ACS Catalysis 最新文献

{"title":"Chiral 3,4-H2-Dihydro-Monothiobinaphthol-Derived Bifunctional Catalysts: Design, Synthesis, and Application to Enantioselective Disulfuration of Aza[5]Helicenes","authors":"Ze-Long Li,&nbsp;Qing-Yun Cai,&nbsp;Yu-Xuan Huo,&nbsp;Xue-Qing Gong,&nbsp;Hui-Yun Luo,&nbsp;Zhi-Min Chen","doi":"10.1021/acscatal.6c06318","DOIUrl":"10.1021/acscatal.6c06318","url":null,"abstract":"<p>We herein report the design and synthesis of a class of 3,4-dihydro-monothiobinaphthol (3,4-H₂-MTB)-derived bifunctional catalysts and their application in the asymmetric electrophilic C–H disulfuration of aza[5]helicenes. These catalysts feature a cooperative dual-activation motif: the thioether moiety acts as a Lewis base to activate the disulfurating reagent, while the phenolic hydroxyl group serves as a hydrogen-bond donor to engage the cocatalyst diphenyl phosphate. The reaction proceeds via a dynamic kinetic resolution mechanism, delivering a range of helically chiral aza[5]helicenes in good yields (up to 99%) and high enantioselectivities (up to 97% enantiomeric excess). The resulting enantioenriched products can be readily converted into helically chiral thiophenols, silyl sulfides, thioesters, and other derivatives. Mechanistic studies, including control experiments and density functional theory calculations, reveal that enantiocontrol arises from a synergistic network of noncovalent interactions including O–H···O hydrogen bonding, C–H···O interactions, and multiple C–H···π interactions facilitated by the 3,4-dihydro-binaphthyl framework. These features enable the in situ assembly of a chiral Lewis base/Brønsted acid catalytic manifold, which is instrumental in governing the observed enantioselectivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20700–20711"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092021","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":"The Chameleon Role of Interfacial Hydroxyls: Reaction-Condition-Dependent Dynamics in Methanol Electro-Oxidation","authors":"Hongkai Bu,&nbsp;Yang-Gang Wang","doi":"10.1021/acscatal.6c06067","DOIUrl":"10.1021/acscatal.6c06067","url":null,"abstract":"<p>The electrocatalytic oxidation of methanol on platinum represents a model system for alcohol fuel-cell chemistry, yet the precise role of interfacial hydroxyl (OH*), a key oxidative species, remains contentious and is often viewed simplistically as either a co-reactant or a poison. Herein, ab initio molecular dynamics simulations with explicit solvation were employed to transcend this binary perspective, revealing OH* as a dynamic interfacial mediator whose coverage influences methanol activation and mechanistic pathways. Under oxidative potentials, increasing OH* coverage leads to the formation of an interfacial adsorbate layer interconnected by hydrogen bonds. Frequent proton transfer within this layer facilitates spontaneous O–H bond cleavage of methanol, while fluctuations in the hydrogen-bond network further promote its pre-oxidation and activation. In contrast, OH*-mediated C–H oxidation involves a high free-energy barrier, and increasing OH* coverage reduces the availability of Pt sites required for C–H dissociation, potentially contributing to surface poisoning. Importantly, site competition induced by high OH* coverage also alters the configuration of the reaction-generated HCHO intermediate, reducing the accessibility of further C–H cleavage toward CO* while enabling direct reaction with OH* toward formate through a CO*-free pathway. Together, these results reveal a coverage-dependent trade-off among O–H activation, the availability of Pt sites for C–H bond cleavage, and subsequent pathway selection. Regulating interfacial OH* coverage therefore provides a possible means to tune methanol oxidation activity and pathway selectivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20645–20654"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092029","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":"Selective Cleavage of Carbon–Carbon Bonds of Aryl Ketones by Photocatalysis","authors":"Hao-Yuan Li,&nbsp;Xiu-Long Yang,&nbsp;Ke-Hang Zhang,&nbsp;Xiaoying Niu,&nbsp;Qing-Yuan Meng","doi":"10.1021/acscatal.6c05776","DOIUrl":"10.1021/acscatal.6c05776","url":null,"abstract":"<p>Selective cleavage of inert C─C bonds in unstrained molecules under mild conditions remains a long-standing challenge in synthetic chemistry. In preorganized unstrained aryl ketones, Ar─C(O) bonds are particularly recalcitrant because of their high bond dissociation energy and low polarization, and their selective activation typically requires strained rings, directing groups, or harsh conditions. Here, we report a visible-light-driven triplet energy-transfer strategy that enables selective cleavage of the Ar─C(O) bond in these preorganized aryl ketones through intramolecular 1,3-acyl migration, thereby providing direct access to aliphatic ketones embedded in 9,10-dihydrophenanthrene scaffolds under mild conditions. Mechanistic experiments and density functional theory (DFT) calculations support a sequence involving triplet-state 6π photocyclization, dearomatization, and rearomatization-driven 1,3-acyl migration. This work provides a conceptually distinct photochemical solution to Ar─C(O) bond cleavage in preorganized unstrained aryl ketones and highlights rearomatization-enabled acyl migration as a useful design principle for C─C bond activation.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20586–20595"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092420","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":"Enantiocomplementary Total Biosynthesis of Cyclic Imino Acids Enabled by an SN2 Reaction Catalyzed by a Class I Aldolase and a Transaminase","authors":"Qiaoqiao Li,&nbsp;Yulian Li,&nbsp;Zunyun Fu,&nbsp;Chunping Tang,&nbsp;Yang Ye,&nbsp;Xingxing Wu,&nbsp;Mingyue Zheng,&nbsp;Rui Zhang,&nbsp;Cangsong Liao","doi":"10.1021/acscatal.6c04987","DOIUrl":"10.1021/acscatal.6c04987","url":null,"abstract":"<p>Cyclic noncanonical imino acids are highly valuable in drug design due to their rigid conformational constraints. However, their structural complexity has limited the development of robust synthetic methods. Herein, we report a concise strategy for the enantiocomplementary total synthesis of these compounds. This route is driven by two key biocatalytic steps: a non-natural S_N2 reaction catalyzed by a class I pyruvate aldolase, followed by an enantiocomplementary reductive amination catalyzed by amino acid transaminases. We successfully implement this synthesis in <em>E. coli</em> whole-cell catalysts for streamlined production. From simple precursors, we synthesize 42 cyclic imino acids, including the natural product proferrorosamine A, in yields of up to 98% and with enantioselectivity up to &gt;99% <em>ee</em>. This work underscores the potential of leveraging non-natural activities of class I aldolases to create concise enzymatic routes for synthesizing complex chiral heterocycles beyond imino acids.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20287–20296"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151165","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":"Metal Speciation in Hierarchical ZSM-5 Programs Ethylene Oligomerization Selectivity","authors":"Hend Omar Mohamed,&nbsp;Vijay K. Velisoju,&nbsp;Rushana Khairova,&nbsp;Polina Tolstova,&nbsp;Stefan Adrian F. Nastase,&nbsp;David Trueba,&nbsp;Naydu Zambrano,&nbsp;Muhammad Arief Shafarifky,&nbsp;Mohamed Ben Hassine,&nbsp;Mohamed N. Hedhili,&nbsp;Edy Abou-Hamad,&nbsp;Selvedin Telalovic,&nbsp;Takato Mitsudome,&nbsp;Luigi Cavallo,&nbsp;Pedro Castaño","doi":"10.1021/acscatal.6c03322","DOIUrl":"10.1021/acscatal.6c03322","url":null,"abstract":"<p>Metal cations in zeolites can redirect alkene oligomerization from Brønsted-acid-mediated secondary chemistry toward coordination-insertion pathways; however, controlling whether metal precursors form accessible cationic sites or oxide nanoparticles remains challenging. Here, we prepared hierarchical ZSM-5 by polymeric templating (PT) at a common nominal loading of 3 wt % and compared the protonic parent H/PT with Ni/PT, Cr/PT, and Zr/PT to determine how metal speciation governs ethylene oligomerization. X-ray diffraction, N₂ physisorption, microscopy, X-ray photoelectron spectroscopy, in situ X-ray absorption spectroscopy, CO-DRIFTS, pyridine-FTIR, and multinuclear solid-state NMR show that Ni/PT is dominated by accessible, framework-interacting Ni²⁺ Lewis sites, with a minor NiO-like contribution. Cr/PT contains accessible Cr-associated Lewis sites together with CrO_<em>x</em>-like domains that evolve toward Cr₂O₃ during pretreatment, whereas Zr/PT is dominated by ZrO₂ nanoparticles and retains more Brønsted acidity than Ni/PT and Cr/PT. These differences reshape catalytic activity: Ni/PT achieves 92% combined C₄–C₈ olefin selectivity with a butene-rich, dimerization-dominated slate, whereas Cr/PT gives a C₆-rich distribution from a mixed network of Cr-associated Lewis sites and residual acid-mediated chemistry; H/PT and Zr/PT instead favor hydrogen transfer, aromatization, and paraffin formation. Density functional theory on an initiated [Ni(II)–ethyl]⁺ model places β-hydrogen transfer/chain termination 10 kJ mol^–1 below further ethylene insertion, rationalizing the C₄-rich response. The coke content increases in the order H/PT &lt; Ni/PT &lt; Cr/PT &lt; Zr/PT, whereas total retained-deposit content follows H/PT &lt; Cr/PT &lt; Ni/PT &lt; Zr/PT. Thus, olefin selectivity and deposit formation do not vary in parallel. Within this matched catalyst series, chain-length selectivity and deactivation reflect the coupled effects of metal speciation, site accessibility, thermal evolution, and residual acidity rather than nominal metal loading, total Lewis acidity, or texture alone.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19985–20000"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915586","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":"What Drives the Selectivity of 5-(Hydroxymethyl)furfural Electroreduction over Copper in Mildly Basic Medium?","authors":"Fabio Loprete,&nbsp;Giovanni Malagoli,&nbsp;Adriano Sacco,&nbsp;Riccardo Tarroni,&nbsp;Stephan N. Steinmann,&nbsp;Ivan Rivalta,&nbsp;Carine Michel,&nbsp;Patricia Benito","doi":"10.1021/acscatal.6c05142","DOIUrl":"10.1021/acscatal.6c05142","url":null,"abstract":"<p>2,5-Bishydroxymethylfuran (BHMF) is an important bio-based monomer that can be produced via the electrochemical reduction of 5-(hydroxymethyl)furfural (HMF) on Cu electrocatalysts. Under mildly alkaline conditions, however, BHMF formation competes with hydrodimerization to 5,5′-bis(hydroxymethyl)hydrofuroin (BHH) and oligomerization, particularly at HMF concentrations relevant for scale-up. Here, we combine electrochemical experiments and grand-canonical density functional theory (GC-DFT) to elucidate the origin of these competing pathways during HMF electroreduction on Cu-based foam catalysts at pH 9.2. Our results suggest that BHH formation and oligomerization arise from two distinct mechanisms: hydrodimerization might proceed via surface-catalyzed C–C coupling between adsorbed HMF species, whereas oligomerization is associated with the desorption of a ketyl intermediate into the electrochemical double layer. In contrast, BHMF formation preferentially occurs through the hydrogenation of an alkoxyl intermediate. The relative contribution of these pathways is modulated by catalyst morphology and the electroactive Cu surface area. Increasing the surface area through Cu nanoparticle electrodeposition enhances BHMF selectivity from 40% to 58% at 50 mM HMF and significantly suppresses oligomerization at –0.51 V vs RHE. Overall, our results highlight the importance of balancing HMF surface availability and H* availability and provide a mechanistic framework linking catalyst morphology and electrochemical conditions to control the selective HMF electroreduction on Cu and offer design principles for maximizing BHMF yields while minimizing hydrodimerization and carbon loss.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20358–20371"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050264","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":"Non-innocent Bromide Redirects Sulfur Oxygenation through O–O Bond Cleavage in a Nonheme Fe(III)–Superoxo System","authors":"Dongru Sun,&nbsp;Jolene P. Reid","doi":"10.1021/acscatal.6c05295","DOIUrl":"10.1021/acscatal.6c05295","url":null,"abstract":"<p>Thiol dioxygenase chemistry requires nonheme iron centers to activate triplet O₂ while controlling a sequence of short-lived Fe/O₂ intermediates, O–O bond cleavage or reorganization, and selective oxygen-atom delivery to sulfur. However, the identity and ordering of these intermediates remain difficult to define, and proposed mechanisms differ in whether sulfur oxygenation precedes, accompanies, or follows O–O bond cleavage. Here, we employ density functional theory (DFT) to interrogate the conversion of a metastable side-on Fe(III)–superoxo intermediate to an Fe^II–sulfinate product in a sulfur-ligated biomimetic system. The calculations show that the expected oxygenation pathways are kinetically disfavored, as direct sulfur oxygenation from the side-on Fe(III)–superoxo species requires a barrier of 22.4 kcal mol^–1 and side-on-to-end-on isomerization does not provide an efficient cysteine dioxygenase (CDO)-like oxygen-transfer pathway. Instead, the reaction proceeds through a bromide-assisted O–O cleavage mechanism, in which outer-sphere Br^– promotes O–O bond cleavage to generate an Fe^IV=O(OBr) intermediate as the competent oxygenating species. Subsequent coordination reorganization and second-sphere hydrogen bonding enable sequential oxygen transfer to sulfur, ultimately forming the Fe^II–sulfinate product. Reaction-coordinate, bonding, and topological analyses show that O–O cleavage is a cooperative bond-reorganization event involving Br–O interaction formation, O–O weakening, and ferryl-like Fe–O strengthening. Comparative Br-assisted, Cl-assisted, and halide-free models further establish that halide participation lowers the O–O cleavage barrier, with Br-assisted cleavage either kinetically favored over or comparable to its Cl-assisted counterpart. These findings reveal a non-innocent role of outer-sphere bromide in modulating the identity of the oxygenating species and the sequence of sulfur oxygenation in this biomimetic nonheme iron system.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20392–20403"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050268","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":"(ProPhos)Ni-Catalyzed Suzuki–Miyaura Coupling of (Hetero)aryl Pseudohalides under Homogeneous Conditions","authors":"Jonathan R. E. Cobb,&nbsp;Jonathan Yuan,&nbsp;Jiaojiao Wang,&nbsp;Matthew J. Goldfogel,&nbsp;Benjamin G. Hejna,&nbsp;Eric M. Simmons,&nbsp;Steven R. Wisniewski,&nbsp;Tianning Diao","doi":"10.1021/acscatal.6c05705","DOIUrl":"10.1021/acscatal.6c05705","url":null,"abstract":"<p>Suzuki–Miyaura coupling (SMC) of phenol-derived pseudohalides represents a compelling methodology for biaryl synthesis, given the ubiquity of phenolic motifs in active pharmaceutical ingredients (APIs) and the orthogonal reactivity of pseudohalides toward other common functional groups. Aryl sulfamates generally exhibit low reactivity with palladium catalysts due to slow oxidative addition. In contrast, nickel catalysts show significantly higher reactivity toward aryl sulfamates, but their application has been hampered by limited process compatibility in existing nickel-catalyzed protocols. Herein, we report a robust (ProPhos)Ni-SMC of aryl and heteroaryl pseudohalides, including sulfamates, triflates, and tosylates. Employing DIPEA as the base and an environmentally friendly <em>i</em>-PrOH/H₂O solvent mixture enables a monophasic, homogeneous condition well-suited for scale-up. This method exhibits a broad scope across pharmaceutically relevant heterocycles and demonstrates notable tolerance for heteroatoms proximal to the reactive C–O bond. By leveraging palladium’s orthogonal reactivity toward sulfamates, a “mixed aryl (pseudo)halide” was telescoped in a Pd-SMC/Ni-SMC sequence to form multi-aryls while minimizing purification steps and waste generation.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20596–20602"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090614","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":"How Far Does an Active Site Reach? Defining Interaction Radii in Covalent Organic Framework Electrocatalysts for Nitrate Reduction","authors":"Tsukasa Irie,&nbsp;Saikat Das,&nbsp;Yuichi Negishi","doi":"10.1021/acscatal.6c05600","DOIUrl":"10.1021/acscatal.6c05600","url":null,"abstract":"<p>Electrocatalytic nitrate reduction to ammonia has emerged as a compelling strategy for simultaneously closing the anthropogenic nitrogen cycle and enabling decentralized ammonia production. Despite substantial advances in catalyst development, the origin of high selectivity in porous electrocatalysts remains incompletely understood because current interpretations overwhelmingly regard active sites as localized catalytic points. In this Perspective, we argue that this description neglects a fundamental length scale governing multistep nitrate electroreduction. We introduce the concept of an interaction radius, defined as the spatial domain over which an active site measurably perturbs the energetics, dynamics, and transport of reactants, intermediates, and transition states. Within covalent organic frameworks (COFs), this interaction radius emerges from the coupled action of electronic delocalization, electrostatic fields, hydrogen-bonding networks, steric confinement, and solvent organization, transforming the active site from a discrete coordination center into a spatially distributed catalytic entity. We discuss how interaction radii evolve under electrochemical bias, overlap to produce cooperative reaction domains, and ultimately determine intermediate retention, pathway bifurcation, and ammonia selectivity. We further propose experimental and computational strategies for quantifying interaction radii and establish design principles that relate framework chemistry, pore architecture, site spacing, and local solvation to the reaction length scales of nitrate reduction. By reframing COF electrocatalysis through a spatially resolved perspective, this work establishes interaction radius as a quantitative organizing framework with the potential to evolve into a predictive descriptor for rational catalyst design, while providing a transferable conceptual basis for understanding complex electrocatalytic reactions beyond nitrate reduction.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19693–19724"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092024","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":"Computational Insights into Catalytic Hydrogenation over M6O8-Node MOFs: From Active-Site Engineering to Data-Driven Catalyst Design","authors":"Wenting Ding,&nbsp;Zuoshuai Xi,&nbsp;Shuanglong Li,&nbsp;Yongquan Niu,&nbsp;Wenqing Li,&nbsp;Yujing Ji,&nbsp;Jingjing Wang,&nbsp;Hongyi Gao,&nbsp;Ge Wang","doi":"10.1021/acscatal.6c05813","DOIUrl":"10.1021/acscatal.6c05813","url":null,"abstract":"<p>Metal–organic frameworks (MOFs) containing M₆O₈ secondary building units (SBUs) have attracted considerable attention as hydrogenation catalysts because of their structural robustness, tunable coordination environments, and diverse opportunities for active-site engineering. In recent years, density functional theory (DFT) and related computational approaches have become indispensable tools for elucidating catalytic mechanisms and guiding catalyst design. This review summarizes recent theoretical advances in catalytic hydrogenation over M₆O₈-node MOFs, with particular emphasis on active-site engineering strategies, including metal doping, single-atom anchoring, metal cluster encapsulation, and ligand functionalization. Their effects on key catalytic processes, such as H₂ activation, intermediate stabilization, and reaction energy barriers, are systematically discussed. We further highlight the electronic structure origins of catalytic performance, focusing on descriptors such as charge transfer, d-band center modulation, and frontier orbital interactions that govern activity and selectivity. In addition, emerging data-driven approaches are reviewed for their potential to establish structure–property relationships, enable high-throughput screening, and accelerate catalyst discovery. Current challenges in theoretical studies, including model idealization and the limited description of realistic reaction environments, are also discussed.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19752–19782"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092074","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}