ACS Catalysis 最新文献

{"title":"Stereodivergent Construction of Enamides via a Radical-Mediated Isodesmic Reaction","authors":"Yingying Xu, Xin Zhang, Xiao Kang, Kai Xu, Gangguo Zhu, Xi-Jia Liu","doi":"10.1021/acscatal.5c00583","DOIUrl":"https://doi.org/10.1021/acscatal.5c00583","url":null,"abstract":"Stereodivergent synthesis from the same starting materials is highly attractive but challenging in chemistry. Here, an unprecedented radical-mediated isodesmic reaction between aryl methylenemalononitriles and <i>N</i>-methyl amides is described. This integrated photochemical strategy enables the divergent synthesis of both (<i>E</i>)- and (<i>Z</i>)-enamides under very mild conditions. Particularly, it can prepare modularly (<i>E</i>)-α-deuterium enamides with &gt;95% deuterium incorporation, representing a highly valuable addition to the research toolkit for enamide production. The utility of this protocol is also demonstrated by the synthesis of natural product alatamide and its deuterium-labeled analog. Mechanistic studies reveal that two sequential alkyl radical generations via photoinduced hydrogen atom transfer (HAT) in the presence of a sodium decatungstate (NaDT) catalyst are essential for this isodesmic reaction, and <i>E</i>/<i>Z</i> selectivities are adjusted by cocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"59 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819712","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}

{"title":"Engineering a Biosynthetic Pathway to Produce (+)-Brevianamides A and B","authors":"Casandra P. Sandoval Hurtado, Samantha P. Kelly, Vikram V. Shende, Makayla Perez, Brian J. Curtis, Sean A. Newmister, Kaleb Ott, Filipa Pereira, David H. Sherman","doi":"10.1021/acscatal.5c00753","DOIUrl":"https://doi.org/10.1021/acscatal.5c00753","url":null,"abstract":"The privileged fused-ring structure comprising the bicyclo[2.2.2]diazaoctane (BDO) core is prevalent in diketopiperazine (DKP) natural products that exhibit potent and diverse biological activities. Typically, only low yields of these compounds can be extracted from native fungal producing strains and accessing them diastereoselectively remains challenging using available synthetic routes. BDO-containing DKPs including (+)-brevianamides A <b>5</b> and B <b>6</b> are assembled via multienzyme biosynthetic pathways incorporating nonribosomal peptide synthetases, prenyltransferases, flavin monooxygenases, cytochromes P450, and isomerases. To simplify access to this class of alkaloids, we designed an engineered biosynthetic pathway in <i>Escherichia coli</i>, composed of six enzymes sourced from different kingdoms of life. The pathway includes a cyclodipeptide synthase from <i>Streptomyces</i> sp. CMB-MQ030 (NascA), cyclodipeptide oxidase from <i>Streptomyces</i> sp. F5123 (DmtD2/DmtE2), prenyltransferase from <i>Aspergillus</i> sp. MF297–2 (NotF), flavin-dependent monooxygenase from <i>Penicillium brevicompactum</i> (BvnB), and kinases from <i>Shigella flexneri</i> and <i>Thermoplasma acidophilum</i> (PhoN and IPK). Cultivated in glycerol media supplemented with prenol, the engineered <i>E. coli</i> strain produces 5.3 mg/L of (<b>−</b>)-dehydrobrevianamide E <b>4</b>, which undergoes a previously reported lithium hydroxide rearrangement cascade to yield <b>5</b> and <b>6</b>, with a combined 70% yield and a 94:6 diastereomeric ratio. Additionally, titers of <b>4</b> were increased to 20.6 mg/L by enhancing NADPH pools in the engineered strain. Overall, our study combines <i>de novo</i> biosynthetic pathway engineering and chemical synthesis approaches to generate complex indole alkaloids.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"65 1","pages":"6711-6720"},"PeriodicalIF":12.9,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813892","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}

{"title":"Is Carbon Heteroatom Doping the Key to Active and Stable Carbon Supported Cobalt Fischer–Tropsch Catalysts?","authors":"Felix Herold*,&nbsp;Dominic de Oliveira,&nbsp;Göran Baade,&nbsp;Jens Friedland,&nbsp;Robert Güttel,&nbsp;Michael Claeys and Magnus Rønning*,&nbsp;","doi":"10.1021/acscatal.4c0809210.1021/acscatal.4c08092","DOIUrl":"https://doi.org/10.1021/acscatal.4c08092https://doi.org/10.1021/acscatal.4c08092","url":null,"abstract":"<p >Carbon supports are an interesting alternative to established oxidic catalyst supports for Co-based Fischer–Tropsch synthesis (FTS) catalysts as they allow high Co reducibility and do not suffer from the formation of Co/support compounds. To optimize Co-based carbon-supported FTS catalysts, significant research has focused on doping carbon supports with heteroatoms, aiming to enhance both catalytic activity and stability. While improvements in FTS performance have been reported for N-doped carbon supports, the exact effects of heteroatom doping are still poorly understood, largely due to difficulties in directly comparing Co FTS catalysts supported on doped versus nondoped carbon materials. In this study, we synthesized a series of highly comparable N-, S-, and P-doped carbon nanofiber (CNF) model supports, which were combined with size-controlled, colloidal Co nanoparticles to create well-defined model FTS catalysts. Comprehensive characterization of these catalysts using in situ X-ray absorption spectroscopy (XAS), in situ X-ray diffraction (XRD), and in situ magnetometry revealed that the presence of dopants significantly altered the structure and properties of the catalytically active Co⁰ phase, affecting Co coordination numbers, crystal phase composition, and magnetic behavior. Challenging optimistic literature reports, our findings demonstrate that all the studied heteroatoms negatively impact either FTS activity or catalyst stability. Co on N-doped CNFs experienced rapid deactivation due to increased sintering as well as Co phase transformations, which were not observed for Co on nondoped CNFs. Co on S-doped CNF suffered from instability of carbon-bound S species in a hydrogen atmosphere, contributing to low FTS performance by S-poisoning. Finally, Co on P-doped CNFs displayed strong metal–support interactions that improved sintering stability, but FTS activity was hampered by low Co reducibility and the loss of active Co⁰ due to a complex sequence of cobalt phosphide formation and its subsequent decomposition into phosphorus oxides and cobalt oxide species under FTS conditions.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 8","pages":"6673–6689 6673–6689"},"PeriodicalIF":11.3,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscatal.4c08092","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842506","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective Hydrogenation of Furfural Acetone over a Cu Catalyst: Combined Theoretical and Experimental Study","authors":"Michael Rebarchik, Evangelos Smith, Hochan Chang, James A. Dumesic, Manos Mavrikakis","doi":"10.1021/acscatal.4c07231","DOIUrl":"https://doi.org/10.1021/acscatal.4c07231","url":null,"abstract":"The selective hydrogenation of biomass-derived hydroxymethyl furfural (HMF)-acetone-HMF (HAH) presents an alternative route to producing highly functionalized polyesters and polyurethanes. While HAH undergoes furan ring hydrogenation over Pd, Ru, and Ni catalysts, furan ring hydrogenation is not observed over Cu. Herein, we combine reaction kinetics experiments and density functional theory calculations to elucidate the selective hydrogenation behavior of HAH over Cu catalysts. We identified furfural acetone (FAc) as a suitable surrogate for modeling HAH hydrogenation over Cu surfaces and performed reaction kinetics experiments between temperatures of 313–393 K and a H₂ partial pressure of 55 bar. Similar to the behavior of HAH, hydrogenation of FAc follows a consecutive two-step hydrogenation pathway over Cu and does not undergo furan ring hydrogenation. The apparent activation energy barriers for hydrogenation of the aliphatic double bond (0.58 eV) and carbonyl (0.43 eV) of FAc measured in a continuous flow reactor setup are consistent with those reported in prior studies for batch HAH hydrogenation. Reaction orders with respect to each reactant, including H₂ and FAc, were determined to be nearly one. Density functional theory (DFT; GGA-PBE-D3) calculations on Cu(111) showed that the hydrogenation of the aliphatic double bond of FAc is more facile than the hydrogenation of the furan ring, which displays weak interactions with the Cu surface. We determined an apparent activation energy barrier for FAc hydrogenation (0.58 eV) that agreed with our DFT predictions (highest barrier for FAc hydrogenation of 0.57 eV). Our DFT calculations further show that weak interactions between the furan ring and Cu surface are responsible for the selective hydrogenation behavior.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"183 1","pages":"6662-6672"},"PeriodicalIF":12.9,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813452","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}

{"title":"Activation and Reactivity of Vinylcyclobutane with Phosphine Nickel Catalysts","authors":"Cherish Nie,&nbsp;Chloe Park,&nbsp;Junho Kim and Paul J. Chirik*,&nbsp;","doi":"10.1021/acscatal.5c0092010.1021/acscatal.5c00920","DOIUrl":"https://doi.org/10.1021/acscatal.5c00920https://doi.org/10.1021/acscatal.5c00920","url":null,"abstract":"<p >A series of monodentate phosphine ligands was evaluated for the nickel-mediated activation of vinylcyclobutane (VCB) by oxidative addition to form the corresponding η¹,η³-metallacycles. The addition of VCB to equimolar mixtures of phosphine and Ni(COD)₂ (COD = 1,5-cyclooctadiene) produced a mixture of P₂Ni(COD), P₂Ni(VCB), and/or P₁Ni(VCB)₂. The accessibility of a VCB-derived P₁Ni(II) alkyl,allyl-metallacycle correlated with an increasing number of alkyl substituents on the phosphine. Among trialkyl phosphines, PCy₃ and P^<i>i</i>Pr₃ were the most effective for metallacycle formation. The VCB-derived metallacycles (Cy₃P)Ni(C₆H₁₀) and (^<i>i</i>Pr₃P)Ni(C₆H₁₀) were isolated and characterized by NMR spectroscopy and single-crystal X-ray diffraction. The thermal and photochemical reactivity of (Cy₃P)Ni(C₆H₁₀) was explored and compared to related (NHC)Ni(C₆H₁₀) metallacycles (NHC = <i>N</i>-heterocyclic carbene). Catalytic VCB-activation was observed with (Cy₃P)Ni(C₆H₁₀) at 120 °C and furnished products from retro-[2 + 2] cycloaddition – ethylene, vinylcyclohexene, and cyclooctadiene – as well as 2,4-hexadiene arising from β-H elimination. Catalytic activation of VCB was observed upon irradiation of (Cy₃P)Ni(C₆H₁₀) with blue light at 60 °C with improved selectivity for retro-[2 + 2] products over β-Η elimination and [2 + 1] cycloaddition products compared to NHC analogues. (Cy₃P)Ni(C₆H₁₀) was also found to catalyze the retro-[2 + 2] depolymerization of (1,<i>n</i>′-divinyl)oligocyclobutane, but the presence of substituents on the cyclobutane ring resulted in an increased preference for β-H elimination.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 8","pages":"6652–6661 6652–6661"},"PeriodicalIF":11.3,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842195","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}

{"title":"Is Carbon Heteroatom Doping the Key to Active and Stable Carbon Supported Cobalt Fischer–Tropsch Catalysts?","authors":"Felix Herold, Dominic de Oliveira, Göran Baade, Jens Friedland, Robert Güttel, Michael Claeys, Magnus Rønning","doi":"10.1021/acscatal.4c08092","DOIUrl":"https://doi.org/10.1021/acscatal.4c08092","url":null,"abstract":"Carbon supports are an interesting alternative to established oxidic catalyst supports for Co-based Fischer–Tropsch synthesis (FTS) catalysts as they allow high Co reducibility and do not suffer from the formation of Co/support compounds. To optimize Co-based carbon-supported FTS catalysts, significant research has focused on doping carbon supports with heteroatoms, aiming to enhance both catalytic activity and stability. While improvements in FTS performance have been reported for N-doped carbon supports, the exact effects of heteroatom doping are still poorly understood, largely due to difficulties in directly comparing Co FTS catalysts supported on doped versus nondoped carbon materials. In this study, we synthesized a series of highly comparable N-, S-, and P-doped carbon nanofiber (CNF) model supports, which were combined with size-controlled, colloidal Co nanoparticles to create well-defined model FTS catalysts. Comprehensive characterization of these catalysts using in situ X-ray absorption spectroscopy (XAS), in situ X-ray diffraction (XRD), and in situ magnetometry revealed that the presence of dopants significantly altered the structure and properties of the catalytically active Co⁰ phase, affecting Co coordination numbers, crystal phase composition, and magnetic behavior. Challenging optimistic literature reports, our findings demonstrate that all the studied heteroatoms negatively impact either FTS activity or catalyst stability. Co on N-doped CNFs experienced rapid deactivation due to increased sintering as well as Co phase transformations, which were not observed for Co on nondoped CNFs. Co on S-doped CNF suffered from instability of carbon-bound S species in a hydrogen atmosphere, contributing to low FTS performance by S-poisoning. Finally, Co on P-doped CNFs displayed strong metal–support interactions that improved sintering stability, but FTS activity was hampered by low Co reducibility and the loss of active Co⁰ due to a complex sequence of cobalt phosphide formation and its subsequent decomposition into phosphorus oxides and cobalt oxide species under FTS conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"75 1","pages":"6673-6689"},"PeriodicalIF":12.9,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813453","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}

{"title":"Activation and Reactivity of Vinylcyclobutane with Phosphine Nickel Catalysts","authors":"Cherish Nie, Chloe Park, Junho Kim, Paul J. Chirik","doi":"10.1021/acscatal.5c00920","DOIUrl":"https://doi.org/10.1021/acscatal.5c00920","url":null,"abstract":"A series of monodentate phosphine ligands was evaluated for the nickel-mediated activation of vinylcyclobutane (VCB) by oxidative addition to form the corresponding η¹,η³-metallacycles. The addition of VCB to equimolar mixtures of phosphine and Ni(COD)₂ (COD = 1,5-cyclooctadiene) produced a mixture of P₂Ni(COD), P₂Ni(VCB), and/or P₁Ni(VCB)₂. The accessibility of a VCB-derived P₁Ni(II) alkyl,allyl-metallacycle correlated with an increasing number of alkyl substituents on the phosphine. Among trialkyl phosphines, PCy₃ and P^<i>i</i>Pr₃ were the most effective for metallacycle formation. The VCB-derived metallacycles (Cy₃P)Ni(C₆H₁₀) and (^<i>i</i>Pr₃P)Ni(C₆H₁₀) were isolated and characterized by NMR spectroscopy and single-crystal X-ray diffraction. The thermal and photochemical reactivity of (Cy₃P)Ni(C₆H₁₀) was explored and compared to related (NHC)Ni(C₆H₁₀) metallacycles (NHC = <i>N</i>-heterocyclic carbene). Catalytic VCB-activation was observed with (Cy₃P)Ni(C₆H₁₀) at 120 °C and furnished products from retro-[2 + 2] cycloaddition – ethylene, vinylcyclohexene, and cyclooctadiene – as well as 2,4-hexadiene arising from β-H elimination. Catalytic activation of VCB was observed upon irradiation of (Cy₃P)Ni(C₆H₁₀) with blue light at 60 °C with improved selectivity for retro-[2 + 2] products over β-Η elimination and [2 + 1] cycloaddition products compared to NHC analogues. (Cy₃P)Ni(C₆H₁₀) was also found to catalyze the retro-[2 + 2] depolymerization of (1,<i>n</i>′-divinyl)oligocyclobutane, but the presence of substituents on the cyclobutane ring resulted in an increased preference for β-H elimination.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"33 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806379","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}

{"title":"Selective Hydrogenation of Furfural Acetone over a Cu Catalyst: Combined Theoretical and Experimental Study","authors":"Michael Rebarchik,&nbsp;Evangelos Smith,&nbsp;Hochan Chang,&nbsp;James A. Dumesic and Manos Mavrikakis*,&nbsp;","doi":"10.1021/acscatal.4c0723110.1021/acscatal.4c07231","DOIUrl":"https://doi.org/10.1021/acscatal.4c07231https://doi.org/10.1021/acscatal.4c07231","url":null,"abstract":"<p >The selective hydrogenation of biomass-derived hydroxymethyl furfural (HMF)-acetone-HMF (HAH) presents an alternative route to producing highly functionalized polyesters and polyurethanes. While HAH undergoes furan ring hydrogenation over Pd, Ru, and Ni catalysts, furan ring hydrogenation is not observed over Cu. Herein, we combine reaction kinetics experiments and density functional theory calculations to elucidate the selective hydrogenation behavior of HAH over Cu catalysts. We identified furfural acetone (FAc) as a suitable surrogate for modeling HAH hydrogenation over Cu surfaces and performed reaction kinetics experiments between temperatures of 313–393 K and a H₂ partial pressure of 55 bar. Similar to the behavior of HAH, hydrogenation of FAc follows a consecutive two-step hydrogenation pathway over Cu and does not undergo furan ring hydrogenation. The apparent activation energy barriers for hydrogenation of the aliphatic double bond (0.58 eV) and carbonyl (0.43 eV) of FAc measured in a continuous flow reactor setup are consistent with those reported in prior studies for batch HAH hydrogenation. Reaction orders with respect to each reactant, including H₂ and FAc, were determined to be nearly one. Density functional theory (DFT; GGA-PBE-D3) calculations on Cu(111) showed that the hydrogenation of the aliphatic double bond of FAc is more facile than the hydrogenation of the furan ring, which displays weak interactions with the Cu surface. We determined an apparent activation energy barrier for FAc hydrogenation (0.58 eV) that agreed with our DFT predictions (highest barrier for FAc hydrogenation of 0.57 eV). Our DFT calculations further show that weak interactions between the furan ring and Cu surface are responsible for the selective hydrogenation behavior.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 8","pages":"6662–6672 6662–6672"},"PeriodicalIF":11.3,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842505","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}

{"title":"Unveiling Universal Reactivity Descriptors of Metal Clusters toward Dinitrogen Activation: A Machine Learning Protocol with Three-Level Feature Extraction","authors":"Li-Hui Mou,&nbsp;Gui-Duo Jiang,&nbsp;Chao Wang,&nbsp;Xin Cheng,&nbsp;Jia Yu*,&nbsp;Zi-Yu Li* and Jun Jiang*,&nbsp;","doi":"10.1021/acscatal.5c0137910.1021/acscatal.5c01379","DOIUrl":"https://doi.org/10.1021/acscatal.5c01379https://doi.org/10.1021/acscatal.5c01379","url":null,"abstract":"<p >The activation of dinitrogen (N₂) by metal clusters is a fundamental challenge in chemistry and has been extensively studied. However, previous studies have primarily focused on case-by-case interpretations of experimental reactivity, resulting in a lack of universal reactivity descriptors and predictive models that can quantitatively estimate reaction rates and elucidate structure–activity relationships. In this study, we develop predictive, interpretable, and transferable machine learning models for metal cluster reactivity toward N₂, employing a systematic and hierarchical feature extraction strategy that generates electronic and intrinsic features from three structural levels. Crucial features influencing cluster reactivity were identified, and the mechanisms by which these features govern reactivity were elucidated. To enhance model robustness and transferability, pairwise learning (data augmentation) and feature interaction (feature augmentation) strategies were employed, leading to a deep neural network model that correlates feature differences with reaction rate differences. Trained on 159 homonuclear metal clusters, the model demonstrates satisfactory transferability to 57 heteronuclear metal clusters, enabling reaction rate predictions based on their feature differences. This work presents an expert-guided machine learning protocol for developing generalizable models to predict and understand metal cluster reactivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 8","pages":"6618–6627 6618–6627"},"PeriodicalIF":11.3,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842391","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}

{"title":"Unveiling Universal Reactivity Descriptors of Metal Clusters toward Dinitrogen Activation: A Machine Learning Protocol with Three-Level Feature Extraction","authors":"Li-Hui Mou, Gui-Duo Jiang, Chao Wang, Xin Cheng, Jia Yu, Zi-Yu Li, Jun Jiang","doi":"10.1021/acscatal.5c01379","DOIUrl":"https://doi.org/10.1021/acscatal.5c01379","url":null,"abstract":"The activation of dinitrogen (N₂) by metal clusters is a fundamental challenge in chemistry and has been extensively studied. However, previous studies have primarily focused on case-by-case interpretations of experimental reactivity, resulting in a lack of universal reactivity descriptors and predictive models that can quantitatively estimate reaction rates and elucidate structure–activity relationships. In this study, we develop predictive, interpretable, and transferable machine learning models for metal cluster reactivity toward N₂, employing a systematic and hierarchical feature extraction strategy that generates electronic and intrinsic features from three structural levels. Crucial features influencing cluster reactivity were identified, and the mechanisms by which these features govern reactivity were elucidated. To enhance model robustness and transferability, pairwise learning (data augmentation) and feature interaction (feature augmentation) strategies were employed, leading to a deep neural network model that correlates feature differences with reaction rate differences. Trained on 159 homonuclear metal clusters, the model demonstrates satisfactory transferability to 57 heteronuclear metal clusters, enabling reaction rate predictions based on their feature differences. This work presents an expert-guided machine learning protocol for developing generalizable models to predict and understand metal cluster reactivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"21 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798450","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}