ACS Catalysis 最新文献_第3页

Dual-Enzyme Relay Catalysis Enables Asymmetric Construction of Nonadjacent Stereocenters in Polycyclic Alcohols 双酶接力催化使多环醇非相邻立体中心的不对称结构成为可能

IF 12.9 1区化学

ACS Catalysis Pub Date : 2026-10-19 DOI: 10.1021/acscatal.6c05074

Fengxi Li,Shenhan Xie,Xinjia Yu,Meijiao Gao,Qi Sun,Chuang Du,Zhi Wang,Lei Wang

{"title":"Dual-Enzyme Relay Catalysis Enables Asymmetric Construction of Nonadjacent Stereocenters in Polycyclic Alcohols","authors":"Fengxi Li,Shenhan Xie,Xinjia Yu,Meijiao Gao,Qi Sun,Chuang Du,Zhi Wang,Lei Wang","doi":"10.1021/acscatal.6c05074","DOIUrl":"https://doi.org/10.1021/acscatal.6c05074","url":null,"abstract":"The asymmetric construction of nonadjacent stereocenters in a single catalytic system remains a significant challenge due to the difficulty in controlling stereochemical relay between sequential transformations. Herein, we report a dual-enzyme relay catalytic system that integrates an artificial streptavidin-based copper metalloenzyme (Sav-Cu) with an engineered ketoreductase (KRED) for the one-pot synthesis of polycyclic alcohols bearing 1,3-non-adjacent stereocenters. In this relay process, the engineered SavDMase variant (S112A/K121D) catalyzes a non-natural decarboxylative Mannich reaction to establish the R-configured stereocenter in the enantioenriched ketone intermediate, which is then recognized by the engineered KREDAV mutant (S96A/Y190V) and reduced with high diastereo- and enantioselectivity to install the S-configured alcohol stereocenter, thereby furnishing the (R,S)-configured product as the dominant stereoisomer. The optimized system furnishes the products in up to 83% yield, 99% ee, and 96% de across a broad substrate scope, and is readily applicable to 2 mmol-scale synthesis. Structural analysis, docking, and molecular dynamics simulations support complementary roles of the two catalytic modules: SavDMase promotes productive organization of the Mannich step, while KREDAV stabilizes the reactive binding pose and constrains the hydride-transfer trajectory to enforce stereoselective reduction. This work demonstrates how artificial and natural enzymes can be integrated in relay catalysis to solve challenging stereochemical relay problems beyond the reach of individual biocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The Two Opposite Faces of Ceria as Redox Mediator in Methane Dry Reforming 甲烷干重整中氧化还原介质氧化铈的两个对立面

IF 12.9 1区化学

ACS Catalysis Pub Date : 2026-10-19 DOI: 10.1021/acscatal.6c04731

Mahdi Hosseinpour,Thomas F. Winterstein,Benjamin Pichler,Hans Krammer,Bernhard Klötzer,Simon Penner

{"title":"The Two Opposite Faces of Ceria as Redox Mediator in Methane Dry Reforming","authors":"Mahdi Hosseinpour,Thomas F. Winterstein,Benjamin Pichler,Hans Krammer,Bernhard Klötzer,Simon Penner","doi":"10.1021/acscatal.6c04731","DOIUrl":"https://doi.org/10.1021/acscatal.6c04731","url":null,"abstract":"We investigate the interplay between carbon accumulation and redox-driven deactivation pathways in cerium-containing nickel (NiCe) and palladium (PdCe) bimetallic precursor materials upon eventual decomposition into a Ni- or Pd-ceria interfacial system during dry reforming of methane (DRM). By probing defined intermediate states, information from surface electronic structure, morphology, and bulk structure to track structural and chemical changes across several reaction, deactivation, and CO2 titration cycles is combined to identify how carbon accumulation, oxygen transfer, and dynamic metal–ceria interfacial interactions evolve under DRM reaction conditions. Despite their similar cerium-containing precursor architecture and surface composition, the two systems allow studying two detrimental deactivation processes. Bimetallic NiCe decomposes more readily into a Ni-ceria interface, where carbon formation is progressively suppressed. Loss of activity is a result of oxidation of Ni particles mediated by enhanced oxygen transfer from ceria. In contrast, bimetallic PdCe is much more decomposition-resistant, and the localized Pd-ceria interface exhibits high activity throughout multiple DRM cycles, even in the presence of substantial carbon deposition and filamentous carbon growth. The results demonstrate an intrinsic coupling between carbon accumulation and oxygen transfer to the metallic component, with carbon acting as a competing sink for reactive oxygen species. We emphasize the significance of dynamic interfacial structures and show that ceria-mediated oxygen transfer produces contrasting, metal-dependent catalytic outcomes. Whereas in NiCe, efficient oxygen delivery suppresses carbon accumulation, but progressively oxidizes Ni and diminishes methane activation, in PdCe, carbon generation outpaces oxygen-mediated removal, yielding a carbon-rich yet catalytically persistent surface.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"13 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chemoenzymatic Cascade Recycling and Upcycling of Polyurethane Elastomers 聚氨酯弹性体的化学酶级联回收和升级回收

IF 12.9 1区化学

ACS Catalysis Pub Date : 2026-10-19 DOI: 10.1021/acscatal.6c07295

Shengwei Sun,Erik N. A. Sundén,Marcus Moldenhauer,Diana Bernin,Uwe T. Bornscheuer,Minna Hakkarainen,Per-Olof Syrén

{"title":"Chemoenzymatic Cascade Recycling and Upcycling of Polyurethane Elastomers","authors":"Shengwei Sun,Erik N. A. Sundén,Marcus Moldenhauer,Diana Bernin,Uwe T. Bornscheuer,Minna Hakkarainen,Per-Olof Syrén","doi":"10.1021/acscatal.6c07295","DOIUrl":"https://doi.org/10.1021/acscatal.6c07295","url":null,"abstract":"The complex structure of polyurethanes (PURs) presents a major barrier to their efficient recycling. Here, we report a chemoenzymatic cascade that enables the simultaneous recycling and upcycling of PUR through rapid alkaline pretreatment followed by urethanase-catalyzed depolymerization. Using in-house-synthesized model polyether- and polyester-based PUR elastomers, we establish that soft-segment chemistry dictates the composition, morphology, and accessibility of the pretreated residues, thereby governing the efficiency of the subsequent enzymatic hydrolysis. This insight enabled translation of the cascade to a commercial PUR elastomer, achieving >93% chemical conversion and recovery of up to 1 mM 4,4′-methylenedianiline (MDA) (97.2% purity), corresponding to a 40-fold increase over the nonenzymatic control, together with polyols obtained in 95% isolated yield that were directly reused for PUR synthesis. Mechanistic studies further show that alkaline pretreatment enhances substrate accessibility for the enzyme, and structural analysis of urethanase SP2 reveals a carbamate-specific hydrogen-bonding interaction that promotes urethane hydrolysis while minimizing esterase activity. The cascade was additionally applied to highly crosslinked commercial PUR foams and adhesives, demonstrating its versatility toward industrially relevant waste streams. Overall, this work establishes a mechanistically informed chemoenzymatic platform for PUR depolymerization and provides a strategy for converting chemically recalcitrant PUR waste into reusable molecular building blocks.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"66 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Multiobjective Optimization of Synthetically Accessible Homogeneous Catalysts Reveals Tradeoffs for Methane-to-Methanol Conversion 合成可及均相催化剂的多目标优化揭示了甲烷转化为甲醇的权衡

IF 12.9 1区化学

ACS Catalysis Pub Date : 2026-10-19 DOI: 10.1021/acscatal.6c03365

Husain Adamji,Ilia Kevlishvili,David W. Kastner,Ralf Meyer,Yuriy Román-Leshkov,Heather J. Kulik

{"title":"Multiobjective Optimization of Synthetically Accessible Homogeneous Catalysts Reveals Tradeoffs for Methane-to-Methanol Conversion","authors":"Husain Adamji,Ilia Kevlishvili,David W. Kastner,Ralf Meyer,Yuriy Román-Leshkov,Heather J. Kulik","doi":"10.1021/acscatal.6c03365","DOIUrl":"https://doi.org/10.1021/acscatal.6c03365","url":null,"abstract":"The selective conversion of methane to methanol remains a major challenge in catalysis, and no earth-abundant homogeneous catalyst has been demonstrated to carry out this transformation with high turnover. To explore previously synthesized complexes that might be amenable for this transformation, we start from macrocyclic ligands from experimental structures in the Cambridge Structural Database. After expanding this set of ligands with Hammett-tuning functionalization, we construct a design space of 21.9 million Mn and Fe catalysts. We employ active learning using neural network surrogate models with quantified uncertainty to efficiently identify catalysts with optimal methane-to-methanol turnover. We do this by jointly optimizing density functional theory (DFT)-computed hydrogen atom transfer (HAT) and methyl radical rebound energetics. Square planar tetraaza-based macrocycles in combination with low-spin Fe(II) or Mn(II) emerge as a privileged class of transition metal complexes within the Pareto-optimal set, with Mn(II) catalysts exhibiting balanced energetic tradeoffs of the two steps. In contrast, porphyrin catalysts exhibit favorable HAT but unfavorable rebound, and seesaw catalysts, which are not widely employed, are indeed the least favorable in our set. Full reaction coordinate analysis of representative Pareto-optimal catalysts reveals that HAT and rebound thermodynamics no longer govern turnover, which is instead determined by the stability of the metal–oxo intermediate and the rebound kinetic barrier. Nonetheless, the resulting energetic spans for these catalysts remain competitive with known earth-abundant, methane-to-methanol catalysts, underscoring the effectiveness of active learning for discovering previously unexplored, synthetically accessible catalysts and unraveling catalyst design principles for methane-to-methanol reactivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"33 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218860","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Curvature-Induced Pentagonal Oxide Motif Governs Ethylene Epoxidation Selectivity on Silver Nanoparticles 曲率诱导的五边形氧化基序控制银纳米颗粒上乙烯环氧化的选择性

IF 12.9 1区化学

ACS Catalysis Pub Date : 2026-10-19 DOI: 10.1021/acscatal.6c05052

Si-Rui Zhan,Xian-Yang Zhang,Xin-Ping Wu,Xue-Qing Gong

{"title":"A Curvature-Induced Pentagonal Oxide Motif Governs Ethylene Epoxidation Selectivity on Silver Nanoparticles","authors":"Si-Rui Zhan,Xian-Yang Zhang,Xin-Ping Wu,Xue-Qing Gong","doi":"10.1021/acscatal.6c05052","DOIUrl":"https://doi.org/10.1021/acscatal.6c05052","url":null,"abstract":"Silver-catalyzed ethylene epoxidation is a cornerstone of the chemical industry, yet the operando surface structure of Ag nanoparticles and the identity of selectivity-governing active sites remain elusive. Here, we integrate machine learning potentials, stochastic surface walking global optimization, molecular dynamics simulation, and statistical analysis to resolve the surface landscape of Ag nanoparticles approaching experimentally relevant sizes under reaction conditions. Oxygen-induced reconstruction transforms pristine Ag facets into a globally amorphous oxide layer composed of three types of locally ordered ring motifs interspersed with structural defects. A pentagonal motif (ring5), topologically required to accommodate nanoparticle curvature and absent in conventional slab models, dominates the surface across all investigated particle sizes. Its recessed central Ag atom acts as an electronic charge buffer that weakens the critical C–Ag bond in the oxametallacycle intermediate, conferring high intrinsic ethylene oxide selectivity. Microkinetic analyses confirm that the oxygen species of ring5 regulate ethylene oxide yield, peaking at a nanoparticle oxidation degree of O/Ag ≈ 0.3–0.4. This work establishes a statistical paradigm for decoding active phases on realistic catalyst surfaces through dynamic structural ensembles.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"45 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218856","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Direct Amidination of Alkenes Via C–H Activation of Pyridinyl Formimidamide Synthon 碳-氢活化吡啶基甲米酰胺合成烯烃的直接酰胺化

IF 12.9 1区化学

ACS Catalysis Pub Date : 2026-10-19 DOI: 10.1021/acscatal.6c06650

Gao-Lei Song,Qing-Bo Zhang,Xia-Wei Xu,Yu-Rou Yang,Zhao-Guo Zhang,Fa-Jun Nan

{"title":"Direct Amidination of Alkenes Via C–H Activation of Pyridinyl Formimidamide Synthon","authors":"Gao-Lei Song,Qing-Bo Zhang,Xia-Wei Xu,Yu-Rou Yang,Zhao-Guo Zhang,Fa-Jun Nan","doi":"10.1021/acscatal.6c06650","DOIUrl":"https://doi.org/10.1021/acscatal.6c06650","url":null,"abstract":"Alkenes are among the most abundant and versatile feedstocks in synthetic chemistry, yet methods for their direct and regioselective conversion into nitrogen-containing frameworks remain scarce. In particular, the direct catalytic amidination of alkenes has remained underdeveloped. Herein, we report a rhodium-catalyzed anti-Markovnikov amidination of alkenes using a stable pyridinyl formimidamide synthon. This reaction enables the direct installation of amidine moieties onto a wide range of alkenes, including styrenes, aliphatic alkenes, and challenging internal alkenes that undergo efficient chain-walking with high regioselectivity and broad functional group tolerance, accommodating unprotected amines, phenols, and halides. The resulting pyridyl amidines can be readily transformed into amides, carboxylic acids and esters, establishing a practical platform for alkene diversification. Notably, late-stage functionalization of complex bioactive molecules, including cyclosporine A, FK506, and quinine etc., provides access to previously inaccessible analogues. Mechanistic investigations, highlighted by the crystallographic capture of a key rhodium–aminopyridinyl formimidamide intermediate, provide compelling evidence for the proposed catalytic cycle. Collectively, this work not only fills a critical gap in alkene functionalization but also offers a concise and general route to high-value nitrogen-containing architectures.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"56 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Direct Tunnel Channeling of Unstable Amino Aldehyde Intermediates Enables Stepwise Diamination in Transaminases 不稳定氨基醛中间体的直接隧道通道使转氨酶的逐步二聚成为可能

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-28 DOI: 10.1021/acscatal.6c06622

Mingzhe Ma, Meng Sun, Xiaoling Xu, Xianjie Fang

{"title":"Direct Tunnel Channeling of Unstable Amino Aldehyde Intermediates Enables Stepwise Diamination in Transaminases","authors":"Mingzhe Ma, Meng Sun, Xiaoling Xu, Xianjie Fang","doi":"10.1021/acscatal.6c06622","DOIUrl":"10.1021/acscatal.6c06622","url":null,"abstract":"Amino aldehyde intermediates exhibit extreme chemical lability, undergoing nonproductive cyclization and polymerization in bulk solvent at rates orders of magnitude faster than enzymatic recapture. This kinetic mismatch has posed a fundamental bottleneck for transaminase-mediated stepwise diamination. Here, we resolve this long-standing challenge by discovering a previously unrecognized trans-subunit tunnel within a homodimeric transaminase that directly channels the unstable amino aldehyde intermediate between the two pyridoxal-5′-phosphate (PLP) active sites, bypassing release and rebinding. Mechanism-guided semi-rational engineering of the trans-subunit tunnel in Shimia marina transaminase (SMTA) yielded the S122G/Y324N with 1.98-fold enhanced catalytic efficiency (kcat/KM) for the stepwise diamination of 2,5-diformylfuran (DFF) to bis(aminomethyl)furan (BAMF). Stopped-flow kinetics and molecular dynamics simulations revealed that the mutations shift the tunnel from a tight-binding locked state to a dynamic-transport regime, reducing steric hindrance and optimizing electrostatic guidance to accelerate inter-subunit intermediate transit. A whole-cell cascade converting renewable 5-hydroxymethylfurfural (5-HMF) to BAMF—a promising bio-based diamine for advanced polyamides—was subjected to techno-economic (TEA) and life cycle (LCA) analyses. Together, these findings establish tunnel engineering as a generalizable paradigm for sequential biocatalytic amination. This work provides a mechanism-driven blueprint for efficient transaminase-mediated stepwise diamination, enabling biocatalytic production of bio-based diamines from renewable feedstocks.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20751–20763"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Selective Nitrate-to-Nitrite Electroreduction on Ag/Au Core-Shell Nanocubes 银/金核壳纳米立方的选择性硝酸盐-亚硝酸盐电还原

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-07 DOI: 10.1021/acscatal.6c05278

Qingdian Liao, Renata Sechi, Jian Zhou, Elena L. Gubanova, Lewin Deville, Pantila Jührendt, Sebastian Sturm, Ludwig Maximilian Hanauske, Knut Müller-Caspary, Arghya Bhowmik, Elena V. Sturm, Heine Anton Hansen, Aliaksandr S. Bandarenka

{"title":"Selective Nitrate-to-Nitrite Electroreduction on Ag/Au Core-Shell Nanocubes","authors":"Qingdian Liao, Renata Sechi, Jian Zhou, Elena L. Gubanova, Lewin Deville, Pantila Jührendt, Sebastian Sturm, Ludwig Maximilian Hanauske, Knut Müller-Caspary, Arghya Bhowmik, Elena V. Sturm, Heine Anton Hansen, Aliaksandr S. Bandarenka","doi":"10.1021/acscatal.6c05278","DOIUrl":"10.1021/acscatal.6c05278","url":null,"abstract":"Electrochemical nitrate reduction (NO3RR) offers a promising route for the production of valuable fertilizers and nitrites (common food preservatives), yet the relevant active sites remain poorly defined. Here, we combine density functional theory (DFT) with operando electrochemical scanning tunneling microscopy (n-EC-STM) to analyze tunneling current noise and establish structure–activity relationships in Ag/Au(111) and Ag/Au(100) model systems. DFT calculations show that Ag overlayers strengthen nitrate adsorption relative to bare Au and facilitate the initial NO3* → NO2* step. The adsorption energetics depend on both the structure of the surface facet and adsorption geometry, with tridentate nitrate adsorption generally favored on Au(100)-based surfaces and more variable behavior on Au(111)-based surfaces. Experimentally, Ag-coated Au(111) and Au(100) exhibit strong coverage-dependent NO3RR activity, with maximum activity near completion of an Ag monolayer on both facets. AgML/Au(100) consistently outperforms AgML/Au(111). n-EC-STM identifies Ag(100)-like monolayer terraces as the dominant active sites for NO3RR, whereas adjacent Au sites remain inactive. The same design principle is reproduced in Au{100} nanocubes, where Ag5nm@Au43nm/C with a thinner Ag shell outperforms Ag11nm@Au43nm/C and Au43nm/C. Together, these results identify terrace-confined Ag monolayers on Au as the key active sites for the electrochemical nitrate reduction reaction and highlight the roles of strain, ligand presence, and electronic effects at the Ag/Au–electrolyte interface.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20404–20418"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

From Semiempirical Descriptors to Catalyst Discovery: Interpretable Machine Learning for Ethylene Polymerization 从半经验描述符到催化剂发现：乙烯聚合的可解释机器学习

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-06 DOI: 10.1021/acscatal.6c02331

Youcai Zhu, Yue Mu, Yongqing Li, Shu Yang, Xuping Luo, Xiaoke Shi, Li Sun, Zhen Liu, Yucai Cao

{"title":"From Semiempirical Descriptors to Catalyst Discovery: Interpretable Machine Learning for Ethylene Polymerization","authors":"Youcai Zhu, Yue Mu, Yongqing Li, Shu Yang, Xuping Luo, Xiaoke Shi, Li Sun, Zhen Liu, Yucai Cao","doi":"10.1021/acscatal.6c02331","DOIUrl":"10.1021/acscatal.6c02331","url":null,"abstract":"The discovery of high-performance ethylene polymerization catalysts remains challenging because catalytic behavior is governed by a complex interplay between ligand structure, conformational flexibility, and reaction conditions. Herein, we present a data-driven framework for catalyst discovery that integrates semiempirical descriptor engineering, interpretable machine learning, and DFT analysis. Using an automated workflow based on SMILES-derived structures, conformer sampling, and xTB/RDKit descriptors, chemically meaningful representations were constructed for a diverse set of Co- and Fe-based bis(imino)pyridyl catalysts. The resulting structure-condition models accurately predict catalytic activity, achieving an R2 of 0.86 with the optimized XGBoost model. Interpretable analysis establishes a local angular descriptor associated with the N-aryl substituent geometry as an important structural factor governing catalytic activity, which is further supported by DFT calculations. Guided by these insights, systematic ligand design establishes practical rules favoring reduced proximal steric congestion and electronically tunable ortho substituents, enabling the identification of promising Fe/Co catalyst candidates. This framework provides a general strategy for accelerating the rational discovery and design of homogeneous polymerization catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19889–19898"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Advanced Metal-Phthalocyanine-Based Catalysts with Enhanced Oxygen Reduction Reaction Activity for High-Performance Anion-Exchange Membrane Fuel Cells 高性能阴离子交换膜燃料电池氧还原反应活性增强的新型金属-酞菁基催化剂

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-26 DOI: 10.1021/acscatal.6c03312

John C. Douglin, Kosuke Ishibashi, Yutaro Hirai, Yasutaka Matsuo, Koji Suto, Pankaj Kumar, Maytal Caspary Toroker, Hiroshi Yabu, Dario R. Dekel

{"title":"Advanced Metal-Phthalocyanine-Based Catalysts with Enhanced Oxygen Reduction Reaction Activity for High-Performance Anion-Exchange Membrane Fuel Cells","authors":"John C. Douglin, Kosuke Ishibashi, Yutaro Hirai, Yasutaka Matsuo, Koji Suto, Pankaj Kumar, Maytal Caspary Toroker, Hiroshi Yabu, Dario R. Dekel","doi":"10.1021/acscatal.6c03312","DOIUrl":"10.1021/acscatal.6c03312","url":null,"abstract":"Metal phthalocyanine (MPc)-based catalysts offer a structurally tunable platform for the oxygen reduction reaction (ORR) in alkaline media, yet their application in anion-exchange membrane fuel cells (AEMFCs) has been limited by insufficient performance. Here, we report two iron tetra-azaphthalocyanine catalysts, AZ-FT-30 and AZ-FO-30, evaluated in AEMFCs. Both catalysts exhibit comparable electrochemical surface areas (∼156–158 m2 g–1), enabling isolation of intrinsic activity. AZ-FO-30 demonstrates better catalyst activity toward alkaline ORR and enhanced cathode performance, achieving a peak power density of 902 mW cm–2 under H2–O2 conditions, representing the highest reported value for MPc-based AEMFC cathodes to date. Notably, the AZ-FO-30-based cell sustains stable operation over 35 h at 400 mA cm–2 with a minimal voltage decay (2.4 mV h–1), demonstrating the capability of MPc systems to achieve extended device-level durability. Density functional theory calculations demonstrate that AZ-FO-30 exhibits the shortest Fe–O bond distance, indicative of the strongest OH adsorption at the Fe active site, a trend consistently observed with the model containing one explicit water molecule, confirming its good adsorption characteristics. These findings demonstrate that targeted modification of the phthalocyanine framework enables the development of high-performance and durable cathode materials for platinum-group metal-free AEMFCs.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19972–19984"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050265","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0