Pub Date : 2026-10-20DOI: 10.1021/acscatal.6c05077
Liyuan Long,Junjun Zhang,Wenqing Li,Yu Qian,Gangyang Lv,Peiran Feng,Gang Zhou,Dunhui Wang
Defect engineering is promising to solve the photocarrier dynamics mismatch between rapid bulk recombination and sluggish surface oxygen evolution reaction (OER) in PEC water splitting but is limited by forming random or bulk defects. Herein, we adopt a phase and facet modulation strategy to construct a 2D defective spinel β-In2S3 photoanode with highly exposed, well-ordered indium vacancies (VIn). These VIn introduce a shallow acceptor level near the valence band (VB), which induces selective photohole capture to VIn shallow traps. The efficient and fast (∼0.13 ps) photohole transfer from the VB to the VIn state and the sharply elongated lifetime for photoholes accumulated at VIn, by facilitating band-edge exciton dissociation, induce separation efficiency nearly 100% even at low bias. Meanwhile, surface VIn lowers the OER barrier by boosting the conversion of *OH to *O and promotes surface reaction kinetics, enabling the photohole transfer efficiency to reach 95%. Thus, VIn simultaneously acts as photohole-capture centers and surface-active sites to optimize photohole separation and interfacial transfer dynamics. Through introducing and exposing ordered VIn to reaction interfaces, the β-In2S3-2D photoanode achieves a record-high photocurrent density of 9.7 mA cm–2 at 1.23 VRHE and an IPCE reaching 80% without hole scavengers. Such a regulation mechanism can guide reverse design of defective semiconductor photoanodes for efficient PEC conversion.
缺陷工程有望解决PEC水裂解过程中快速体重组与缓慢表面析氧反应（OER）之间的光载流子动力学不匹配问题，但受随机缺陷或体缺陷的限制。在此，我们采用相位和面调制策略构建了具有高度暴露，有序铟空位（VIn）的二维缺陷尖晶石β-In2S3光阳极。这些VIn在价带（VB）附近引入了一个浅受体能级，诱导了VIn浅阱的选择性光孔捕获。从VB态到VIn态的高效、快速（约0.13 ps）的光空穴转移，以及在VIn态积累的光空穴寿命的急剧延长，通过促进带边激子解离，即使在低偏压下也能诱导出接近100%的分离效率。同时，表面VIn通过促进*OH到*O的转化降低OER势垒，促进表面反应动力学，使光孔转移效率达到95%。因此，VIn同时充当光空穴捕获中心和表面活性位点，以优化光空穴分离和界面传递动力学。通过在反应界面上引入和暴露有序的VIn，在1.23 VRHE下，β-In2S3-2D光阳极获得了创纪录的9.7 mA cm-2的光电流密度，在没有空穴清除剂的情况下，IPCE达到80%。这种调节机制可以指导缺陷半导体光阳极的反向设计，以实现高效的PEC转换。
{"title":"Achieving Ordered-Cationic-Vacancy-Mediated Photohole Transfer Dynamics via Phase and Facet Engineering toward Highly Efficient Photoelectrochemical Water Splitting","authors":"Liyuan Long,Junjun Zhang,Wenqing Li,Yu Qian,Gangyang Lv,Peiran Feng,Gang Zhou,Dunhui Wang","doi":"10.1021/acscatal.6c05077","DOIUrl":"https://doi.org/10.1021/acscatal.6c05077","url":null,"abstract":"Defect engineering is promising to solve the photocarrier dynamics mismatch between rapid bulk recombination and sluggish surface oxygen evolution reaction (OER) in PEC water splitting but is limited by forming random or bulk defects. Herein, we adopt a phase and facet modulation strategy to construct a 2D defective spinel β-In2S3 photoanode with highly exposed, well-ordered indium vacancies (VIn). These VIn introduce a shallow acceptor level near the valence band (VB), which induces selective photohole capture to VIn shallow traps. The efficient and fast (∼0.13 ps) photohole transfer from the VB to the VIn state and the sharply elongated lifetime for photoholes accumulated at VIn, by facilitating band-edge exciton dissociation, induce separation efficiency nearly 100% even at low bias. Meanwhile, surface VIn lowers the OER barrier by boosting the conversion of *OH to *O and promotes surface reaction kinetics, enabling the photohole transfer efficiency to reach 95%. Thus, VIn simultaneously acts as photohole-capture centers and surface-active sites to optimize photohole separation and interfacial transfer dynamics. Through introducing and exposing ordered VIn to reaction interfaces, the β-In2S3-2D photoanode achieves a record-high photocurrent density of 9.7 mA cm–2 at 1.23 VRHE and an IPCE reaching 80% without hole scavengers. Such a regulation mechanism can guide reverse design of defective semiconductor photoanodes for efficient PEC conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"13 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221522","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}
Pub Date : 2026-10-20DOI: 10.1021/acscatal.6c07216
Christopher Weike,Simon Teeuwen,Anh Kieu Phan,Max N. Kliemann,Thomas Weyhermüller,Walter Leitner,Giancarlo Franciò
The rhodium-catalyzed asymmetric hydroformylation (AHF) of vinyl ethers provides a powerful synthetic step to yield chiral aldehydes as products or intermediates for industrially relevant fine chemicals. Out of the 40 chiral ligands tested, the phosphine-phosphorodiamidite (S,S,RP,S)-BettiPhos L7 and the phosphine-phosphoramidite ligand L6 performed best in this transformation, combining high activity, regio- and enantioselectivity. Branched 2-aryloxypropionaldehydes (16 examples) were obtained with b/l-ratios ranging from 3.1:1 to exclusive branched products, and with enantioselectivities between 79 and 94% ee. Interestingly, for these substrates, the selective decomposition of the linear aldehydes to the respective arenols and acrolein via β-hydride elimination was observed. Branched 2-alkyloxypropionaldehydes (3 examples) were obtained with fair b/l-ratios (1.7:1–2.6:1) and good to high enantioselectivities (85–95% ee). The utility of this transformation was demonstrated by synthesizing the commercial herbicide (R)-Mecoprop on a gram scale in 69% yield and 91% ee via hydroformylation of 4-chloro-2-methyl-1-(vinyloxy)benzene, followed by oxidation. The catalytic system could also be used under slightly modified reaction conditions for reductive asymmetric hydroformylation to produce in one-pot chiral 2-aryloxypropanols. The synthetic potential was further explored by applying the tandem asymmetric hydrohydrazonemethylation (AHHM) followed by reduction, yielding γ-chiral N′-substituted acetohydrazides as shown for 6 examples. Hydrogenolysis of the crude product mixtures results in the corresponding chiral primary amines, as demonstrated in the synthesis of 2-phenoxypropanamine from (vinyloxy)benzene with an overall yield of 74% and 94% ee on a gram scale. Moreover, another tandem reaction—specifically, the asymmetric hydrosulfiniminomethylation (AHSM)—enables access to halogen-containing chiral primary amines, as demonstrated by the synthesis of 2-(4-chlorophenoxy)propanamine in an overall yield of 53% and >99% ee.
{"title":"Rhodium-Catalyzed Asymmetric Hydroformylation of Vinyl Ethers as a Key Step in the Synthesis of Chiral Fine Chemicals","authors":"Christopher Weike,Simon Teeuwen,Anh Kieu Phan,Max N. Kliemann,Thomas Weyhermüller,Walter Leitner,Giancarlo Franciò","doi":"10.1021/acscatal.6c07216","DOIUrl":"https://doi.org/10.1021/acscatal.6c07216","url":null,"abstract":"The rhodium-catalyzed asymmetric hydroformylation (AHF) of vinyl ethers provides a powerful synthetic step to yield chiral aldehydes as products or intermediates for industrially relevant fine chemicals. Out of the 40 chiral ligands tested, the phosphine-phosphorodiamidite (S,S,RP,S)-BettiPhos L7 and the phosphine-phosphoramidite ligand L6 performed best in this transformation, combining high activity, regio- and enantioselectivity. Branched 2-aryloxypropionaldehydes (16 examples) were obtained with b/l-ratios ranging from 3.1:1 to exclusive branched products, and with enantioselectivities between 79 and 94% ee. Interestingly, for these substrates, the selective decomposition of the linear aldehydes to the respective arenols and acrolein via β-hydride elimination was observed. Branched 2-alkyloxypropionaldehydes (3 examples) were obtained with fair b/l-ratios (1.7:1–2.6:1) and good to high enantioselectivities (85–95% ee). The utility of this transformation was demonstrated by synthesizing the commercial herbicide (R)-Mecoprop on a gram scale in 69% yield and 91% ee via hydroformylation of 4-chloro-2-methyl-1-(vinyloxy)benzene, followed by oxidation. The catalytic system could also be used under slightly modified reaction conditions for reductive asymmetric hydroformylation to produce in one-pot chiral 2-aryloxypropanols. The synthetic potential was further explored by applying the tandem asymmetric hydrohydrazonemethylation (AHHM) followed by reduction, yielding γ-chiral N′-substituted acetohydrazides as shown for 6 examples. Hydrogenolysis of the crude product mixtures results in the corresponding chiral primary amines, as demonstrated in the synthesis of 2-phenoxypropanamine from (vinyloxy)benzene with an overall yield of 74% and 94% ee on a gram scale. Moreover, another tandem reaction—specifically, the asymmetric hydrosulfiniminomethylation (AHSM)—enables access to halogen-containing chiral primary amines, as demonstrated by the synthesis of 2-(4-chlorophenoxy)propanamine in an overall yield of 53% and >99% ee.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221619","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}
Present herein is a gold(I)-catalyzed asymmetric cascade reaction of 1-(1-alkynyl)cyclobutyl ketones. Upon activation by a chiral phosphoric-acid-tethered gold(I) complex, they undertake intramolecular 5-endo-dig cyclization, and the resulting oxocarbenium species engage in an asymmetric 1,2-alkyl migration to generate gold-containing cyclopenta[b]furan carbocations, which can be intercepted by a broad range of nucleophiles, including indoles, pyrroles, alcohols, and amines, providing efficient access to synthetically challenging tetrahydro-4H-cyclopenta[b]furans bearing vicinal bridged quaternary stereocenters with fair to high enantioselectivity. The intermediates can also participate in (3 + 2) annulations with suitable 1,3-dipoles to afford polycyclic architectures with high molecular complexity. Mechanistic studies and density function theory calculations elucidate the key factors governing the catalytic pathways and stereochemical outcomes.
{"title":"Gold(I)-Catalyzed Asymmetric Transformations of 1-(1-Alkynyl)cyclobutyl Ketones: Access to Enantioenriched Cyclopenta[b]furans Bearing Vicinal Bridged Quaternary Stereocenters","authors":"Bao-Rui Kong,Shi-Cun Li,Qiao-Yang Liu,Ke Xie,Zhi-Chao Chen,Qin Ouyang,Wei Du,Ying-Chun Chen","doi":"10.1021/acscatal.6c06220","DOIUrl":"https://doi.org/10.1021/acscatal.6c06220","url":null,"abstract":"Present herein is a gold(I)-catalyzed asymmetric cascade reaction of 1-(1-alkynyl)cyclobutyl ketones. Upon activation by a chiral phosphoric-acid-tethered gold(I) complex, they undertake intramolecular 5-endo-dig cyclization, and the resulting oxocarbenium species engage in an asymmetric 1,2-alkyl migration to generate gold-containing cyclopenta[b]furan carbocations, which can be intercepted by a broad range of nucleophiles, including indoles, pyrroles, alcohols, and amines, providing efficient access to synthetically challenging tetrahydro-4H-cyclopenta[b]furans bearing vicinal bridged quaternary stereocenters with fair to high enantioselectivity. The intermediates can also participate in (3 + 2) annulations with suitable 1,3-dipoles to afford polycyclic architectures with high molecular complexity. Mechanistic studies and density function theory calculations elucidate the key factors governing the catalytic pathways and stereochemical outcomes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"33 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221620","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}
Highly active water oxidation catalysts based on earth-abundant elements are strongly demanded for practical application of artificial photosynthesis. An iron complex with a chlorin ligand derived from chlorophyll-a demonstrated the highest turnover frequency (= 21.3 ± 0.3 s–1) and turnover number (= 6920 ± 110) among homogeneous catalysts reported for photocatalytic water oxidation utilizing [RuII(bpy)3]2+ (bpy: 2,2′-bipyridine) and S2O82– as a photosensitizer and a sacrificial electron acceptor, respectively. The molecular nature of the Fe chlorin complex during the photocatalytic water oxidation was confirmed by dynamic light scattering analysis and electrospray ionization time-of-flight mass spectrometry. Also, kinetic studies suggested that the rate-determining step is O–O bond formation via coupling of two high-valent iron–oxo species formed by three-electron oxidation of the mononuclear Fe chlorin unit with water. The high planarity of the chlorin ligand enables the high-valent iron–oxo species to approach another iron–oxo unit closely, thereby facilitating O–O bond formation.
{"title":"Extremely High Turnover Number and Turnover Frequency of an Iron Chlorin Complex for Photocatalytic Water Oxidation","authors":"Takashi Nakazono,Ryo Mitsuda,Shinsuke Nakamura,Yuma Kawai,Daichi Sugawara,Tohru Wada,Hitoshi Tamiaki,Yusuke Yamada","doi":"10.1021/acscatal.6c02830","DOIUrl":"https://doi.org/10.1021/acscatal.6c02830","url":null,"abstract":"Highly active water oxidation catalysts based on earth-abundant elements are strongly demanded for practical application of artificial photosynthesis. An iron complex with a chlorin ligand derived from chlorophyll-a demonstrated the highest turnover frequency (= 21.3 ± 0.3 s–1) and turnover number (= 6920 ± 110) among homogeneous catalysts reported for photocatalytic water oxidation utilizing [RuII(bpy)3]2+ (bpy: 2,2′-bipyridine) and S2O82– as a photosensitizer and a sacrificial electron acceptor, respectively. The molecular nature of the Fe chlorin complex during the photocatalytic water oxidation was confirmed by dynamic light scattering analysis and electrospray ionization time-of-flight mass spectrometry. Also, kinetic studies suggested that the rate-determining step is O–O bond formation via coupling of two high-valent iron–oxo species formed by three-electron oxidation of the mononuclear Fe chlorin unit with water. The high planarity of the chlorin ligand enables the high-valent iron–oxo species to approach another iron–oxo unit closely, thereby facilitating O–O bond formation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"37 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221521","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}
Pub Date : 2026-10-20DOI: 10.1021/acscatal.6c04858
Loïc Bénariac-Doumal,Milivoj Plodinec,Luca Artiglia,René Verel,Aram Bugaev,Patrick Hemberger,Andras Bodi,Catherine Dejoie,Thomas C. Hansen,Jeroen A. van Bokhoven,Przemyslaw Rzepka,Vladimir Paunović
The incorporation of selected extraframework cations is a common approach to tuning the performance of zeolite catalysts in industrially relevant methanol-to-hydrocarbons (MTH) conversion processes, although the mechanistic origin of their effects remains incompletely understood. In this study, we investigated the relationships between MTH and coking kinetics, the nature and distribution of coke deposits, and the positions of extraframework calcium and zinc species in the ZSM-5 catalyst, which promote alkene and aromatic formation, respectively. At comparable Brønsted acid site densities, enhanced aromatics formation over zinc-containing ZSM-5 is accompanied by a 2× higher intrinsic MTH activity and a 150× faster active site loss than over the calcium-containing catalyst. Photoelectron photoion coincidence spectroscopy shows that faster coke-forming kinetics over the zinc-containing catalyst is linked to enhanced formaldehyde formation via methanol dehydrogenation, triggering a cascade of intermediates, such as dienes and aromatics, a pathway inhibited in the calcium-containing catalyst. This also leads to a higher fraction of high-molecular-weight coke in the zinc-containing catalyst and a predominance of surface graphitic coke in the calcium-containing catalyst, as revealed by complementary thermogravimetric, microscopic, and spectroscopic analyses. Powder neutron diffraction indicates that coke preferentially occupies the channel intersections and extends along the straight channels in both catalysts. However, the average coke orientation differs as calcium-containing ZSM-5 comprises more distorted intrapore aromatic deposits, whereas zinc-containing ZSM-5 accommodates more planar aromatic coke. The confinement of coke in micropores is consistent with the preferential location of cations determined by high-resolution X-ray diffraction analysis, which shows that calcium occupies two sites in the sinusoidal channels, with one of these pointing toward the channel intersections, whereas the smaller zinc-associated density is found at sites in five- and six-membered rings between main channels, at the expense of occupancy of sinusoidal channel-based positions. Consequently, faster coke-forming kinetics linked to the dehydrogenation activity of extraframework zinc species, together with lower spatial strain at channel intersections, favor the formation of more condensed, planar-like coke in zinc-containing catalysts. Conversely, the larger size and higher channel occupancy of calcium sites destabilize aromatics and hinder coke formation in this key intersecting zone. These results show that extraframework species influence not only the reaction kinetics but also the local organization and orientation of confined coke, in part through steric constraints associated with their crystallographic location.
{"title":"Influence of Extraframework Metal Species on the Kinetics and Spatial Distribution of Coke during Methanol-to-Hydrocarbons Conversion over ZSM-5 Catalysts","authors":"Loïc Bénariac-Doumal,Milivoj Plodinec,Luca Artiglia,René Verel,Aram Bugaev,Patrick Hemberger,Andras Bodi,Catherine Dejoie,Thomas C. Hansen,Jeroen A. van Bokhoven,Przemyslaw Rzepka,Vladimir Paunović","doi":"10.1021/acscatal.6c04858","DOIUrl":"https://doi.org/10.1021/acscatal.6c04858","url":null,"abstract":"The incorporation of selected extraframework cations is a common approach to tuning the performance of zeolite catalysts in industrially relevant methanol-to-hydrocarbons (MTH) conversion processes, although the mechanistic origin of their effects remains incompletely understood. In this study, we investigated the relationships between MTH and coking kinetics, the nature and distribution of coke deposits, and the positions of extraframework calcium and zinc species in the ZSM-5 catalyst, which promote alkene and aromatic formation, respectively. At comparable Brønsted acid site densities, enhanced aromatics formation over zinc-containing ZSM-5 is accompanied by a 2× higher intrinsic MTH activity and a 150× faster active site loss than over the calcium-containing catalyst. Photoelectron photoion coincidence spectroscopy shows that faster coke-forming kinetics over the zinc-containing catalyst is linked to enhanced formaldehyde formation via methanol dehydrogenation, triggering a cascade of intermediates, such as dienes and aromatics, a pathway inhibited in the calcium-containing catalyst. This also leads to a higher fraction of high-molecular-weight coke in the zinc-containing catalyst and a predominance of surface graphitic coke in the calcium-containing catalyst, as revealed by complementary thermogravimetric, microscopic, and spectroscopic analyses. Powder neutron diffraction indicates that coke preferentially occupies the channel intersections and extends along the straight channels in both catalysts. However, the average coke orientation differs as calcium-containing ZSM-5 comprises more distorted intrapore aromatic deposits, whereas zinc-containing ZSM-5 accommodates more planar aromatic coke. The confinement of coke in micropores is consistent with the preferential location of cations determined by high-resolution X-ray diffraction analysis, which shows that calcium occupies two sites in the sinusoidal channels, with one of these pointing toward the channel intersections, whereas the smaller zinc-associated density is found at sites in five- and six-membered rings between main channels, at the expense of occupancy of sinusoidal channel-based positions. Consequently, faster coke-forming kinetics linked to the dehydrogenation activity of extraframework zinc species, together with lower spatial strain at channel intersections, favor the formation of more condensed, planar-like coke in zinc-containing catalysts. Conversely, the larger size and higher channel occupancy of calcium sites destabilize aromatics and hinder coke formation in this key intersecting zone. These results show that extraframework species influence not only the reaction kinetics but also the local organization and orientation of confined coke, in part through steric constraints associated with their crystallographic location.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221621","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}
8,12-Guaianolides are a class of sesquiterpene lactones that exhibit diverse biological activities, which are often strongly influenced by structural variations, including the stereochemistry of the C8 oxygen substituent. Here, we report a concise, diastereodivergent approach to both 8α,12- and 8β,12-guaianolide scaffolds from santonin-derived triene 5 by combining engineered cytochrome P450 BM3-catalyzed allylic C–H hydroxylation with a photochemical rearrangement. The P450 BM3 mutant LG-23 selectively hydroxylates the C8α position of 5, whereas a single additional mutation, L437I, inverts the facial selectivity to favor C8β hydroxylation. Structure-guided mutagenesis and docking studies suggest that the β-methyl group of Ile437 remodels the active site and enforces a flipped substrate binding mode that directs the opposite C8 C–H bond toward the heme iron. The utility of this enzymatic stereochemical switch was demonstrated by the synthesis of the 8α,12-guaianolides xerantholide (1) and mikanokryptin (2) and the 8β,12-guaianolide 11,13-dehydroachalensolide (4). This study demonstrates that a single active-site mutation in P450 BM3 can switch the facial selectivity of C–H hydroxylation at one carbon center, providing a strategy for stereodivergent enzymatic oxidation in complex-molecule synthesis.
{"title":"Diastereodivergent Synthesis of 8,12-Guaianolides Using Engineered P450 BM3","authors":"Ryota Sakamoto,Yuki Okamoto,Ryotaro Hara,Jun Ogawa,Takatsugu Hirokawa,Toshiyuki Sakaki,Kaori Yasuda,Kazuo Nagasawa","doi":"10.1021/acscatal.6c05934","DOIUrl":"https://doi.org/10.1021/acscatal.6c05934","url":null,"abstract":"8,12-Guaianolides are a class of sesquiterpene lactones that exhibit diverse biological activities, which are often strongly influenced by structural variations, including the stereochemistry of the C8 oxygen substituent. Here, we report a concise, diastereodivergent approach to both 8α,12- and 8β,12-guaianolide scaffolds from santonin-derived triene 5 by combining engineered cytochrome P450 BM3-catalyzed allylic C–H hydroxylation with a photochemical rearrangement. The P450 BM3 mutant LG-23 selectively hydroxylates the C8α position of 5, whereas a single additional mutation, L437I, inverts the facial selectivity to favor C8β hydroxylation. Structure-guided mutagenesis and docking studies suggest that the β-methyl group of Ile437 remodels the active site and enforces a flipped substrate binding mode that directs the opposite C8 C–H bond toward the heme iron. The utility of this enzymatic stereochemical switch was demonstrated by the synthesis of the 8α,12-guaianolides xerantholide (1) and mikanokryptin (2) and the 8β,12-guaianolide 11,13-dehydroachalensolide (4). This study demonstrates that a single active-site mutation in P450 BM3 can switch the facial selectivity of C–H hydroxylation at one carbon center, providing a strategy for stereodivergent enzymatic oxidation in complex-molecule synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"45 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221520","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}
Pub Date : 2026-10-20DOI: 10.1021/acscatal.6c07316
Jaeha Lee,Arik Beck
Adsorbate site hopping, defined here as surface-confined migration of adsorbed species or adsorbate equivalents between distinct sites, is a widespread phenomenon in heterogeneous catalysis and includes spillover between different surface phases. Because it enables communication between spatially separated functionalities, site hopping has often been viewed as a route to bifunctional catalytic synergy and, in some cases, to performance beyond constraints imposed by Brønsted–Evans–Polanyi relationships. However, its catalytic value is conditional rather than universal. Downhill migration to a stronger binding site may increase local barriers for subsequent transformation or introduce site-regeneration penalties, while kinetically accessible hopping may remain irrelevant if it does not reduce the energetic span of the catalytic cycle. In addition, apparent rate enhancements assigned to site hopping can arise from other modes of intersite communication, including desorption–readsorption, subsurface or bulk diffusion, ion–electron intersite coupling, catalyst restructuring, or changes in active-site identity. This Perspective develops a thermodynamic and kinetic framework for distinguishing these processes and assessing when site hopping becomes catalytically consequential. We discuss driving forces, hopping barriers, coverage and dynamic surface effects, kinetic signatures, and diagnostic pitfalls, with the aim of clarifying when site hopping can be used as a catalyst design principle.
{"title":"Adsorbate Site Hopping—More Facts and Fiction: Driving Forces and Relevance for Heterogeneous Catalysis","authors":"Jaeha Lee,Arik Beck","doi":"10.1021/acscatal.6c07316","DOIUrl":"https://doi.org/10.1021/acscatal.6c07316","url":null,"abstract":"Adsorbate site hopping, defined here as surface-confined migration of adsorbed species or adsorbate equivalents between distinct sites, is a widespread phenomenon in heterogeneous catalysis and includes spillover between different surface phases. Because it enables communication between spatially separated functionalities, site hopping has often been viewed as a route to bifunctional catalytic synergy and, in some cases, to performance beyond constraints imposed by Brønsted–Evans–Polanyi relationships. However, its catalytic value is conditional rather than universal. Downhill migration to a stronger binding site may increase local barriers for subsequent transformation or introduce site-regeneration penalties, while kinetically accessible hopping may remain irrelevant if it does not reduce the energetic span of the catalytic cycle. In addition, apparent rate enhancements assigned to site hopping can arise from other modes of intersite communication, including desorption–readsorption, subsurface or bulk diffusion, ion–electron intersite coupling, catalyst restructuring, or changes in active-site identity. This Perspective develops a thermodynamic and kinetic framework for distinguishing these processes and assessing when site hopping becomes catalytically consequential. We discuss driving forces, hopping barriers, coverage and dynamic surface effects, kinetic signatures, and diagnostic pitfalls, with the aim of clarifying when site hopping can be used as a catalyst design principle.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"88 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221618","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}
Transition-metal-catalyzed cyclization of 1,n-enynes represents a versatile platform for the construction of structurally diverse chiral heterocycles. Despite substantial advances in this field, the enantioselective cyclizative alkylation of 1,n-enynes remains a formidable synthetic challenge, primarily due to the inherent difficulty in simultaneous control of regio-, chemo-, and stereoselectivity. Herein, we disclose a highly enantioselective cyclizative alkylation of 1,6-enynes employing two complementary alkylating reagents: diazo compounds and readily available alkyl iodides. This protocol proceeds under mild conditions and features broad substrate scope, delivering enantioenriched γ-lactams and pyrrolidine derivatives bearing quaternary stereogenic centers in good yields (up to 81%) and enantioselectivities (53 examples, up to 98% ee). Mechanistic studies corroborate that these two types of alkylating reagents follow entirely distinct catalytic pathways.
{"title":"Nickel-Catalyzed Enantioselective Cyclizative Alkylation of 1,6-Enynes with Diazo Compounds and Alkyl Halides","authors":"Yongli Liu,Shengwei Hu,Wangqing Kong,Yuanyuan Ping","doi":"10.1021/acscatal.6c05711","DOIUrl":"https://doi.org/10.1021/acscatal.6c05711","url":null,"abstract":"Transition-metal-catalyzed cyclization of 1,n-enynes represents a versatile platform for the construction of structurally diverse chiral heterocycles. Despite substantial advances in this field, the enantioselective cyclizative alkylation of 1,n-enynes remains a formidable synthetic challenge, primarily due to the inherent difficulty in simultaneous control of regio-, chemo-, and stereoselectivity. Herein, we disclose a highly enantioselective cyclizative alkylation of 1,6-enynes employing two complementary alkylating reagents: diazo compounds and readily available alkyl iodides. This protocol proceeds under mild conditions and features broad substrate scope, delivering enantioenriched γ-lactams and pyrrolidine derivatives bearing quaternary stereogenic centers in good yields (up to 81%) and enantioselectivities (53 examples, up to 98% ee). Mechanistic studies corroborate that these two types of alkylating reagents follow entirely distinct catalytic pathways.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"7 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218884","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}
Pub Date : 2026-10-19DOI: 10.1021/acscatal.6c06363
Jie Zhou,Zeyu Wu,Yang Zhang,Kai Zhang,Guihua Liu,Lanlan Wu,Jingde Li
Efficient activation of interfacial water molecules and fast proton transfer are critical but challenging for the acidic oxygen evolution reaction (OER). Herein, a Lewis–Brønsted dual-acid catalyst design strategy is proposed to achieve accelerated acidic OER by synergistically optimizing the configuration of interfacial water molecules and proton transfer kinetics on Mn-doped IrO2. In this catalyst, the Mn dopant serves as a Lewis acid site that readily captures hydroxyl groups, which perturbs the local hydrogen-bonding network and induces interfacial water molecules to form an H-down configuration toward surface active sites, thereby promoting the enrichment and dissociation of reactive interfacial water. On this basis, the formation of the Mn–Obri–Ir local structure enhances the Brønsted acidity of the bridge oxygen (Obri) site, accelerates the deprotonation of the Obri–H bond, promotes the formation of key OER intermediates and accelerates the reaction kinetics. Mn dopant also induces electron enrichment around Ir, suppresses excessive oxidation and dissolution of Ir species, and enhances catalyst stability performance. These synergistic effects enable Mn-IrO2 to achieve a 160 mV overpotential at 10 mA cm–2 and to operate stably for 1500 h at 10 mA cm–2 and 1200 h at 1.0 A cm–2 in proton exchange membrane water electrolysis (PEMWE), demonstrating the promising potential of the Lewis–Brønsted dual-acid strategy in acidic OER catalyst design.
界面水分子的高效活化和快速质子转移是酸性析氧反应（OER）的关键和难点。本文提出Lewis-Brønsted双酸催化剂设计策略，通过协同优化界面水分子构型和mn掺杂IrO2上的质子转移动力学，实现加速酸性OER。在该催化剂中，Mn掺杂物作为路易斯酸位点，容易捕获羟基，扰乱局部氢键网络，诱导界面水分子向表面活性位点形成H-down构型，从而促进活性界面水的富集和解离。在此基础上，Mn-Obri-Ir局部结构的形成增强了桥氧（Obri）位点的Brønsted酸性，加速了Obri - h键的去质子化，促进了关键OER中间体的形成，加速了反应动力学。Mn掺杂还能诱导Ir周围的电子富集，抑制Ir的过度氧化和溶解，提高催化剂的稳定性。这些协同效应使Mn-IrO2在10 mA cm-2下达到160 mV的过电位，并在10 mA cm-2下稳定运行1500小时，在1.0 a cm-2下稳定运行1200小时，在质子交换膜电解（PEMWE）中，展示了louis - br ønsted双酸策略在酸性OER催化剂设计中的潜力。
{"title":"Lewis–Brønsted Dual-Acid Sites Induced H-Down Interfacial Water Configuration and Accelerated Proton Transfer toward Enhanced Acidic Oxygen Evolution","authors":"Jie Zhou,Zeyu Wu,Yang Zhang,Kai Zhang,Guihua Liu,Lanlan Wu,Jingde Li","doi":"10.1021/acscatal.6c06363","DOIUrl":"https://doi.org/10.1021/acscatal.6c06363","url":null,"abstract":"Efficient activation of interfacial water molecules and fast proton transfer are critical but challenging for the acidic oxygen evolution reaction (OER). Herein, a Lewis–Brønsted dual-acid catalyst design strategy is proposed to achieve accelerated acidic OER by synergistically optimizing the configuration of interfacial water molecules and proton transfer kinetics on Mn-doped IrO2. In this catalyst, the Mn dopant serves as a Lewis acid site that readily captures hydroxyl groups, which perturbs the local hydrogen-bonding network and induces interfacial water molecules to form an H-down configuration toward surface active sites, thereby promoting the enrichment and dissociation of reactive interfacial water. On this basis, the formation of the Mn–Obri–Ir local structure enhances the Brønsted acidity of the bridge oxygen (Obri) site, accelerates the deprotonation of the Obri–H bond, promotes the formation of key OER intermediates and accelerates the reaction kinetics. Mn dopant also induces electron enrichment around Ir, suppresses excessive oxidation and dissolution of Ir species, and enhances catalyst stability performance. These synergistic effects enable Mn-IrO2 to achieve a 160 mV overpotential at 10 mA cm–2 and to operate stably for 1500 h at 10 mA cm–2 and 1200 h at 1.0 A cm–2 in proton exchange membrane water electrolysis (PEMWE), demonstrating the promising potential of the Lewis–Brønsted dual-acid strategy in acidic OER catalyst design.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"33 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221624","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}
Pub Date : 2026-10-19DOI: 10.1021/acscatal.6c06565
Shangkun Li,Zhongyuan Wei,Yuping Yang,Yanhui Yi,Nick Gerrits,Erik C. Neyts,Bart Partoens,Annemie Bogaerts
Selective one-step conversion of methane (CH4) to methanol (CH3OH) remains a grand challenge in catalysis, constrained by the trade-off between C─H bond activation and product overoxidation. Here, we integrate density functional theory (DFT) calculations with plasma-catalytic experiments to investigate direct CH4-to-CH3OH conversion using H2O as the sole oxidant on CuxOy clusters within MOR zeolite, compared to the CuO(111) surface. We show that C─H bond activation proceeds preferentially via homolytic H-abstraction on zeolite-confined CuxOy clusters, with Cu3O3/MOR exhibiting a low activation barrier of only 0.21 eV, more than three times lower than that on CuO(111). Vibrational mode-specificity analysis shows that the C─H stretching modes couple most effectively on higher-barrier surfaces. Importantly, we demonstrate that plasma-generated radical intermediates (CH3·, H·, OH·) reshape the reaction thermodynamics, with the Gibbs free energy shifting from endothermic (+1.13 eV) to exothermic (–3.21 eV and –8.25 eV), enabling pathways inaccessible under thermal conditions. Experimentally, Cu/MOR catalysts prepared by ion exchange, which favor well-dispersed zeolite-confined Cu-oxo sites, achieve the highest CH3OH production rate (0.26 mmol/h) at low plasma power (6.5 W), outperforming catalysts prepared by wetness impregnation. This work bridges Cu-oxo site topology, vibrational mode specificity, and radical-mediated thermodynamics, offering valuable insights for plasma-catalytic selective CH4-to-CH3OH conversion.
{"title":"Plasma-Enabled Direct Methane-to-Methanol Conversion on Zeolite-Confined Copper-Oxo Clusters: Insight into Vibrational Excitation and Radical-Mediated Process","authors":"Shangkun Li,Zhongyuan Wei,Yuping Yang,Yanhui Yi,Nick Gerrits,Erik C. Neyts,Bart Partoens,Annemie Bogaerts","doi":"10.1021/acscatal.6c06565","DOIUrl":"https://doi.org/10.1021/acscatal.6c06565","url":null,"abstract":"Selective one-step conversion of methane (CH4) to methanol (CH3OH) remains a grand challenge in catalysis, constrained by the trade-off between C─H bond activation and product overoxidation. Here, we integrate density functional theory (DFT) calculations with plasma-catalytic experiments to investigate direct CH4-to-CH3OH conversion using H2O as the sole oxidant on CuxOy clusters within MOR zeolite, compared to the CuO(111) surface. We show that C─H bond activation proceeds preferentially via homolytic H-abstraction on zeolite-confined CuxOy clusters, with Cu3O3/MOR exhibiting a low activation barrier of only 0.21 eV, more than three times lower than that on CuO(111). Vibrational mode-specificity analysis shows that the C─H stretching modes couple most effectively on higher-barrier surfaces. Importantly, we demonstrate that plasma-generated radical intermediates (CH3·, H·, OH·) reshape the reaction thermodynamics, with the Gibbs free energy shifting from endothermic (+1.13 eV) to exothermic (–3.21 eV and –8.25 eV), enabling pathways inaccessible under thermal conditions. Experimentally, Cu/MOR catalysts prepared by ion exchange, which favor well-dispersed zeolite-confined Cu-oxo sites, achieve the highest CH3OH production rate (0.26 mmol/h) at low plasma power (6.5 W), outperforming catalysts prepared by wetness impregnation. This work bridges Cu-oxo site topology, vibrational mode specificity, and radical-mediated thermodynamics, offering valuable insights for plasma-catalytic selective CH4-to-CH3OH conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"7 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218857","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}
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