JACS AuPub Date : 2025-09-10eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c01074
Hao Zhao, Fernando Bresme
{"title":"Recrystallization Mechanisms of Aluminum and Aluminum Oxide Interfaces through Reactive Simulations.","authors":"Hao Zhao, Fernando Bresme","doi":"10.1021/jacsau.5c01074","DOIUrl":"10.1021/jacsau.5c01074","url":null,"abstract":"<p><p>Aluminum and alumina are essential materials used in various energy processes and devices. In this study, we conduct an atomic-level investigation into the microscopic mechanisms that govern the recrystallization (crystal growth from its melt) of aluminum and aluminum oxide interfaces. We utilize a reactive force field (ReaxFF) along with bond-orientational order parameters and unsupervised clustering algorithms to clarify the barrierless nature of the ultrafast metallic growth processes of aluminum. Our analysis provides valuable insights into the microscopic mechanisms that facilitate the incorporation of atoms into alumina, which is a crucial step in the crystal growth of this metal oxide. For the crystal growth of alumina we identify a sequential process where oxygen atoms first occupy lattice sites before aluminum atoms are integrated. This mechanism involves energy barriers that may explain the slow crystal growth rates reported in the crystallization of aluminum oxide. Furthermore, we report a significant correlation between the incorporation of oxygen into the crystal structure and the modification of the atomic charge. These findings enhance our understanding of the distinct crystallization behaviors of metals and metal oxide interfaces, offering microscopic insights for developing materials with improved performance characteristics.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4625-4635"},"PeriodicalIF":8.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458036/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
JACS AuPub Date : 2025-09-09eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c00602
Martin F Köllen, Maximilian G Schuh, Robin Kretschmer, Joshua Hesse, Dominik Schum, Junhong Chen, Annkathrin I Bohne, Dominik P Halter, Stephan A Sieber
{"title":"Generative Deep Learning Pipeline Yields Potent Gram-Negative Antibiotics.","authors":"Martin F Köllen, Maximilian G Schuh, Robin Kretschmer, Joshua Hesse, Dominik Schum, Junhong Chen, Annkathrin I Bohne, Dominik P Halter, Stephan A Sieber","doi":"10.1021/jacsau.5c00602","DOIUrl":"10.1021/jacsau.5c00602","url":null,"abstract":"<p><p>The escalating crisis of multiresistant bacteria demands the rapid discovery of novel antibiotics that transcend the limitations imposed by the biased chemical space of current libraries. To address this challenge, we introduce an innovative deep learning-driven pipeline for <i>de novo</i> antibiotic design. Our unique approach leverages a chemical language model to generate structurally unprecedented antibiotic candidates. The model was trained on a diverse chemical space of drug-like molecules and natural products. We then applied transfer learning using a data set of diverse antibiotic scaffolds to refine its generative capabilities. Using predictive modeling and expert curation, we prioritized the most promising compounds for synthesis. This pipeline identified a lead candidate with potent activity against methicillin-resistant <i>Staphylococcus aureus</i>. We then performed iterative refinement by synthesizing 40 derivatives of the lead compound. This effort produced a suite of active compounds, with 30 showing activity against <i>S. aureus</i> and 17 against <i>Escherichia coli</i>. Among these, lead compound <b>D8</b> exhibited remarkable submicromolar and single-digit micromolar potency against the aforementioned pathogens, respectively. Mechanistic investigations point to the reductive generation of reactive species as its primary mode of action. This work validates a deep-learning pipeline that explores chemical space to generate antibiotic candidates. This process yields a potent nitrofuran derivative and a set of experimentally validated scaffolds to seed future antibiotic development.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4249-4259"},"PeriodicalIF":8.7,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458054/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
JACS AuPub Date : 2025-09-08eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c00884
Damiano Diprima, Thomas Terp Paulsen, Antonio Pulcinella, Stefano Bonciolini, Alexis L Gabbey, Robin Stuhr, Thomas Bjørnskov Poulsen, Timothy Noël
{"title":"Modular Synthesis of Substituted Lactams via a Deoxygenative Photochemical Alkylation-Cyclization Cascade of Secondary Amides in Flow.","authors":"Damiano Diprima, Thomas Terp Paulsen, Antonio Pulcinella, Stefano Bonciolini, Alexis L Gabbey, Robin Stuhr, Thomas Bjørnskov Poulsen, Timothy Noël","doi":"10.1021/jacsau.5c00884","DOIUrl":"10.1021/jacsau.5c00884","url":null,"abstract":"<p><p>γ-Lactams are crucial scaffolds in many bioactive compounds and pharmaceutical agents, yet their synthesis featuring diverse γ- and <i>N</i>-substitution remains a significant synthetic challenge. Current methods often lack modularity and efficiency, particularly when targeting sterically hindered or highly functionalized analogues. Herein, we report a modular, three-step strategy for the systematic synthesis of γ- and <i>N</i>-substituted γ-lactams from readily available primary amines and carboxylic acids. The sequence includes deoxygenative activation of secondary amides using triflic anhydride, a photochemical silane-mediated radical alkylation, and intramolecular cyclization. The alkylation-lactamization cascade proceeds under additive-free, continuous-flow photochemical conditions, enabling rapid reaction times (20 min) and scalable operation. Compared to conventional <i>N</i>-alkylation approaches, this method broadens access to sterically hindered analogues and offers a valuable platform for medicinal chemistry applications.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4584-4592"},"PeriodicalIF":8.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458026/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152371","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
JACS AuPub Date : 2025-09-08eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c00842
Shengyang Cai, Jingwei Weng, Igor Ying Zhang, Yichun Zhu
{"title":"Unraveling the Catalytic Mechanism and Substrate Selectivity of HDAC10: A Dual-Filter Approach for Polyamine Deacetylation.","authors":"Shengyang Cai, Jingwei Weng, Igor Ying Zhang, Yichun Zhu","doi":"10.1021/jacsau.5c00842","DOIUrl":"10.1021/jacsau.5c00842","url":null,"abstract":"<p><p>The histone deacetylase (HDAC) family plays a crucial role in regulating acetylation-dependent cellular processes, with dysregulation linked to diseases ranging from cancer to neurodegeneration. HDAC10, the sole polyamine deacetylase in the HDAC family, uniquely influences pathologies such as tumor immunity, autophagy, inflammation, virus infection, silicosis, <i>etc</i>. Despite its therapeutic potential, the molecular basis of HDAC10's catalytic activity and substrate selectivity remains poorly understood, hindering rational drug design. Here, we address this gap by integrating density functional theory (DFT) and molecular dynamics simulation to systematically investigate HDAC10's catalytic activity and substrate selectivity. Utilizing a 330-atom quantum cluster model, we evaluated five distinct reaction pathways. The double-proton transfer mechanism (D'D) is dominant, featuring a concerted double-proton transfer step and a rate-limiting protonation of the substrate's amide nitrogen (20.4 kcal/mol barrier). Substrate selectivity arises from synergistic effects: <i>N</i> <sup>8</sup>-acetylspermidine benefits from enhanced binding <i>via</i> active-site hydrogen-bond networks and reduced catalytic barriers compared to <i>N</i> <sup>1</sup>-acetylspermidine, which suffers from electrostatic repulsion and dynamic instability. This study provides the first atomic-resolution framework for HDAC10's catalysis and selectivity, resolving long-standing mechanistic ambiguities. By identifying critical interactions governing substrate recognition and turnover, our work establishes a foundation for designing isoform-specific HDAC10 inhibitors, offering strategic avenues to target its roles in disease.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4491-4505"},"PeriodicalIF":8.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458008/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152515","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
JACS AuPub Date : 2025-09-06eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c00898
Yuting Luo, Kang Li, Pu Wang, Yong Pei
{"title":"Structural Flexibility-Driven Dual Emission Switching in Ultrathin Gold Nanorod Clusters.","authors":"Yuting Luo, Kang Li, Pu Wang, Yong Pei","doi":"10.1021/jacsau.5c00898","DOIUrl":"10.1021/jacsau.5c00898","url":null,"abstract":"<p><p>Recently, the unique dual emission phenomena of gold nanoclusters (AuNCs) have been reported, but the relationship between their emission characteristics and cluster structure and size remains unclear. This study focuses on atomically precise one-dimensional (1D) ultrathin rod-shaped AuNC systems (<b>Au<sub>24</sub></b> , <b>Au<sub>42</sub></b> , and <b>Au<sub>60</sub></b> ), revealing the structure-size dependency of their dual emission mechanisms using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The results show that as the aspect ratio (AR) increases (from 3.1 to 6.2 to 9.4), the core structure transitions from flexible to rigid, with enhanced <i>x</i>-axis transition dipole moments (<i>μ</i> <sub><i>x</i></sub> , from 0.58 or 1.00 to 6.31 and then to 10.73 D), narrowing the adiabatic energy gap (Δ<i>E</i> <sub>ST</sub>) between singlet (S<sub>1</sub>) and triplet (T<sub>1</sub>) states (from 0.50 or 0.81 eV to 0.37-0.57 eV). This leads to elevated fluorescence radiative rate constants (<i>k</i> <sub>r</sub> <sup>F</sup>) and intersystem crossing rate constants (<i>k</i> <sub>ISC</sub>) in the 10<sup>8</sup> s<sup>-1</sup> regime. Consequently, shorter clusters exhibit dual fluorescence emission (<i>F</i>1+<i>F</i>2), while elongated systems show fluorescence-phosphorescence dual emission (<i>F</i> + <i>P</i>). Electronic structure analysis reveals that increased size weakens charge transfer excitation while enhancing excited state localization. This work establishes a quantitative framework linking size, flexibility, and dual emission mechanisms in anisotropic AuNCs, offering design principles for tunable dual emission probes in optical imaging and sensing applications.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4593-4603"},"PeriodicalIF":8.7,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458031/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152517","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
JACS AuPub Date : 2025-09-05eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c00855
Chao Zhang, Linjie Chen, Jin Zhao, Hrvoje Petek
{"title":"An Atomic-Scale Mechanism of Potassium-Oxygen Redox Chemistry.","authors":"Chao Zhang, Linjie Chen, Jin Zhao, Hrvoje Petek","doi":"10.1021/jacsau.5c00855","DOIUrl":"10.1021/jacsau.5c00855","url":null,"abstract":"<p><p>The interaction between K atoms and oxygen molecules on solid surfaces is of topical interest to oxidation-reduction processes in K-O<sub>2</sub> batteries. Alkali metals have one <i>ns</i> electron in their valence shell, making them highly chemically reactive toward oxidizing reactants. Mechanistic information on the oxygen reduction by K at the atomic level is scarce despite its key role in defining the alkali metal-O<sub>2</sub> battery performance. Here, we use scanning tunneling microscopy and density functional theory to investigate the reduction of a single oxygen molecule by K atoms codeposited on the Ag(111) surface. Our study provides fundamental chemical information on the binary and collective interactions between the O<sub>2</sub> and K atoms on metal surfaces.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4530-4538"},"PeriodicalIF":8.7,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458050/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
JACS AuPub Date : 2025-09-05eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c00748
Dulce M Sánchez-Cerrillo, Kouichi Shiraishi, Lucía Mallen-Huertas, Remi Peters, Daniela A Wilson, Kevin Neumann
{"title":"Introducing Sulfur Ylides as Charge-Neutral Termini for Mitigating Poly(ethylene glycol) Antigenicity in Nanomedicine.","authors":"Dulce M Sánchez-Cerrillo, Kouichi Shiraishi, Lucía Mallen-Huertas, Remi Peters, Daniela A Wilson, Kevin Neumann","doi":"10.1021/jacsau.5c00748","DOIUrl":"10.1021/jacsau.5c00748","url":null,"abstract":"<p><p>The widespread use of polyethylene glycol (PEG) in biomedical applications has led to the emergence of anti-PEG antibodies, which accelerate systemic clearance and undermine the performance of PEGylated systems, including those of nanomedicines. Antibody recognition often involves the hydrophobic PEG terminus, highlighting the need for alternative end-functionalization strategies that enhance hydrophilicity while maintaining stealth properties. Here, we introduce a novel PEGylation concept using sulfur ylides bearing tri- and pentapeptides as terminal modifications. These ylide-PEG (yPEG) conjugates were integrated into polymeric nanoparticles as a model system, demonstrating that ylide functionalization maintains key physicochemical properties, such as ζ-potential and antifouling behavior. Crucially, antibody binding assays with monoclonal IgM and IgG anti-PEG antibodies revealed that the ylide terminus significantly reduces recognition by both main chain- and terminus-specific anti-PEG antibodies. Experiments with polyclonal anti-PEG antibodies from mPEG-immunized mice suggest that increasing the chemical complexity of the PEG terminus with a strongly hydrophilic yet overall charge-neutral group effectively prevents antigenicity from extending to the terminus, ultimately reducing PEG-specific recognition. This modular and scalable strategy of yPEGs offers a new paradigm for engineering stealth-functionalized polymers with broad implications for nanomedicine, biomaterials, and surface coatings.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4378-4388"},"PeriodicalIF":8.7,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12457994/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
JACS AuPub Date : 2025-09-04eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c00694
Richard M Meade, Scott G Allen, Amy J Lopez, Christopher Williams, Iona Thomas-Wright, Rachel Heon-Roberts, Mara Carey-Wood, T M Simon Tang, Julia E Sero, Vicky L Hunt, Richard Wade-Martins, Matthew P Crump, Jody M Mason
{"title":"Stabilizing a Native Fold of Alpha-Synuclein with Short Helix-Constrained Peptides.","authors":"Richard M Meade, Scott G Allen, Amy J Lopez, Christopher Williams, Iona Thomas-Wright, Rachel Heon-Roberts, Mara Carey-Wood, T M Simon Tang, Julia E Sero, Vicky L Hunt, Richard Wade-Martins, Matthew P Crump, Jody M Mason","doi":"10.1021/jacsau.5c00694","DOIUrl":"10.1021/jacsau.5c00694","url":null,"abstract":"<p><p>Preventing the aggregation of α-synuclein (αS) into toxic oligomers and conformers is a major therapeutic goal in conditions such as Parkinson's disease and Lewy body dementia. However, the large intracellular protein-protein interfaces within such aggregates make this a challenging target for small molecule approaches or biologics, which often lack cell permeability. Peptides occupy a suitable middle ground and are increasingly being explored as preventative treatments. We previously showed that the N-terminal lipid binding region (αS<sub>1-25</sub>) inhibits αS aggregation. Building on this, we designed a series of N- and C-terminal truncations to systematically reduce the peptide length, enabling a 56% downsizing (i.e., truncating 92% of the full-length αS protein), to identify the smallest functional unit capable of binding αS and potently blocking its aggregation and toxicity. We next introduced seven systematic i → i + 4 helix constraints to assess impact on (i) α-helicity, (ii) aggregation inhibition, (iii) serum stability, (iv) neuronal uptake, and (v) phenotypic rescue. This work maps key amphipathic features and identifies residues that are critical for αS engagement and inhibitory activity. The most effective helix-constrained peptide, αS<sub>2-12</sub>(L6), showed marked improvements across all metrics and represents a strong candidate for further therapeutic development.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4321-4336"},"PeriodicalIF":8.7,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458024/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152496","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
JACS AuPub Date : 2025-09-04eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c00769
Giselle Castano, Remy Dou, Ngan Linh, Nadya Mohammed, Andrea Lopez, Sonia M Underwood
{"title":"Identity Development in Chemistry: The Social Functionality and Moral Significance of Being (Considered) a \"Real\" Chemist.","authors":"Giselle Castano, Remy Dou, Ngan Linh, Nadya Mohammed, Andrea Lopez, Sonia M Underwood","doi":"10.1021/jacsau.5c00769","DOIUrl":"10.1021/jacsau.5c00769","url":null,"abstract":"<p><p>As chemistry expands across interdisciplinary boundaries and diverse career sectors, examining how professional identity is constructed becomes crucial for understanding field dynamics and career development patterns. This study investigates how individuals at various levels of education and professional careers in chemistry define and describe chemistry identity. Using semistructured interviews with undergraduate students and chemistry professionals across academic, industry, and government job sectors, we investigated the ways participants (<i>N</i> = 43) described and characterized a chemist or a \"chemistry person,\" including how this characterization influenced self-identification and evaluation of others in the field. Drawing on Social Identity Theory, our analysis reveals that there is a notion of a \"true\" or more \"legitimate\" chemist within the community based on a \"pure chemist\" stereotype, which is characterized by having a chemistry degree, conducting research in academia, and doing molecular-level work. In practice, this means that there are groups within the community excluded, including biochemists, chemical engineers, chemistry education researchers, and chemists in industry, based on ideals of \"academic purity\" that privilege and reserve rigor only to certain chemistry subdisciplines and job sectors. The results indicate a basic tension between the characterization of chemistry as the \"central science,\" and the increasingly bounded identity practices that limit impositions of interdisciplinary views. Deeper examination of our data reflects how chemistry identity is constructed within practices of morality that place \"pure\" chemistry at the top, while systematically marginalizing those who work across disciplinary lines. These exclusionary practices continue, as they are framed to be maintaining scientific integrity, and not bias, making them difficult to challenge while also creating sustained problems for diversity and retention in the field.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4408-4426"},"PeriodicalIF":8.7,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458046/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
JACS AuPub Date : 2025-09-04eCollection Date: 2025-09-22DOI: 10.1021/jacsau.5c00887
Eunwon Lee, Jongchan Bu, Sungha Hwang, Jinu Choi, Hyeongdong Jung, Yongwoo Kim, Hyokyoung Lee, Chang Hwan Kim, Jong Suk Yoo, Do Heui Kim
{"title":"Effects of Pd/CeO<sub>2</sub> on the Abatement of Unburnt Hydrocarbon Emissions from Gasoline Vehicles during the Cold-Start Period.","authors":"Eunwon Lee, Jongchan Bu, Sungha Hwang, Jinu Choi, Hyeongdong Jung, Yongwoo Kim, Hyokyoung Lee, Chang Hwan Kim, Jong Suk Yoo, Do Heui Kim","doi":"10.1021/jacsau.5c00887","DOIUrl":"10.1021/jacsau.5c00887","url":null,"abstract":"<p><p>Unburnt hydrocarbon emissions from gasoline vehicles contribute to air pollution and pose health risks, necessitating effective removal strategies. Conventional three-way catalysts (TWCs) effectively oxidize hydrocarbons to CO<sub>2</sub> at temperatures above 250 °C. However, the increasing adoption of turbocharged gasoline engines, which emit exhaust gases at significantly lower temperatures (∼300 °C versus ∼ 800 °C in conventional vehicles), has renewed concerns over hydrocarbon emissions. The primary challenge is the prolonged warm-up time of catalytic converters, during which TWCs remain largely ineffective. To address this, we developed a dual-function Pd/CeO<sub>2</sub> catalyst capable of retaining unburnt hydrocarbons through adsorption during cold start and promoting their oxidation at elevated temperatures. Propylene (C<sub>3</sub>H<sub>6</sub>), a representative short-chain olefin in gasoline exhaust, was used as a probe molecule to evaluate the catalyst's hydrocarbon abatement performance under realistic conditions. Periodic density functional theory calculations were conducted to investigate and compare C<sub>3</sub>H<sub>6</sub> oxidation pathways on pure Pd and the Pd-CeO<sub>2</sub> interface. O<sub>2</sub> dissociation was identified as the most kinetically hindered step on pure Pd, whereas OH* formation was the rate-limiting step at the Pd-CeO<sub>2</sub> interface. Consequently, the Pd surface exhibits sluggish oxidation activity, whereas the interface is prone to O-poisoning, which suppresses catalytic turnover. Interestingly, the coexistence of pure Pd and Pd-CeO<sub>2</sub> sites induces a synergistic effect mediated by intermediate spillover, which significantly enhances C<sub>3</sub>H<sub>6</sub> oxidation. Considering the simultaneous emission of C<sub>3</sub>H<sub>6</sub> and NO in gasoline exhaust, we also investigated their interaction and found a mutual inhibitory effect, with NO more strongly suppressing C<sub>3</sub>H<sub>6</sub> oxidation. This suppression is linked to high NO <sub><i>x</i></sub> * coverage at the Pd-CeO<sub>2</sub> interface, which hinders O* diffusion to the Pd surface. Our work reveals the mechanistic basis of Pd/CeO<sub>2</sub>'s dual functionality and offers a framework for designing TWCs effective at hydrocarbon abatement during cold-start in modern gasoline engines.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4570-4583"},"PeriodicalIF":8.7,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458003/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145152424","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}