ACS Catalysis 最新文献

{"title":"Cation Effects on the Brønsted Acidity of Solid Tungstosilicic Acid Clusters","authors":"Guangming Cai, Prashant Deshlahra, Ya-Huei Cathy Chin","doi":"10.1021/acscatal.4c03233","DOIUrl":"https://doi.org/10.1021/acscatal.4c03233","url":null,"abstract":"Rigorous kinetic assessments, pyridine chemical titration and desorption, together with density functional theory calculations establish the trends in the modulation of chemical identity, valence, site density, and strength of Brønsted acid sites by counter cations (Na⁺, K⁺, Cu²⁺, Mg²⁺, and Al³⁺) on Keggin-type polyoxometalate tungstosilicic acid clusters (H₄SiW₁₂O₄₀, POM). Monovalent cations (Na⁺ and K⁺) exchange protons and decrease the acid strength of the residual protons, as indicated by the deprotonation energy (DPE) that increases from 1100 to 1175 kJ mol^–1 with an increasing extent of proton exchange (decreasing the nominal H⁺-to-POM ratio). In contrast, di- and trivalent cations preferentially exchange protons in the form of hydroxides (Y^<i>z</i>+(OH)_<i>m</i>, Y^<i>z</i>+ = Cu²⁺, Mg²⁺, or Al³⁺, 0 &lt; <i>m</i> &lt; <i>z</i>), resulting in an average DPE value on both POM clusters and associated hydroxides ranging between 1100 and 1150 kJ mol^–1. A portion of these cations disperse on the silica support, generating Lewis acid sites. The exchanged cations modulate the charge within the W₁₂O₃₆ oxide shell, rather than the central SiO₄^4– tetrahedron, which mainly modifies the ionic component of DPE values. Monovalent cations with smaller electronegativities than di- and trivalent cations donate more electrons, which increases the electrostatic interaction of residual protons with conjugate POM^– anions and leads to higher DPE values (weaker acids). This study expands the library of Brønsted acidic catalysts with flexibility in tuning their acid strengths and densities, thus providing a series of samples for constructing structure–reactivity relationships and probing site electrostatic correlations on structurally constrained domains.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276781","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":"Gold(I)-Catalyzed Access to 1-Alkynyl C-Glycosides from 1-Silylated Alkynes: An Alternative Paradigm for the Direct and α-Stereoselective Alkynylation of Glycosides","authors":"Eliot Starck, Mathieu Pascaretti, Catherine Taillier, Aurélien Blanc, Vincent Dalla, Patrick Pale, Jean-Marc Weibel","doi":"10.1021/acscatal.4c04293","DOIUrl":"https://doi.org/10.1021/acscatal.4c04293","url":null,"abstract":"Analogous to <i>O</i>-glycosides, <i>C</i>-glycosides are natural products exhibiting various bioactivities. Alkynyl <i>C</i>-glycosides represent important key intermediates toward more complex derivatives; however, a convenient access through a single catalytic and highly stereocontrolled step remains an important and only partially solved challenge. Here, a mechanistically designed gold(I)-catalyzed silyl-assisted efficient and highly α-stereoselective process is reported. The postulated mechanism has been ascertained by combining ¹H, ³¹P and VT NMR and in situ MS experiments.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317234","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":"Novel Descriptor-Driven Design of Molten Alloys for Methane Pyrolysis","authors":"Seung Ju Han, Jeong-Cheol Seo, Gyungah Park, Ju Ho Son, Yunjo Lee, Seok Ki Kim","doi":"10.1021/acscatal.4c04480","DOIUrl":"https://doi.org/10.1021/acscatal.4c04480","url":null,"abstract":"Clean hydrogen production via methane pyrolysis using molten metal alloy catalysts is an interesting approach. However, the high temperatures and dynamic conditions required for pyrolysis render <i>in situ</i> observation of the molten metal system difficult. In this study, we identified two descriptors (H* formation energy and solute metal diffusivity) based on <i>ab initio</i> molecular dynamics simulations to predict the catalytic activity of Bi-based binary alloys (M = Ni, Pt, Cu, Ag) in methane pyrolysis. The solute metals were active sites for strong hydrogen adsorption, whereas solute metal diffusivity determined the extent of its exposure on the surface of the molten metal bubbles. Based on these findings, we identified two ternary alloys (Bi–Ni–Cu and Bi–Ni–Mn) that are catalytically more active than the binary Bi–Ni alloy. This study promotes the theory-based screening of highly active alloy catalysts for methane pyrolysis, thus contributing to the advancement of hydrogen society.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276780","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":"High-Entropy Effect Breaking the Oxo Wall for Selective High-Valent Metal–Oxo Species Generation","authors":"Zhonglian Shi, Chao Li, Wei Liu, Ziyi Jiang, Haohao Chen, Xin Ying Kong, Li Wang, Yingping Huang, Dehua Xia, Liqun Ye","doi":"10.1021/acscatal.4c03327","DOIUrl":"https://doi.org/10.1021/acscatal.4c03327","url":null,"abstract":"The advancement of multiphase catalysts that consist of multiple active sites is the key to improving the catalytic activity of peroxymonosulfate (PMS)-based Fenton catalysts. However, enormous challenges remain in rationally regulating the electronic configuration of each metal center to further improve the PMS activation kinetics. The generation of high-valent metal–oxygen species (e.g., Co (IV)═O and Cu (III)-O) poses as a major obstacle due to the “oxo wall” rule. Herein, we introduce high-entropy engineering, which cleverly and rationally utilizes the high-entropy effect to extract electrons from the d-orbitals of target metals through the asymmetric co-coordination of metal atoms with different electronegativities, thereby promoting the electron delocalization of the target metals. The electronic structure of each site of the high-entropy oxides (HEOs) (ZnMg)(MnCoCu)₂O₄ was further adjusted to promote the activation kinetics of PMS, which facilitates the efficient and sustainable generation of late transition high-valent metal–oxygen species. Both experimental results and theoretical calculations show that the interaction of various metal atoms with different electronegativities reduces the electron density of the Cu and Co sites, and shifts the d-band centers downward, thus optimizing the adsorption energy for PMS activation. Finally, the HEOs catalyst was prepared on the polyester fiber cotton for the flow-through device to achieve continuous and efficient removal of micropollutants (degradation efficiency &gt;90% after 24 h of operation). This work provides new insights into the modulation of the electronic structure of targeted metal centers and the conformational relationships at the atomic level.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276779","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":"Microenvironment Effect Catalysis with Phosphoric Acid-Based Covalent Organic Frameworks","authors":"Wenqi Qiu, Jialin Cui, Kejin Zhu, Meng Gao, Xuhan Zheng, Hui Liu, Zongxia Guo, Zhenxiu Zhang, Yingjie Zhao","doi":"10.1021/acscatal.4c04877","DOIUrl":"https://doi.org/10.1021/acscatal.4c04877","url":null,"abstract":"Drawing inspiration from enzymatic catalysis, a phosphoric acid-based covalent organic framework (<b>PA-COF</b>) was engineered for the efficient synthesis of optically pure lactide. <b>PA-COF</b> catalyst features precisely engineered microenvironments within well-defined porous channels decorated with phosphoric acid as the catalytically active sites. Much like enzymatic catalysis, where product selectivity is governed by the protein pocket, <b>PA-COF</b> provides precise microenvironments due to its highly ordered channels and adjustable structures. The phosphoric acids in the channels as catalytically active sites play key roles in directly converting lactic acid monomers into the cyclic dimer lactide. The process effectively avoided oligomerization, achieving an excellent yield of approximately 95%. This approach significantly differs from the traditional two-step strategy. It avoids the use of metal catalysts and high-temperature (∼200 °C) reaction conditions, thus avoiding metal residues and racemization. This microenvironment effect catalysis strategy provides a new pathway for the synthesis of lactide and may be extended to other useful condensation reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142273617","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":"Confinement Catalysis of Reaction Intermediates in Ag@Cu2O Cascade Nanoreactors toward Boosted Electrochemical C–C Coupling","authors":"Yonglian Lu, Honglin Li, Hongman Sun, Jiatai Zhao, Yu Zhang, Youhe Wang, Chuanyong Zhu, Dunfeng Gao, Yongxiao Tuo, Jingbin Zeng, De Chen, Zifeng Yan","doi":"10.1021/acscatal.4c04115","DOIUrl":"https://doi.org/10.1021/acscatal.4c04115","url":null,"abstract":"Cascade nanoreactors provide an ideal platform for multicomponent sequential reactions and synergistic transformations. However, the effects of morphology modulation on confinement catalysis, particularly regarding the generation, diffusion, and dimerization of reaction intermediates in CO₂RR are less discerned. Herein, we synthesized a series of Ag@Cu₂O cascade nanoreactors with tunable shell thicknesses by a two-step seeded growth method, observing an obvious volcano-type curve in C₂₊ products generation. The variant with a medium shell thickness (Ag@Cu₂O-40) achieved the highest Faradaic efficiency (FE) of C₂₊ up to 78.5% at −1.6 V (vs RHE). In situ Raman and density functional theory (DFT) calculations indicate that CO generated on the Ag core spills over and becomes confined at the Cu₂O shell, which is crucial in boosting C–C coupling rather than forming C₁ products (CO, CH₃OH, and CH₄). Finite element method (FEM) simulations further reveal that the optimal thickness of the Cu₂O shell accommodates CO₂ diffusion and CO confinement capabilities, thereby maximizing CO concentration for the formation of C₂₊ products. Our findings exemplify the potential of rationally designed cascade nanoreactors for optimizing reaction intermediates through confinement catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246884","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":"Disentangling the Catalytic Mechanisms of C60-Buffered Cu/SiO2 Catalyst for DMO-to-EG Conversion","authors":"Jianzhi Xu, Zhen-Chao Long, Zuo-Chang Chen, Chang-Feng Zhu, Hong-Guang Xu, Jian-Wei Zheng, Ewald Janssens, Wei-Jun Zheng, Gao-Lei Hou, Su-Yuan Xie","doi":"10.1021/acscatal.4c03943","DOIUrl":"https://doi.org/10.1021/acscatal.4c03943","url":null,"abstract":"Both ethylene glycol and methyl glycolate, which can be synthesized by hydrogenating dimethyl oxalate, are important chemical feedstocks, and understanding the mechanistic details underlying those hydrogenation reactions is of pivotal importance for the design of high-performance catalysts. In this work, we employ carefully constructed model cluster catalysts, including Cu₄, C₆₀Cu, C₆₀Cu₃, and C₆₀Cu₄, to mimic the widely utilized Cu/SiO₂ catalyst and the recently discovered C₆₀-buffered Cu/SiO₂ catalyst based on joint efforts from mass spectrometry, photoelectron spectroscopy, density functional theory calculations, and molecular dynamics simulations. We explored the catalytic mechanisms of the hydrogenation of dimethyl oxalate catalyzed by our model cluster catalysts and uncovered the possibility to tune the product selectively by changing the copper cluster size. Our results reveal important geometric and electronic effects of C₆₀ in promoting the catalytic reactions by reversibly accepting and donating, i.e., serving as an electron buffer, electrons to the adsorbed copper, resulting in the alternating formation of Cu⁰ and Cu^δ+ sites in different steps of the hydrogenation reactions. These oxidation state changes are crucial for the hydrogenation and stabilization of the reaction intermediates.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246883","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":"Development of Tunable Mechanism-Based Carbasugar Ligands that Stabilize Glycoside Hydrolases through the Formation of Transient Covalent Intermediates","authors":"Sandeep Bhosale, Sachin Kandalkar, Pierre-André Gilormini, Oluwafemi Akintola, Rhianna Rowland, Pal John Pal Adabala, Dustin King, Matthew C. Deen, Xi Chen, Gideon J. Davies, David J. Vocadlo, Andrew J. Bennet","doi":"10.1021/acscatal.4c04549","DOIUrl":"https://doi.org/10.1021/acscatal.4c04549","url":null,"abstract":"Mutations in many members of the set of human lysosomal glycoside hydrolases cause a wide range of lysosomal storage diseases. As a result, much effort has been directed toward identifying pharmacological chaperones of these lysosomal enzymes. The majority of the candidate chaperones are active site-directed competitive iminosugar inhibitors but these have met with limited success. As a first step toward an alternative class of pharmacological chaperones we explored the potential of small molecule mechanism-based reversible covalent inhibitors to form transient enzyme–inhibitor adducts. By serial synthesis and kinetic analysis of candidate molecules, we show that rational tuning of the chemical reactivity of glucose-configured carbasugars delivers cyclohexenyl-based allylic carbasugar that react with the lysosomal enzyme β-glucocerebrosidase (GCase) to form covalent enzyme-adducts with different half-lives. X-ray structural analysis of these compounds bound noncovalently to GCase, along with the structures of the covalent adducts of compounds that reacted with the catalytic nucleophile of GCase, reveal unexpected reactivities of these compounds. Using differential scanning fluorimetry, we show that formation of a transient covalent intermediate stabilizes the folded enzyme against thermal denaturation. In addition, these covalent adducts break down to liberate the active enzyme and a product that is no longer inhibitory. We further show that the one compound, which reacts through an unprecedented S_N1′-like mechanism, exhibits exceptional reactivity–illustrated by this compound also covalently labeling an α-glucosidase. We anticipate that such carbasugar-based single turnover covalent ligands may serve as pharmacological chaperones for lysosomal glycoside hydrolases and other disease-associated retaining glycosidases. The unusual reactivity of these molecules should also open the door to creation of new chemical biology probes to explore the biology of this important superfamily of glycoside hydrolases.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142273619","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":"Carbon-Chain Elongation by Co-Catalyzed Selective C–C Bond Cleavage and Subsequent Silylperoxylation of Alkene Substrates","authors":"Jia-Hao Xie, Terumasa Kato, Keiji Maruoka","doi":"10.1021/acscatal.4c04886","DOIUrl":"https://doi.org/10.1021/acscatal.4c04886","url":null,"abstract":"A Co-catalyzed selective C–C bond cleavage followed by the silylperoxylation of alkene substrates generated a series of alkylsilyl peroxides with good yields and selectivities. Further transformation through transition-metal-catalyzed cleavage of the resulting alkylsilyl peroxides and subsequent functionalization with coupling partners could generate a series of dicarbonyl compounds. This two-step transformation was carried out in a one-pot manner, which enhances the practicability of this approach. A plausible reaction mechanism was proposed to interpret the C–C bond cleavage and subsequent silylperoxylation of the alkene substrates.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246885","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":"Enantioselective Synthesis of P-Chiral Phosphine Oxides Bearing an All-Carbon Quaternary Stereogenic Center via Palladium-Catalyzed Domino Heck–Suzuki Reaction","authors":"Siyu Zhao, Jiahao Liu, Xunfang Xu, Xuemei Chen, Terumasa Kato, Zhe Wang, Yan Liu, Keiji Maruoka","doi":"10.1021/acscatal.4c04958","DOIUrl":"https://doi.org/10.1021/acscatal.4c04958","url":null,"abstract":"An approach has been developed for the enantioselective synthesis of <i>P</i>-chiral phosphine oxides bearing an all-carbon quaternary stereogenic center via a Pd-catalyzed domino Heck–Suzuki reaction. The origin of the mechanistic preference leading to high diastereo- and enantioselectivities under the Pd catalysis based on a TADDOL-derived phosphoramidite ligand was rationalized on the basis of DFT calculations.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142273620","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}