ACS Catalysis 最新文献

{"title":"Developing Dual-Atom Catalysts with Tunable Electron Synergistic Effect via Photoinduced Ligand Exchange Strategy","authors":"Yamei Pang, Xu Zhang, Pengfei Li, Guang-Jie Xia, Xupeng Zong, Yichang Liu, Dan Qu, Kun Zheng, Li An, Xiayan Wang, Zaicheng Sun","doi":"10.1021/acscatal.4c06059","DOIUrl":"https://doi.org/10.1021/acscatal.4c06059","url":null,"abstract":"Dual-atom catalysts (DACs) are promising for various catalytic reactions. However, synthesis challenges have hindered their development. Herein, we propose a universal approach using photoinduced ligand exchange (PILE) to create DACs with high proportions of dual-atom pairs, fixed interatomic distances, and tunable metal ratios and types. By cocrystallizing two metal acetylacetonates on graphitic carbon nitride (CN) nanosheets, the metal types and ratios in DACs can be precisely controlled. Remarkably, over 90% of dual-atom pairs follow the metal atom distances of 2.4 and 7.3 Å. During the photocatalytic H₂ production, the heteronuclear DAC (Pt₁Pd₂/CN) delivers a performance of ∼15.9 mmol·g^–1·h^–1 under AM1.5 light irradiation due to the electron synergistic effect, which overperforms not only the single-atom catalysts (Pt/CN and Pd/CN) but also the homonuclear DACs (PtPt/CN and PdPd/CN). X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge structure (XANES), and density functional theory (DFT) calculations reveal that Pt draws electrons from Pd, modulating its charge state, lowering the d-orbital center and approaching the more proper H adsorption free energy, thereby enhancing H₂ production. As a pioneering strategy, PILE offers a straightforward and powerful route to synthesize both homonuclear and heteronuclear DACs, holding immense promise for revolutionizing a broad spectrum of catalytic applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917845","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":"Boosting the Water Gas Shift Reaction Rate on Au Nanocatalysts through Collaborative Synthesis of Warm and Cold Plasmas","authors":"Ye-Cheng Li, Xiao-Song Li, Jing-Lin Liu, Bin Zhu, Guanghui Zhang, Dongdong Liu, Wei Liu, Xinwen Guo, Ai-Min Zhu","doi":"10.1021/acscatal.4c05657","DOIUrl":"https://doi.org/10.1021/acscatal.4c05657","url":null,"abstract":"TiO₂-supported Au nanocatalysts are highly attractive for the water gas shift (WGS) reaction due to their high catalytic activity at low temperatures. Herein, the (Au/TiO_2–<i>x</i>)_OP catalyst synthesized by the combination of warm and cold plasmas exhibits a high WGS reaction rate of 1.63 mol·g_Au^–1·h^–1 at 120 °C, being one of the highest WGS rates among Au/TiO₂ catalysts. The warm plasma generates a large amount of oxygen vacancies, while the cold plasma treatment generates small Au nanoparticles and interfacial sites. The (Au/TiO_2–<i>x</i>)_OP catalyst features two kinds of abundant active sites including Au^δ+-O^δ−-Ti⁴⁺ and Au⁰-O_v-Ti³⁺, which accelerate the WGS reaction simultaneously along the intermediate and redox reaction pathways, respectively.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"43 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917797","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":"B/g-C3N4 for Selectively Regulating Oxygen-Guided Photocatalytic Oxidation of Cinnamaldehyde to Benzaldehyde: Effects of Boron Sources","authors":"Xuan Luo, Bingbing Li, Tongming Su, Xinling Xie, Zuzeng Qin, Hongbing Ji","doi":"10.1021/acscatal.4c05427","DOIUrl":"https://doi.org/10.1021/acscatal.4c05427","url":null,"abstract":"Natural benzaldehyde, an important spice-type flavor component and raw pharmaceutical material, is scarcely due to the escalating demand and consumer preference for natural foods. To mitigate this issue, the present study aimed to investigate the oxygen-driven selective oxidation of cinnamaldehyde to benzaldehyde under visible light. K₂B₄O₇·4H₂O and KBH₄ were used as boron sources to modify the g-C₃N₄ photocatalyst for regulating the cinnamaldehyde conversion rate and benzaldehyde selectivity. A series of characterization techniques revealed improvements in the photocatalytic performance of the modified catalysts─that is, g-C₃N₄ doped with boron derived from K₂B₄O₇·4H₂O or KBH₄ (BCN or KBCN, respectively; 10% or 25% increase in cinnamaldehyde conversion rate, 11% or 34% increase in benzaldehyde selectivity). These enhancements were due to the doped boron and the generated nitrogen vacancy. Moreover, the abilities of BCN and KBCN to adsorb oxygen and cinnamaldehyde improved. The conjugated aldehyde group and planar molecular structure of cinnamaldehyde are critical to the selective oxidation of the &gt;C═C&lt; unit to obtain the aldehyde. The mechanism underlying the photocatalytic action of KBCN was established, and the reasons for the superior photocatalytic performance of KBCN compared with that of BCN were determined. Essentially, the reducible boron source─KBH₄─produced a radical boron site on the surface of g-C₃N₄, which collided with ^•O₂^– to generate another vital oxygen species ¹O₂. Subsequently, the electrons transferred to the surface of KBCN could be captured by the adsorbed oxygen molecules to regenerate ^•O₂^–. Furthermore, the hole produced on the catalyst surface during visible-light illumination promoted its reaction with ^•O₂^– by obtaining an electron from the &gt;C═C&lt; unit of cinnamaldehyde. Overall, this study paves the way for future applications and research on the selective oxidation of the &gt;C═C&lt; group in α,β-unsaturated carbonyl compounds.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"55 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917844","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":"Triethoxysilane-Catalyzed Single and Sequential Regioselective Hydroboration of Terminal Alkynes: Sustainable Access to E-Alkenylboronate and Alkyl Gem-Diboronate Esters by Non-Covalent Interactions","authors":"Harleen Kaur, Himani Ahuja, Rebeca Arevalo","doi":"10.1021/acscatal.4c06845","DOIUrl":"https://doi.org/10.1021/acscatal.4c06845","url":null,"abstract":"Triethoxysilane was found to be an efficient catalyst for the synthesis of <i>E</i>-alkenyl- and alkyl-di-boronate esters by the single and sequential hydroboration of terminal alkynes, respectively, with pinacolborane. Mechanistic studies support that the formation of diboronate esters proceeds by a double hydroboration pathway with the steric and electronic profile at Si being key to enabling the second hydroboration step. Weak non-covalent interactions involving the Si and the C≡C or C═C bonds in the alkynes or alkenylboronate esters have been identified as responsible for substrate activation toward the addition of HBPin.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"153 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912050","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":"Redox-Activated Supersaturation of Ceria Solid Solution as a Dynamic Catalyst Enabling Low-Temperature Ethylbenzene Oxidative Dehydrogenation","authors":"Juping Zhang, Wenpei Gao, Kunran Yang, Junchen Liu, Yanping Zheng, Kun Yang, Chao Zhang, Kongzhai Li, Kun Zhao, Hua Wang, Yunfei Gao, Xing Zhu","doi":"10.1021/acscatal.4c05793","DOIUrl":"https://doi.org/10.1021/acscatal.4c05793","url":null,"abstract":"Dynamic structural changes in the reactive environment often lead to catalyst deactivation in the thermal-catalysis field. Taking advantage of the dynamic changes in bulk phases, interfaces, and surface structures to design highly active catalysts is a unique but important strategy. Herein, we report a supersaturated ceria solid solution catalyst enabling a styrene yield of 91.8% over extended redox cycles at 430 °C in the redox oxidative dehydrogenation (ODH) of ethylbenzene. In-situ characterizations reveal that the oxygen anions (O^2–) and transition-metal cations (Fe and Mn) reversibly shuttle through a ceria solid solution (bulk ↔ surface) in a K–Ce_0.47Fe_0.2Mn_0.33O_2−δ catalyst during the redox ODH process. The ceria solid solution acts as a dynamic transition-metal cations/oxygen reservoir, creating atomic interfaces of K–Fe–O/K–Mn–O and an oxygen gateway for efficient ethylbenzene ODH. The findings concerning the formation of a supersaturated ceria solid solution and cations, lattice oxygen migration, and the coupling between oxygen donation and catalytic reactions offer new strategies for designing high-performance dynamic catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"26 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905084","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":"Elucidating the Reaction Mechanism and Deactivation of CO2-Assisted Propane Oxidative Dehydrogenation over VOx/TiO2 Catalysts: A Multiple Operando Spectroscopic Study","authors":"Leon Schumacher, Kathrin Hofmann, Christian Hess","doi":"10.1021/acscatal.4c04900","DOIUrl":"https://doi.org/10.1021/acscatal.4c04900","url":null,"abstract":"The CO₂-assisted oxidative dehydrogenation (ODH) of propane is of great technical importance and enables the use (and thus removal from the atmosphere) of CO₂, a greenhouse gas, in a value-adding process. Supported vanadium oxide (VO_<i>x</i>) catalysts are a promising alternative to more active but toxic chromium oxide catalysts. Despite its common use, TiO₂ has not been investigated as a support material for VO_<i>x</i> in the CO₂–ODH of propane. In this study, we elucidate the interaction between titania (P25) and vanadia in the reaction mechanism by analyzing the reaction network and investigating the catalyst using X-ray diffraction (XRD), multiwavelength Raman, UV–vis and diffuse reflectance IR Fourier transform (DRIFT) spectroscopy. Besides direct and indirect ODH reaction pathways, propane dry reforming (PDR) is identified as a side reaction, which is more prominent on bare titania. The presence of VO_<i>x</i> enhances the stability and the selectivity toward propylene by participating in the redox cycle, activating CO₂ and leading to a higher rate of regeneration. Additionally, VO_<i>x</i> catalyzes the conversion of anatase to rutile, which facilitates CO₂ activation, thereby leading to an encapsulation of vanadium. At higher loadings, reducible VO_<i>x</i> oligomers are present on the surface, facilitating some PDR, but less than on bare P25. As the main deactivation mechanisms of the catalyst system, we propose the reduction of the titania lattice and the consumption of vanadium, while carbon formation appears to be less relevant. Our results highlight the importance of analyzing the CO₂–ODH reaction network and applying a multispectroscopic approach to obtain a detailed mechanistic understanding of CO₂-assisted propane ODH over supported VO_<i>x</i> catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"223 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905031","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":"Expedited Synthesis of Axially Chiral 3-Monosilyl and 3,3′-Bis-silyl Biphenols, Binaphthols, and Phosphoramidites Enabled by Catalytic Two-Fold C–H Silylation with a Traceless Acetal Directing Group","authors":"Hiep H. Nguyen, Suman Das Adhikary, Yao Chung Chang, Peter Zotor, Junha Jeon","doi":"10.1021/acscatal.4c05927","DOIUrl":"https://doi.org/10.1021/acscatal.4c05927","url":null,"abstract":"The design and development of supporting ligands have significantly propelled the discovery of new catalytic reactions and the improvement of existing ones. Among these, axially chiral biphenols and 1,1′-binaphthalene-2,2′-diol (BINOL) are some of the most privileged ligands used in a wide array of enantioselective reactions. Despite the well-established benefits of structural modifications to biphenol and BINOL scaffolds, particularly at their 3,3′-positions─for enhancing reactivity and stereofidelity in catalytic asymmetric transformations─only a limited number of 3,3′-bis-functionalized biphenols and BINOLs are currently available. Here, we report a unified strategy to rapidly access a range of axially chiral 3-monosilyl and 3,3′ bis-silyl-substituted and biphenols and BINOLs as well as their corresponding 3-monosilyl and 3,3′ bis-silyl BINOL-based phosphoramidites. This approach involves traceless acetal-directed, catalytic two-fold C–H silylation of axially chiral biaryls, coupled with selective monoprotodesilylation, expanding the versatility of catalytic C–H functionalization in ligand design and development. Scope studies on the augmentation of the topological space of potentially stereoselectivity-amplifying 3,3′-bis-silyl substituents in axially chiral biphenols and BINOLs were achieved through C–H silylation of biphenols and BINOLs using various dihydrosilanes, as well as the derivatization of 3,3′-silanes, leading to functionalized silane-substituted biphenols and BINOLs. Lastly, the phosphoramidation of newly synthesized 3-monosilyl and 3,3′ bis-silyl BINOL and biphenols with dichlorophosphinamine provided a series of 3-monosilyl and 3,3′ bis-silyl BINOL-based phosphoramidites. The efficiency of this synthetic approach is underscored by its short synthetic steps, expedited reaction times, and minimal purification, making it versatile for the synthesis of a wide array of organosilicon-functionalized axially chiral biaryls and phosphoramidites.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"200 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142908270","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":"Monitoring Radical Intermediates in Photoactivated Palladium-Catalyzed Coupling of Aryl Halides to Arenes by an Aryl Radical Assay","authors":"Seb Tyerman, Donald G. MacKay, Kenneth F. Clark, Alan R. Kennedy, Craig M. Robertson, Laura Evans, Robert M. Edkins, John A. Murphy","doi":"10.1021/acscatal.4c06913","DOIUrl":"https://doi.org/10.1021/acscatal.4c06913","url":null,"abstract":"An aryl radical assay is used to provide information about the formation of aryl radicals from aryl halides in coupling reactions to arenes in the presence of palladium sources and under LED irradiation (λ = 456 nm). The assay uses 2-halo-<i>m</i>-xylenes as substrates. Aryl radical formation is indicated both by a defined product composition and by signature deuterium isotope effects. Comparison with our recently published results for corresponding ground-state palladium-catalyzed reactions shows three principal differences: (i) in the photoactivated reactions, evidence supports the formation of aryl radical intermediates with all the phosphine ligands tested, in contrast to thermal ground-state chemistry where only specific ligands had encouraged this pathway, while others had promoted a nonradical coupling mechanism; (ii) oxidative addition complexes that are formed from the reaction of Pd(0) sources with aryl halides react under photoactivation to form biaryl coupled products through radical intermediates, in contrast to their behavior under thermal activation – so Ar–Pd bonds are homolyzed under LED irradiation; (iii) the photoreactions work well with mild bases like Cs₂CO₃, while the thermal reactions required KO^tBu as the base due to the different roles for base under the thermal versus photochemical mechanisms.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905083","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":"Bioinformatics and Computationally Supported Redesign of Aspartase for β-Alanine Synthesis by Acrylic Acid Hydroamination","authors":"Alejandro Gran-Scheuch, Hein J. Wijma, Nikolas Capra, Hugo L. van Beek, Milos Trajkovic, Kai Baldenius, Michael Breuer, Andy-Mark W. H. Thunnissen, Dick B. Janssen","doi":"10.1021/acscatal.4c05525","DOIUrl":"https://doi.org/10.1021/acscatal.4c05525","url":null,"abstract":"Aspartate ammonia lyases catalyze the reversible amination of fumarate to <span>l</span>-aspartate. Recent studies demonstrate that the thermostable enzyme from <i>Bacillus</i> sp. YM55–1 (AspB) can be engineered for the enantioselective production of substituted β-amino acids. This reaction would be attractive for the conversion of acrylic acid to β-alanine, which is an important building block for the preparation of bioactive compounds. Here we describe a bioinformatics and computational approach aimed at introducing the β-alanine synthesis activity. Three strategies were used: First, we redesigned the α-carboxylate binding pocket of AspB to introduce activity with the acrylic acid. Next, different template enzymes were identified by genome mining, equipped with a redesigned α-carboxylate pocket, and investigated for β-alanine synthesis, which yielded variants with better activity. Third, interactions of the SS-loop that covers the active site and harbors a catalytic serine were computationally redesigned using energy calculations to stabilize reactive conformations and thereby further increase the desired β-alanine synthesis activity. Different improved enzymes were obtained and the best variants showed <i>k</i>_cat values with acrylic acid of at least 0.6–1.5 s^–1 with <i>K</i>_M values in the high mM range. Since the β-alanine production of wild-type enzyme was below the detection limit, this suggests that the <i>k</i>_cat/<i>K</i>_m was improved by at least 1000-fold. Crystal structures of the 6-fold mutant of redesigned AspB and the similarly engineered aspartase from <i>Caenibacillus caldisaponilyticus</i> revealed that their ligand-free structures have the SS-loop in a closed (reactive) conformation, which for wild-type AspB is only observed in the substrate-bound enzyme. AlphaFold-generated models suggest that other aspartase variants redesigned for acrylic acid hydroamination also prefer a 3D structure with the loop in a closed conformation. The combination of binding pocket redesign, genome mining, and enhanced active-site loop closure thus created effective β-alanine synthesizing variants of aspartase.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"71 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905077","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":"Nickel-Catalyzed Synthesis of Silaindanes via Sequential C–H Activating 1,5-Nickel Migration and C–Si Activating 1,4-Nickel Migration","authors":"Donghyeon Lee, Ikuya Fujii, Ryo Shintani","doi":"10.1021/acscatal.4c06910","DOIUrl":"https://doi.org/10.1021/acscatal.4c06910","url":null,"abstract":"Catalytic reactions involving 1,<i>n</i>-metal migration provide a powerful approach for the synthesis of complex molecular skeletons from simple precursors through the activation of unreactive bonds. In this work, a nickel-catalyzed synthesis of 3,3-disubstituted 1-silaindanes, silicon analogues of valuable indanes, was developed by the reaction involving 1,5-nickel migration via C–H bond activation and 1,4-nickel migration via C–Si bond activation. It was found that 1,5-nickel migration not only enabled the C–H bond activation at a remote position but also controlled the regioselectivity of subsequent alkene insertion. The detailed reaction mechanism was investigated by conducting deuterium labeling experiments and DFT calculations. The results obtained here demonstrate the high potential of catalytic reactions involving nickel migrations via C–H and C–Si bond activations for the synthesis of useful cyclic organosilicon compounds.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"172 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905085","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}