ACS Catalysis 最新文献

{"title":"Defluorination of Fluorophenols by a Heme Dehaloperoxidase: Insights into the Defluorination Mechanism","authors":"Yi Zhang, Yuanxin Cao, Chivukula V. Sastri, Sam P. de Visser","doi":"10.1021/acscatal.4c07865","DOIUrl":"https://doi.org/10.1021/acscatal.4c07865","url":null,"abstract":"Fluorinated compounds are extensively used in industry and materials science due to their high stability and physical properties, however, they are poorly biodegradable and lead to environmental accumulation. In this work, we explore heme dehaloperoxidases for the defluorination of fluorinated aromatic compounds. Heme dehaloperoxidases are efficient enzymes that utilize H₂O₂ on a heme-active site to dehalogenate aromatic compounds. They usually operate by dechlorination or debromination, but recent evidence suggests defluorination is also possible; however, details of the mechanism are elusive and remain controversial. To establish the mechanism and feasibility of aromatic defluorination by dehaloperoxidase enzymes for environmental remediation and particularly the detoxification of fluorinated compounds, we performed detailed molecular dynamics (MD) and quantum mechanics studies. A complete enzyme model was created based on the dehaloperoxidase crystal structure and several fluorinated arenes were inserted. Despite the fact that the substrate binding pocket and heme active site are solvent-exposed, actually during the MD simulation, the substrates are locked inside the substrate-binding pocket through tight hydrogen bonding interactions and π-stacking interactions with amino acid residues, including several Phe amino acids and the Tyr₃₈ and His₅₅ side chains. We then created a large cluster model of 324 atoms of a Compound I model with 2,4,6-trifluorophenol bound and included the second-coordination sphere and studied the oxygen activation and defluorination reaction of the substrate via several possible reaction pathways. The calculations reveal a mechanism that starts with a hydrogen atom abstraction from the phenol group followed by OH rebound to the <i>ortho</i>- or <i>para</i>-positions to form 2,4,6-trifluoro-4-hydroxycyclohexadienone and 2,4,6-trifluoro-6-hydroxycyclohexadienone. These products either react inside the protein with the assistance of a proton by fluorine release or escape into the solution where the defluorination happens and the final benzoquinone products are formed. The calculations show that the hydrogen atom abstraction and OH rebound steps have small free energies of activation of &lt;Δ<i>G</i> = 10 kcal mol^–1, while the defluorination is rate-determining. Consequently, our studies predict that heme haloperoxidases have the potential for environmental remediation of fluorophenols from water, although a mixture of <i>ortho</i>- and <i>para</i>-activation will occur.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451571","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":"Discovery of Carbon Reduction Reaction","authors":"Hongyuan Chuai, Weiping Huang, Sheng Zhang","doi":"10.1021/acscatal.4c07793","DOIUrl":"https://doi.org/10.1021/acscatal.4c07793","url":null,"abstract":"High-carbon chemicals, as significant raw materials in the petrochemical industry, possess a tremendous economic value. In a recent breakthrough, we report the synthesis of high-carbon chemicals via the carbon reduction reaction (CRR) under ambient conditions, a departure from conventional thermocatalytic methods that require high temperatures and pressures. Our electrocatalysis study revealed that the carbon membrane electrode was transformed into long-chain hydrocarbons, predominantly C16–C44, with a 40% selectivity for C₄₄H₉₀ after long-term electrolysis. Further investigation indicated that the CRR process was universal, as we achieved the production of high-carbon chemicals (18–35 carbons, with a selectivity of 50% for C₁₈H₃₃N) using biomass-derived carbon. This discovery not only offers a novel approach for the utilization of carbon-containing waste such as biomass and plastics but also establishes a mild and sustainable route for synthesizing high-carbon chemicals through the electroreforming of carbon materials.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"98 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451529","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":"Cobalt-Catalyzed Enantioselective Desymmetrization and Chemodivergent Parallel Kinetic Resolution of Unsaturated Substrates via C(sp3)–H Bond Activation","authors":"Keiji Yamada, Ryo Hashiyama, Takeshi Yasui, Yoshihiko Yamamoto","doi":"10.1021/acscatal.5c00132","DOIUrl":"https://doi.org/10.1021/acscatal.5c00132","url":null,"abstract":"In transition-metal-mediated chemical transformations, chemoselective or chemodivergent activation of inert C–H bonds in the presence of more reactive alkene or alkyne π-bonds is a fundamental challenge. Herein, we report the Co-catalyzed cycloisomerization of unsaturated substrates bearing a 1,6-diyne moiety via enantioselective desymmetrization and parallel kinetic resolution involving the chemoselective and chemodivergent activation of a C(sp³)–H bond. The enantioselective desymmetrization of symmetrical dienediynes was demonstrated using a 1,1′-binaphthyl-based chiral phosphine ligand to afford the corresponding enantioenriched 1,3-diene products. The parallel kinetic resolution of unsymmetrical substrates such as enetriynes, dienediynes, and diynenitriles was also demonstrated, where the chemodivergent activation of a C(sp³)–H bond and an alkene, alkyne, or nitrile π-bond was achieved. The 1,3-diene products were successfully derivatized to 5–8–5 tricyclic compounds via a central-to-helical-to-central chirality transfer involving memory of chirality.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451581","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":"A Comprehensive Theoretical Study of the Mechanism for Dry Reforming of Methane on a Ni4/ZrO2(101) Catalyst Under External Electric Fields: The Role of Interface and Oxygen Vacancy","authors":"Hui Jiao, Gui-Chang Wang","doi":"10.1021/acscatal.4c05758","DOIUrl":"https://doi.org/10.1021/acscatal.4c05758","url":null,"abstract":"Although dry reforming of methane (DRM) reactions is advantageous in environmental and economic aspects, they still face the challenge of catalyst deactivation caused by carbon deposition. Metal-supported catalysts exhibit high activity and stability in DRM reactions due to the ability of strong metal–support interaction (SMSI) to highly disperse Ni nanoparticles and unique interface active sites. Moreover, the external electric field has a significant effect on DRM. Herein, the mechanisms of the DRM reaction on the Ni₄/ZrO₂(101) catalyst under different electric fields were comprehensively investigated using density functional theory (DFT) and microkinetic modeling to better understand the importance of metal-support interfaces and oxygen vacancies in catalysis. The results indicated that the electric fields weaken the interaction between Ni₄ clusters and ZrO₂(101). Species are more easily adsorbed and activated at the interface than at only Ni sites. The negative electric fields enhanced CO₂ activation, while the positive electric fields promoted methane activation and CH_<i>x</i> oxidation, at either the interface or Ni sites. Oxygen vacancies were generated on the Ni₄/ZrO₂ catalysts by H spillover to form water and were facilitated by negative electric fields. The interface and oxygen vacancies significantly enhance DRM reaction activity and reduce carbon deposition. The surface adsorption dipole moment reflects the tendency of the adsorption strength and reaction enthalpy to change with the electric fields. The microkinetic results showed that carbon deposition is easily formed on the Ni₄ cluster, with CH–CH being the predominant type of carbon deposition. Fortunately, the DRM reaction exhibits high reactant conversion under the synergistic effect of Ni clusters and the Zr interface. In addition, oxygen vacancies promote CO₂ activation, thereby reducing carbon deposition and enhancing DRM reaction activity, especially with the application of a negative electric field. The positive electric field has the highest DRM reaction activity on Ni₄/ZrO₂, accompanied by more carbon deposition. Importantly, the negative electric field combines high activity and anticarbon deposition properties. Our results are highly consistent with the experiment. This work emphasizes the importance of interfaces and oxygen vacancies, providing theoretical foundations for a deeper understanding of DRM reaction mechanisms and research in the area of electric- field catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"85 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443857","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":"Nonclassical Nonlinear Effects (nc-NLEs) Provide Mechanistic Insights in Asymmetric Catalytic Cascade Reactions","authors":"Jinhan Yu, Donna G. Blackmond","doi":"10.1021/acscatal.5c00220","DOIUrl":"https://doi.org/10.1021/acscatal.5c00220","url":null,"abstract":"The observation of a nonlinear relationship between product enantiomeric excess and catalyst enantiopurity has become a key tool to probe catalyst active species and reaction mechanisms in asymmetric catalysis. While the phenomenon has primarily been attributed to the involvement of dimeric catalyst species either on or off the catalytic cycle, or to bimolecular reactions between two monomeric catalyst species, a growing body of evidence points to cases in complex reaction networks where the phenomenon cannot be explained by classical nonlinear effect (NLE) models involving higher-order catalyst species. We highlight examples of organocatalytic cascade reaction sequences setting multiple stereocenters where an observation of either a positive or a negative NLE is rationalized without invoking catalyst aggregation or dual-catalyst activation. A general model is developed here for nonclassical NLEs (nc-NLE) observed in parallel-consecutive catalytic networks involving intermediate products that disengage and then re-engage with the catalyst in a further catalytic cycle. These models may provide insights that cannot be understood by treating the system as a simple, single catalytic cycle. The mechanistic understanding afforded by studying these systems may help to inform catalyst and reaction design in reaction networks whose complexity begins to mimic metabolic systems in biology.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451576","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":"Visible-Light-Driven Catalytic Dehalogenation of Trichloroacetic Acid and α-Halocarbonyl Compounds: Multiple Roles of Copper","authors":"Abigail J. Thillman, Erin C. Kill, Alexander N. Erickson, Dian Wang","doi":"10.1021/acscatal.4c07845","DOIUrl":"https://doi.org/10.1021/acscatal.4c07845","url":null,"abstract":"Herein, we report the reaction development and mechanistic studies of visible-light-driven Cu-catalyzed dechlorination of trichloroacetic acid for the highly selective formation of monochloroacetic acid. Visible-light-driven transition metal catalysis via an inner-sphere pathway features the dual roles of transition metal species in photoexcitation and substrate activation steps, and a detailed mechanistic understanding of their roles is crucial for the further development of light-driven catalysis. This catalytic method, which features environmentally desired ascorbic acid as the hydrogen atom source and water/ethanol as the solvent, can be further applied to the dehalogenation of a variety of halocarboxylic acids and amides. Spectroscopic, X-ray crystallographic, and kinetic studies have revealed the detailed mechanism of the roles of copper in photoexcitation, thermal activation of the first C–Cl bond, and excited-state activation of the second C–Cl bond via excited-state chlorine atom transfer.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"25 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451530","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":"Solving the Conundrum of the Influence of Irradiation Power on Photothermal CO2 Hydrogenation","authors":"Horatiu Szalad, Yong Peng, Jonas Werner Gosch, Andrea Baldi, Sven H. C. Askes, Josep Albero, Hermenegildo García","doi":"10.1021/acscatal.5c00247","DOIUrl":"https://doi.org/10.1021/acscatal.5c00247","url":null,"abstract":"Solar photocatalysis appears as a viable approach for the production of value-added chemicals from CO₂. However, up to now, there is no information on the influence of the light intensity on the product distribution of CO₂ hydrogenation and the modeling of the actual local temperature at the catalytic sites for typical nanoparticulate photocatalysts. Herein, it is shown that for a photothermal catalyst containing a high density of homogeneously distributed Ru nanoparticles, the collective heating prevails, resulting in a homogeneous temperature distribution in the material that should be relatively close to that of the support and that can be measured macroscopically. Moreover, light intensity has a clear influence on product distribution due to the differences in the local temperature, and therefore, attention should be paid to stable operating conditions, temperature, and CO₂ conversion that can result in remarkable differences in product selectivity for the same catalyst as a function of light intensity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"13 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443887","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":"Atomically Dispersed Sn Catalysts toward Selective Oxidation of Furfural to Biodegradable Polymer Monomers","authors":"Zhen Ren, Luyao Yu, Xin Song, Si Wang, Haolin Li, Lei Wang, Xin Zhang, Xiangcheng Li, Yusen Yang, Zhendong Wang, Min Wei","doi":"10.1021/acscatal.5c00068","DOIUrl":"https://doi.org/10.1021/acscatal.5c00068","url":null,"abstract":"Succinic acid, an important building block in the polymer industry, is conventionally obtained from fossil resources; its manufacture from renewable biomass provides a promising route but remains a significant challenge. Herein, we report a Sn-doped NiO catalyst prepared via a calcination and deposition–precipitation method, which is featured with atomically dispersed Sn atoms anchored onto NiO support. The resulting 1.1 wt % Sn–NiO catalyst exhibits a satisfactory catalytic performance toward furfural oxidation to succinic acid (conversion: &gt;99%; selectivity: 91.2%) using H₂O₂ as the oxidant, which is superior to other metal oxide catalysts ever reported. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption fine structure and X-ray photoelectron spectroscopy analyses confirm that the Sn species show an atomic dispersion on the surface of NiO with local electron transfer from Sn to Ni. Both spectroscopy experiment investigations and theoretical calculations verify that the synergistic effect of bimetallic sites (Sn–O–Ni) is of pivotal importance in promoting the activated adsorption of reactants and the occurrence of the reaction: H₂O₂ undergoes dissociation to generate hydroxyl radicals at the Sn site while the C═O and C–O bonds in the furan ring experience oxidative decarboxylation and a ring-opening reaction at the Ni site adjacent to Sn. This work not only provides an efficient catalyst toward selective oxidation of furfural to succinic acid but also demonstrates a beneficial route to produce biodegradable polyester monomers from biomass resource.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"64 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435397","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":"Trace of Atomically Dispersed Pd Enables Unprecedented Butadiene Semihydrogenation Performance Over Copper Catalyst","authors":"Zhao Wang, Hao Yuan, Jian Tao, Shu-Lin Liu, Ying Hong, Zhi-Yi Hu, Jian Zhang, Bao-Lian Su","doi":"10.1021/acscatal.4c05528","DOIUrl":"https://doi.org/10.1021/acscatal.4c05528","url":null,"abstract":"Semihydrogenation plays a key role in industrial hydrorefining of light alkenes, with a market above 400 billion by 2027. The high cost of commercial palladium-based catalysts strongly calls for innovation but with great challenges. Herein, copper nanoparticles decorated with a minimized ppm of Pd are developed through a chemical plating process to integrate the catalytic advantages of copper and palladium for achieving maximized catalysis in the semihydrogenation of a fatal impurity of butadiene in alkene feedstocks. The developed Pd–Cu catalyst (i.e., 114 ppm of Pd in Pd_0.0033Cu₁/TiO₂) exhibits an unprecedented catalytic performance superior to commercial Pd/Al₂O₃, with 100% butene selectivity above 90% of butadiene conversion over 130 h on stream at 90 °C. Further exploration reveals that the atomically dispersed Pd on Cu nanoparticles, obtained at ultralow ppm levels of Pd loading, induces a hidden but critical H₂ trap, which concentrates H₂ on the Pd site for further H₂ dissociation that offers intermediate hydrogen atoms to the tandem butadiene semihydrogenation over the third layer of Cu atoms neighboring Pd through hydrogen spillover. Moreover, a threshold on Pd density was identified at Pd/Cu surficial atomic ratio of 1/138 (i.e., Pd_0.0033Cu₁/TiO₂) for maximizing butadiene semihydrogenation performance, based on an extreme collaboration between Pd for H₂ dissociation and Cu for butadiene hydrogenation. This work provides important guidance for developing noble metal-saving catalysts in industrial applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"49 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435393","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":"Direct Synthesis of Hexa-peri-hexabenzocoronene on Au(111) Surfaces: Insights into Intramolecular Dehydrocyclization and Molecular Modification Strategies","authors":"Yuying Wang, Hailong Li, Lina Wang, Tianyu Gao, Haiming Zhang, Klaus Müllen, Miao Xie, William A. Goddard, III, Lifeng Chi","doi":"10.1021/acscatal.4c06226","DOIUrl":"https://doi.org/10.1021/acscatal.4c06226","url":null,"abstract":"Polycyclic aromatic hydrocarbons (PAHs) are widely used in materials science, optoelectronic devices, and supramolecular chemistry because of their unique extended π-conjugated structures. Among numerous PAHs, hexa-peri-hexabenzocoronene (HBC) is a prominent representative of the all-benzene structural building blocks. The synthesis of HBC using hexaphenylbenzene (HPB) is considered the most direct approach, requiring only intramolecular dehydrocyclization. In this study, we calculated the complete reaction pathway for the formation of HBC molecules from HPB molecules on the Au(111) surface. Our study revealed that HBC is formed by sequential phenyl coupling reactions with a maximum energy barrier of 1.86 eV. We also obtained the surface properties of the HPB and HBC molecules, including their charge distributions, migration barriers, and molecular aromaticity. Furthermore, using a 1,2-dibenzobenzene (DBB) model, we introduced para-position electron donor/withdrawing groups to regulate the phenyl coupling reaction. The results showed that this strategy effectively reduces the reaction barrier with electron-donating groups having a more pronounced effect. Our research reveals the influence of functional groups on molecular electronic properties and provides theoretical insights for the design of precursor molecules and surface synthesis strategies.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"80 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435362","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}