various catalysis reactions. However, the mechanisms and true active sites involved in lignin conversion, particularly oxidative depolymerization, remain unclear. Herein, a Ru–N–C SAC with a well-defined configuration, including coordination environment and coordination number, was synthesized via a straightforward ball-milling method for lignin oxidation. The Ru–N–C SAC prepared with 12 h of ball milling demonstrated high catalytic performance in the oxidative depolymerization of various β-O-4 model compounds and diverse lignin feedstocks. Structural analysis via X-ray absorption spectroscopy demonstrated that the Ru–N4 motif constitutes the predominant coordination environment in Ru–N–C, which is regarded as the primary active site in activating O2 into superoxide radicals, as confirmed by free-radical quenching experiments and electron paramagnetic resonance analysis; meanwhile, it also served as a basic site in polarizing Cβ–H bonds in β-O-4 that favored C–O/C–C bond cleavage, which was disclosed by CO2 temperature-programmed desorption and electron localization function analysis. The critical role of Ru–N4 in the activation of O2 and C–O/C–C bond cleavage was further confirmed by density functional theory calculation, which indicated that the Ru–N4 center exhibits strong adsorption toward both the O2 and β-O-4 linkages. This work provides a deep understanding on the active sites within Ru–N–C SACs for lignin oxidative cleavage and offers great potential on the rational design of next-generation SACs in biomass valorization.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"106 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111134","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 : 2026-02-04DOI: 10.1021/acscatal.5c08026
Cristina Duran,Sílvia Osuna
The stand-alone version of the alpha subunit of tryptophan synthase (TrpA), ZmBX1, catalyzes the retro-aldol cleavage of indole-3-glycerol phosphate (IGP) at a catalytic efficiency that is approximately 144,000 times higher than that of isolated ZmTrpA. Available X-ray crystal structures of ZmBX1 and several TrpAs revealed identical overall structures as well as active site geometries, showing high flexibility of the catalytic E49 in both cases. Based on the crystallographic data, E49 was found to adopt an active state in which the carboxylate group is close to IGP for promoting the retro-aldol cleavage as well as an additional inactive state whose catalytic function was unclear. In this work, by using a combination of Molecular Dynamics (MD) simulations and cluster model DFT calculations, we rationalize the effect of the active/inactive conformation of the catalytic E49, as well as how L2 containing the other catalytically relevant residue D60 affects catalysis. The higher levels of retro-aldol activity observed for ZmBX1 are attributed to its dual ability to adopt not only active states of the catalytic E49 crucial for retro-aldol cleavage but also inactive states that position E49 in a noncatalytic orientation for disfavoring the reverse aldol reaction back to IGP after product formation. Our combined MD and QM studies elucidate the mechanistic interplay between conformational changes and catalytic steps in ZmBX1 and TrpA enzymes. This study highlights the importance of optimizing the conformational changes and chemical steps along the catalytic itinerary for altering and/or improving enzymatic function.
{"title":"Inactive but Essential: The Role of the Inactive State of E49 in the Mechanism of the Alpha Subunit of Tryptophan Synthase and Its Stand-Alone Blueprint ZmBX1","authors":"Cristina Duran,Sílvia Osuna","doi":"10.1021/acscatal.5c08026","DOIUrl":"https://doi.org/10.1021/acscatal.5c08026","url":null,"abstract":"The stand-alone version of the alpha subunit of tryptophan synthase (TrpA), ZmBX1, catalyzes the retro-aldol cleavage of indole-3-glycerol phosphate (IGP) at a catalytic efficiency that is approximately 144,000 times higher than that of isolated ZmTrpA. Available X-ray crystal structures of ZmBX1 and several TrpAs revealed identical overall structures as well as active site geometries, showing high flexibility of the catalytic E49 in both cases. Based on the crystallographic data, E49 was found to adopt an active state in which the carboxylate group is close to IGP for promoting the retro-aldol cleavage as well as an additional inactive state whose catalytic function was unclear. In this work, by using a combination of Molecular Dynamics (MD) simulations and cluster model DFT calculations, we rationalize the effect of the active/inactive conformation of the catalytic E49, as well as how L2 containing the other catalytically relevant residue D60 affects catalysis. The higher levels of retro-aldol activity observed for ZmBX1 are attributed to its dual ability to adopt not only active states of the catalytic E49 crucial for retro-aldol cleavage but also inactive states that position E49 in a noncatalytic orientation for disfavoring the reverse aldol reaction back to IGP after product formation. Our combined MD and QM studies elucidate the mechanistic interplay between conformational changes and catalytic steps in ZmBX1 and TrpA enzymes. This study highlights the importance of optimizing the conformational changes and chemical steps along the catalytic itinerary for altering and/or improving enzymatic function.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"8 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111133","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 : 2026-02-04DOI: 10.1021/acscatal.5c08933
Sichun Yang,Haijiao Lu,Rijia Lin,Zhiliang Wang,Penghui Yan,Guangyu Zhao,Jiakang You,Julian A. Steele,Kai Wang,Yanzhao Zhang,Yalong Zou,Yonggang Jin,Lianzhou Wang
Photocatalytic CO2 reduction requires catalysts to simultaneously coordinate two distinct half reactions: CO2 activation and H2O dissociation. However, most current materials lack electronically asymmetric sites capable of simultaneously driving both reactions efficiently. Herein, platinum (Pt) is introduced onto oxygen-vacancy (Ov)-rich InOOH to construct a novel interfacial Pt-Ov-In2+ Lewis pair via dynamic electron regulation, where Pt nanoparticles anchor oxygen vacancy and partially reduce adjacent In3+ to In2+, generating a charge-polarized region. Pt simultaneously modulates the Ov population via a reversible electronic interaction, maintaining an optimal balance of Pt0 and the Ov-In2+ sites. Mechanistically, Pt functions as a Lewis-acid H2O activation site, accelerating O–H splitting, while Ov-In2+ serves as a Lewis-base center for CO2 adsorption and bending, stabilizing *CO2– and *CHO intermediates through strengthened In 5s/CO2 antibonding orbital interactions. As a result, Pt/InOOH-Ov delivers a CH4 formation rate of 227.2 μmol g–1 h–1 with 99.0% selectivity, nearly 3 orders of magnitude higher than vacancy-rich InOOH. This work highlights Lewis-pair engineering across vacancy-rich oxide interfaces as a powerful strategy for multielectron CO2 conversion.
{"title":"Interfacial Pt-Ov-In2+ Lewis Pairs Enable Highly Selective Photocatalytic CO2 Methanation","authors":"Sichun Yang,Haijiao Lu,Rijia Lin,Zhiliang Wang,Penghui Yan,Guangyu Zhao,Jiakang You,Julian A. Steele,Kai Wang,Yanzhao Zhang,Yalong Zou,Yonggang Jin,Lianzhou Wang","doi":"10.1021/acscatal.5c08933","DOIUrl":"https://doi.org/10.1021/acscatal.5c08933","url":null,"abstract":"Photocatalytic CO2 reduction requires catalysts to simultaneously coordinate two distinct half reactions: CO2 activation and H2O dissociation. However, most current materials lack electronically asymmetric sites capable of simultaneously driving both reactions efficiently. Herein, platinum (Pt) is introduced onto oxygen-vacancy (Ov)-rich InOOH to construct a novel interfacial Pt-Ov-In2+ Lewis pair via dynamic electron regulation, where Pt nanoparticles anchor oxygen vacancy and partially reduce adjacent In3+ to In2+, generating a charge-polarized region. Pt simultaneously modulates the Ov population via a reversible electronic interaction, maintaining an optimal balance of Pt0 and the Ov-In2+ sites. Mechanistically, Pt functions as a Lewis-acid H2O activation site, accelerating O–H splitting, while Ov-In2+ serves as a Lewis-base center for CO2 adsorption and bending, stabilizing *CO2– and *CHO intermediates through strengthened In 5s/CO2 antibonding orbital interactions. As a result, Pt/InOOH-Ov delivers a CH4 formation rate of 227.2 μmol g–1 h–1 with 99.0% selectivity, nearly 3 orders of magnitude higher than vacancy-rich InOOH. This work highlights Lewis-pair engineering across vacancy-rich oxide interfaces as a powerful strategy for multielectron CO2 conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"25 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111252","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 : 2026-02-04DOI: 10.1021/acscatal.5c07770
Supriti Dutta, Kristin K. Anderson, Md Raian Yousuf, Ayman M. Karim, John R. Morris, Philippe Sautet
The development of noble metal catalysts with sustained high activity for methanol oxidation is essential for chemical production and for energy transformation with methanol fuel cells. Here, we report Pt oxide clusters supported on anatase TiO2, exhibiting enhanced methanol oxidation performance. Interfacial interactions between oxidized Pt clusters and TiO2 strongly influence electronic states and adsorption of intermediates, thereby shaping catalytic performance. Density functional theory (DFT) combined with Fourier-transform infrared spectroscopy (FTIR) revealed methanol adsorption and oxidation mechanisms. Using grand canonical basin hopping (GCBH), we identified stable and metastable model Pt6Ox clusters on TiO2(101), with Pt6 partially oxidized to Pt6O10 under ambient conditions. Three methanol oxidation pathways were examined: partial oxidation to CO, formation of methyl formate (HCOOCH3) by C–O coupling, and complete oxidation to CO2, proceeding via the *OCH2O (dioxymethylene DOM) intermediate. The formation of DOM enables an alternative pathway in which the C–O bond forms at an early stage, thus offering a CO-free mechanism that prevents CO poisoning. The Pt oxide cluster exhibits dynamic redox behavior, undergoing initial partial reduction followed by reoxidation, highlighting the adaptive nature of the catalytic system. Notably, the catalytic activity is further enhanced when water formation accompanies the reaction pathway. Overall, this work provides insight into how the Pt/TiO2 interface is the origin of a high methanol oxidation activity, consistent with experimental observations. These insights bring a rational framework for designing efficient and durable catalysts for selective oxidation reactions.
{"title":"Unraveling the Methanol Oxidation Mechanism over a Titania-Supported Platinum Catalyst","authors":"Supriti Dutta, Kristin K. Anderson, Md Raian Yousuf, Ayman M. Karim, John R. Morris, Philippe Sautet","doi":"10.1021/acscatal.5c07770","DOIUrl":"https://doi.org/10.1021/acscatal.5c07770","url":null,"abstract":"The development of noble metal catalysts with sustained high activity for methanol oxidation is essential for chemical production and for energy transformation with methanol fuel cells. Here, we report Pt oxide clusters supported on anatase TiO<sub>2</sub>, exhibiting enhanced methanol oxidation performance. Interfacial interactions between oxidized Pt clusters and TiO<sub>2</sub> strongly influence electronic states and adsorption of intermediates, thereby shaping catalytic performance. Density functional theory (DFT) combined with Fourier-transform infrared spectroscopy (FTIR) revealed methanol adsorption and oxidation mechanisms. Using grand canonical basin hopping (GCBH), we identified stable and metastable model Pt<sub>6</sub>O<sub><i>x</i></sub> clusters on TiO<sub>2</sub>(101), with Pt<sub>6</sub> partially oxidized to Pt<sub>6</sub>O<sub>10</sub> under ambient conditions. Three methanol oxidation pathways were examined: partial oxidation to CO, formation of methyl formate (HCOOCH<sub>3</sub>) by C–O coupling, and complete oxidation to CO<sub>2</sub>, proceeding via the *OCH<sub>2</sub>O (dioxymethylene DOM) intermediate. The formation of DOM enables an alternative pathway in which the C–O bond forms at an early stage, thus offering a CO-free mechanism that prevents CO poisoning. The Pt oxide cluster exhibits dynamic redox behavior, undergoing initial partial reduction followed by reoxidation, highlighting the adaptive nature of the catalytic system. Notably, the catalytic activity is further enhanced when water formation accompanies the reaction pathway. Overall, this work provides insight into how the Pt/TiO<sub>2</sub> interface is the origin of a high methanol oxidation activity, consistent with experimental observations. These insights bring a rational framework for designing efficient and durable catalysts for selective oxidation reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"102 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110655","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 : 2026-02-04DOI: 10.1021/acscatal.5c08582
Joaquin Resasco, Jimmy Faria Albanese, Walter Alvarez, Steven Crossley, Gary L. Haller, José E. Herrera, Gary Jacobs, Johannes Lercher, Gengnan Li, Lance Lobban, Fábio Bellot Noronha, M. Pilar Ruiz, Tawan Sooknoi, Bin Wang
In the original manuscript, José E. Herrera was inadvertently omitted from the author list. He contributed to the section on carbon nanotubes. The author list has been corrected to reflect his contribution. This article has not yet been cited by other publications.
{"title":"Correction to “A Career in Catalysis: Daniel Resasco”","authors":"Joaquin Resasco, Jimmy Faria Albanese, Walter Alvarez, Steven Crossley, Gary L. Haller, José E. Herrera, Gary Jacobs, Johannes Lercher, Gengnan Li, Lance Lobban, Fábio Bellot Noronha, M. Pilar Ruiz, Tawan Sooknoi, Bin Wang","doi":"10.1021/acscatal.5c08582","DOIUrl":"https://doi.org/10.1021/acscatal.5c08582","url":null,"abstract":"In the original manuscript, José E. Herrera was inadvertently omitted from the author list. He contributed to the section on carbon nanotubes. The author list has been corrected to reflect his contribution. This article has not yet been cited by other publications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110657","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 : 2026-02-04DOI: 10.1021/acscatal.5c07650
Zhewei Li,Yanhui Tang,Ming Lei
The γ-C(sp3)–H functionalization of carboxylic acids in the presence of β-C(sp3)–H bonds is a tremendous challenge due to the overwhelming formation of five-membered metallacycles over six-membered ones. In this study, the reaction mechanism of the Pd-catalyzed γ-methylene C(sp3)–H (hetero)arylation of cycloalkane carboxylic acids was investigated using the density functional theory method and the nature of the counter-cation effect was unveiled. Different from the previously proposed six-membered palladacyclic intermediate formed by the γ-C(sp3)–H activation, the calculated results indicate that in this reaction, the β-C(sp3)–H bond will be favorably activated at first to form a five-membered palladacyclic intermediate instead of the γ-C(sp3)–H bond and that the achieved β,γ-unsaturated acid after the β- and γ-C(sp3)–H activation is a key feasible transient intermediate for the following γ-C(sp3)–H arylation. The γ-arylation product is obtained by the C–C coupling of β,γ-unsaturated acid with aryl iodide, which could be realized by the Pd–Ag catalytic model via a Pd(0)/Pd(II) mechanism instead of the Pd–Ag–Cs catalytic model via a Pd(II)/Pd(IV) mechanism. The reaction mechanism not only reveals the origin of this reactivity but also successfully explains the experimental phenomenon that the reaction is insensitive to bases, which is significantly different from the previous reports on the β-C(sp3)–H and γ-C(sp3)–H arylation of carboxylic acids.
{"title":"Unveiling the Mechanism of Pd-Catalyzed γ-Methylene C(sp3)–H Arylation of Carboxylic Acids","authors":"Zhewei Li,Yanhui Tang,Ming Lei","doi":"10.1021/acscatal.5c07650","DOIUrl":"https://doi.org/10.1021/acscatal.5c07650","url":null,"abstract":"The γ-C(sp3)–H functionalization of carboxylic acids in the presence of β-C(sp3)–H bonds is a tremendous challenge due to the overwhelming formation of five-membered metallacycles over six-membered ones. In this study, the reaction mechanism of the Pd-catalyzed γ-methylene C(sp3)–H (hetero)arylation of cycloalkane carboxylic acids was investigated using the density functional theory method and the nature of the counter-cation effect was unveiled. Different from the previously proposed six-membered palladacyclic intermediate formed by the γ-C(sp3)–H activation, the calculated results indicate that in this reaction, the β-C(sp3)–H bond will be favorably activated at first to form a five-membered palladacyclic intermediate instead of the γ-C(sp3)–H bond and that the achieved β,γ-unsaturated acid after the β- and γ-C(sp3)–H activation is a key feasible transient intermediate for the following γ-C(sp3)–H arylation. The γ-arylation product is obtained by the C–C coupling of β,γ-unsaturated acid with aryl iodide, which could be realized by the Pd–Ag catalytic model via a Pd(0)/Pd(II) mechanism instead of the Pd–Ag–Cs catalytic model via a Pd(II)/Pd(IV) mechanism. The reaction mechanism not only reveals the origin of this reactivity but also successfully explains the experimental phenomenon that the reaction is insensitive to bases, which is significantly different from the previous reports on the β-C(sp3)–H and γ-C(sp3)–H arylation of carboxylic acids.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111253","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 : 2026-02-03DOI: 10.1021/acscatal.5c06553
Edvin Fako, Sandip De
Understanding interactions between reactive fragments and surfaces is a central objective in functional materials design and discovery. No available computational methods can reliably generate such structures for an arbitrary choice of fragment and surface while explicitly describing the binding mode. As a result, human curation is accepted as the norm, introducing bias and hampering efforts toward computational materials screening and database engineering, limiting the reach and impact of machine learning in the field. By implementing two complementary concepts, surrogate-SMILES (*SMILES) and an atomic-position-only algorithm for surface site identification, we achieve simple parametrization of all fragment-surface configurations. We harness this fully hands-off approach to revisit CO2 reduction on copper, discovering diversity in the adsorption energy spectra, even for this benchmark system. We generate a holistic picture of fragment-surface energy features and compare them across systems and facets. Efficient parametrization and string-based expression provide a strong bridge of our approach to generative, optimization, and language-driven machine learning frameworks. With no domain-specific assertions, this approach extends to all domains in which surface reactivity is key for rational design.
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Pub Date : 2026-02-03DOI: 10.1021/acscatal.5c08818
Sara Ahsan, Sirinada Chanthachaiwat, Alexander Kvit, Siddarth H. Krishna
N-Heterocyclic aromatics can reversibly store H2 through (de)hydrogenation over supported Pd catalysts, but metal nanoparticles often sinter during liquid-phase reactions. Here, we report that the encapsulation of Pd nanoparticles in large-pore zeolites stabilizes Pd catalysts during hydrogenation of N-methylindole (N-MID). Flow reactor studies combined with post-reaction characterizations show that Pd nanoparticles supported on SiO2 or Al2O3 sinter during hydrogenation of N-MID, while Pd/zeolites (particularly Pd/Beta) retain <2 nm particles, likely by suppressing the chelation and migration of Pd by N-MID. This work highlights the potential of zeolitic voids to suppress metal catalyst deactivation in liquid-phase reactions including H2 storage in chemical bonds.
n -杂环芳烃可以通过负载型钯催化剂上的（脱）氢化反应可逆地储存H2，但金属纳米颗粒在液相反应中经常烧结。在这里，我们报道了在n -甲基吲哚（N-MID）加氢过程中，钯纳米粒子在大孔沸石中的包封可以稳定钯催化剂。流动反应器研究结合反应后的表征表明，在N-MID加氢过程中，Pd纳米颗粒被SiO2或Al2O3烧结体支撑，而Pd/沸石（尤其是Pd/Beta）保留了2纳米颗粒，可能是通过抑制N-MID对Pd的螯合和迁移。这项工作强调了沸石孔隙在液相反应中抑制金属催化剂失活的潜力，包括化学键中H2的储存。
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