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Origin of the strong metal-support interaction in Pd/TiO2 Pd/TiO2中强金属-载体相互作用的起源
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-09-22 DOI: 10.1016/j.jcat.2025.116448
Elizaveta Kozyr , Paul Paciok , Kwinten Janssens , Valeria Lagostina , Riccardo Pellegrini , Oleg Usoltsev , Alina Skorynina , Mario Chiesa , Dirk De Vos , Elena Groppo , Lorenzo Mino , Aram Bugaev
{"title":"Origin of the strong metal-support interaction in Pd/TiO2","authors":"Elizaveta Kozyr ,&nbsp;Paul Paciok ,&nbsp;Kwinten Janssens ,&nbsp;Valeria Lagostina ,&nbsp;Riccardo Pellegrini ,&nbsp;Oleg Usoltsev ,&nbsp;Alina Skorynina ,&nbsp;Mario Chiesa ,&nbsp;Dirk De Vos ,&nbsp;Elena Groppo ,&nbsp;Lorenzo Mino ,&nbsp;Aram Bugaev","doi":"10.1016/j.jcat.2025.116448","DOIUrl":"10.1016/j.jcat.2025.116448","url":null,"abstract":"<div><div>Strong metal-support interaction (SMSI) is a crucial factor in stabilizing metal nanoparticles (NPs) on reducible metal-oxides, affecting their dispersion, morphology, and catalytic properties. In this study, we show that tuning the synthesis protocol allows for the preparation of Pd/TiO<sub>2</sub> catalysts with distinctly different metal-support interactions, and we investigate the underlying mechanisms behind these variations. Catalysts prepared via deposition–precipitation exhibit weak Pd-TiO<sub>2</sub> interactions, whereas an evident SMSI effect is observed in the ones prepared by photodeposition. The latter samples demonstrate remarkable stability of the metallic phase even under high-temperature oxidizing conditions, unusual for Pd NPs. A comprehensive multi-technique study allowed attributing the SMSI effect to the presence of Ti<sup>3+</sup> sites at the Pd/TiO<sub>2</sub> interface, detected by electron paramagnetic resonance (EPR) and electron energy loss (EELS) spectroscopies, and direct Pd‒Ti interactions, observed in X-ray absorption spectroscopy (XAS) data, in the photodeposited Pd/TiO<sub>2</sub> catalyst. These features were not observed in the case of the deposition–precipitation method, due to the distinct formation mechanisms of the Pd NPs.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116448"},"PeriodicalIF":6.5,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116723","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}
引用次数: 0
Suitable alkali cations improved Mn(I)-catalyzed hydrogenation of esters: An insight into the effect of bases and ligands’ ring sizes on catalytic performance 合适的碱阳离子改善了Mn(I)催化酯的加氢反应:碱和配体的环大小对催化性能的影响
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-09-18 DOI: 10.1016/j.jcat.2025.116436
Yi Su , Zhifeng Ma , Peng Han , Xiaojian Ren , Ning Ma , Qingbin Liu , Qianrong Cao , Zheng Wang
{"title":"Suitable alkali cations improved Mn(I)-catalyzed hydrogenation of esters: An insight into the effect of bases and ligands’ ring sizes on catalytic performance","authors":"Yi Su ,&nbsp;Zhifeng Ma ,&nbsp;Peng Han ,&nbsp;Xiaojian Ren ,&nbsp;Ning Ma ,&nbsp;Qingbin Liu ,&nbsp;Qianrong Cao ,&nbsp;Zheng Wang","doi":"10.1016/j.jcat.2025.116436","DOIUrl":"10.1016/j.jcat.2025.116436","url":null,"abstract":"<div><div>Pincer Mn(I)-complexes (<strong>Mn-1</strong>–<strong>Mn-9</strong>) bearing a family of ferrocenyl-based PNN-ligands containing the cycloalkyl anywhere ring sizes of from five to eight, were successfully employed as efficient catalysts for ester hydrogenation. Among them, <strong>Mn-1</strong>, in combination with 10 mol% base-containing Li<sup>+</sup> or Na<sup>+</sup> (especially NaBH<sub>4</sub> and LiH), proved to be the highest activity catalyst, further confirming its lowest Gibbs free energy values for H<sub>2</sub> activation. Control experiments and DFT calculations highlight the role and rule of cations and/or anions of bases during heterolytic H<sub>2</sub> cleavage and hydride transfer process for Mn-catalyzed hydrogenation. In particular, either NaBH<sub>4</sub> or LiH as base, their comparative performance was studied and calculated with <strong>Mn-1</strong> as catalyst, two possible cycles of alkali cations participating in the hydrogenation pathway were proposed. Employing suitable alkali cations enhancing the <strong>Mn-H</strong> catalyst, various aromatic and aliphatic esters (37 examples) were hydrogenated to the corresponding bulk and fine alcohols, offering a turnover number (TON) reaching up to 6000.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116436"},"PeriodicalIF":6.5,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084243","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}
引用次数: 0
Catalytic oxidation of sulfides and alcohols by vanadium, molybdenum, and tungsten Schiff base complexes: A combined structural, spectral, and theoretical study 钒、钼和钨希夫碱络合物对硫化物和醇的催化氧化:结构、光谱和理论的综合研究
IF 7.3 1区 化学
Journal of Catalysis Pub Date : 2025-09-18 DOI: 10.1016/j.jcat.2025.116441
Mehdi Fallah-Mehrjardi, Hadi Kargar, Khurram Shahzad Munawar, Muhammad Ashfaq
{"title":"Catalytic oxidation of sulfides and alcohols by vanadium, molybdenum, and tungsten Schiff base complexes: A combined structural, spectral, and theoretical study","authors":"Mehdi Fallah-Mehrjardi, Hadi Kargar, Khurram Shahzad Munawar, Muhammad Ashfaq","doi":"10.1016/j.jcat.2025.116441","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116441","url":null,"abstract":"This review article presents a comprehensive overview of our studies on the catalytic oxidation of sulfides and alcohols using vanadium(V), molybdenum(VI), and tungsten(VI) Schiff base complexes, integrating structural, spectral, and theoretical insights. The novelty of this work lies in combining single-crystal X-ray diffraction (SC-XRD), advanced spectroscopic techniques (FT-IR, NMR, UV–Vis), and density functional theory (DFT) to establish clear structure–property–reactivity relationships. The synthesized hydrazone-based Schiff base complexes are systematically analyzed to elucidate their electronic structures, reactivity trends, and catalytic mechanisms through Mulliken charge distribution and frontier molecular orbital (FMO) studies. Catalytic performance is evaluated in sulfide oxidation (yielding sulfoxides or sulfones) and selective benzyl alcohol oxidation (producing aldehydes), with mechanistic pathways strongly supported by computational modeling. Furthermore, the heterogenization of selected complexes on solid supports demonstrates enhanced recyclability and catalytic efficiency, highlighting their potential applications in sustainable oxidation processes.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"154 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084190","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}
引用次数: 0
Bifunctional C2-symmetric chiral chloramphenicol base-phosphorodiamides as highly active hydrogen bond donor organocatalysts for enantioselective acyl-transfer reaction 双功能c2对称手性氯霉素基磷二胺作为对映选择性酰基转移反应的高活性氢键供体有机催化剂
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-09-18 DOI: 10.1016/j.jcat.2025.116438
Fei Xiong, Jie Xu, Yi Gong, Zhenyu Zhang, Jie Zhong, Junjie Zhan, Xiaoxue Chen, Yiren Zhu
{"title":"Bifunctional C2-symmetric chiral chloramphenicol base-phosphorodiamides as highly active hydrogen bond donor organocatalysts for enantioselective acyl-transfer reaction","authors":"Fei Xiong,&nbsp;Jie Xu,&nbsp;Yi Gong,&nbsp;Zhenyu Zhang,&nbsp;Jie Zhong,&nbsp;Junjie Zhan,&nbsp;Xiaoxue Chen,&nbsp;Yiren Zhu","doi":"10.1016/j.jcat.2025.116438","DOIUrl":"10.1016/j.jcat.2025.116438","url":null,"abstract":"<div><div>A highly efficient, structurally well-designed and recyclable <em>C</em><sub>2</sub>-symmetric tertiary amine-phosphorodiamide organocatalyst for enantioselective acyl-transfer reaction has been elaborated, allowing for stereocontrol and tuning of reactivity. In the presence of only 2 mol% of this organocatalyst, various <em>meso</em>-cyclic anhydrides reacted with alcohol, affording the corresponding chiral hemiesters in high yield (up to 97 %) with excellent stereocontrol (ee, up to 99.8 %). This protocol can be readily extended for the synthesis of chiral drug precursor of (<em>S</em>)-pregabalin with up to 90 % yield and 99.8 % ee, overcoming some of the traditional limitations of using high catalyst loading.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116438"},"PeriodicalIF":6.5,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084239","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}
引用次数: 0
Cationic indium complexes halve H2 partial pressure in CO2 reductive coupling reactions with amines 在与胺的CO2还原偶联反应中,阳离子铟配合物使H2分压减半
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-09-18 DOI: 10.1016/j.jcat.2025.116445
Pritha Saha , Martin Zábranský , Laura E. English , Andrew R. Jupp , Martin Hulla
{"title":"Cationic indium complexes halve H2 partial pressure in CO2 reductive coupling reactions with amines","authors":"Pritha Saha ,&nbsp;Martin Zábranský ,&nbsp;Laura E. English ,&nbsp;Andrew R. Jupp ,&nbsp;Martin Hulla","doi":"10.1016/j.jcat.2025.116445","DOIUrl":"10.1016/j.jcat.2025.116445","url":null,"abstract":"<div><div>Indium-catalysed homogeneous hydrogenations are limited to imine hydrogenation due to the low thermal and hydrolytic stability of In(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>, the only indium Lewis acid used thus far for hydrogenation chemistry. In this study, we present [In(terpy)Cl<sub>2</sub>]<sup>+</sup> cations as Lewis acid catalysts. With an optimal vacant site for H<sub>2</sub> activation and a hydride ion affinity of up to 579 kJ mol<sup>−1</sup>, [In(terpy)Cl<sub>2</sub>]<sup>+</sup> effectively catalysed CO<sub>2</sub> reductive coupling with amines under H<sub>2</sub> (50 bar) and CO<sub>2</sub> (4 bar) pressure, as structurally confirmed by XRD and NMR spectroscopy. By catalysing CO<sub>2</sub> reductive coupling with amines at half the partial pressure of all other main-group catalytic systems with H<sub>2</sub>, cationic indium complexes set a new benchmark for such reactions. Therefore, this study not only expands the scope of indium-based catalysis beyond imine hydrogenation but also highlights the potential of ligand-supported indium Lewis acids as catalytic systems for small-molecule activation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116445"},"PeriodicalIF":6.5,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077884","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}
引用次数: 0
Palladium-catalyzed carbonylative double cyclization leading to indole-fused ε- and ζ-lactones 钯催化羰基双环化反应生成吲哚熔融ε-和ζ-内酯
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-09-18 DOI: 10.1016/j.jcat.2025.116437
Raffaella Mancuso , Patrizio Russo , Alex De Salvo , Haritha Kumari Arram , Sofia Tropiano , Corrado Cuocci , Diego Olivieri , Carla Carfagna , Nicola Della Ca’ , Bartolo Gabriele
{"title":"Palladium-catalyzed carbonylative double cyclization leading to indole-fused ε- and ζ-lactones","authors":"Raffaella Mancuso ,&nbsp;Patrizio Russo ,&nbsp;Alex De Salvo ,&nbsp;Haritha Kumari Arram ,&nbsp;Sofia Tropiano ,&nbsp;Corrado Cuocci ,&nbsp;Diego Olivieri ,&nbsp;Carla Carfagna ,&nbsp;Nicola Della Ca’ ,&nbsp;Bartolo Gabriele","doi":"10.1016/j.jcat.2025.116437","DOIUrl":"10.1016/j.jcat.2025.116437","url":null,"abstract":"<div><div>The reactivity of 5-(2-aminophenyl)-4-yn-1-ols and 6-(2-aminophenyl)-5-yn-1-ols under PdI<sub>2</sub>/KI-catalyzed oxidative carbonylation conditions has been studied. It has been found that, with 5 mol% of PdI<sub>2</sub> and 0.5 equiv. of KI, under 60 bar of a 4:1 mixture of CO-air, in MeOH as the solvent at 100 °C for 24 h, a mixture of isomeric indole-fused ε-lactone and pyranoquinolinone derivatives was formed from 5-(2-aminophenyl)-4-yn-1-ols, deriving from divergent 5-<em>endo</em>-<em>dig N</em>-cyclization ‒ 7-<em>O</em>-cyclocarbonylation and 6-<em>endo</em>-<em>dig O</em>-cyclization – 6-<em>N</em>-cyclocarbonylation pathways, respectively. However, the process could be made selective toward the formation of the indole-fused ε-lactone (oxepinoindolone) product when performed in MeCN, thus establishing an unprecedented cyclization – seven-membered cyclocarbonylation process. Under the optimized conditions, a series of previously unknown 6-substituted 3,4,5,6-tetrahydro-1<em>H</em>-oxepino[4,3-<em>b</em>]indol-1-ones could be synthesized in moderate to satisfactory isolated yields (45–79 %) starting from differently substituted 5-(2-aminophenyl)-4-yn-1-ols. Under the same conditions, 6-(2-aminophenyl)-5-yn-1-ols were converted into indole-fused ζ-lactones through an even more challenging cyclization – eight-membered cyclocarbonylation process. The structures of three representative products have been confirmed by XRD analysis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116437"},"PeriodicalIF":6.5,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084244","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}
引用次数: 0
Atomic-scale hydrogen dynamics on (sub)nano-sized Ir/γ-Al2O3: chemisorption, spillover, and reverse spillover via combined theory-experiment 亚纳米Ir/γ-Al2O3上的原子尺度氢动力学:化学吸附、溢出和理论-实验相结合的反向溢出
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-09-18 DOI: 10.1016/j.jcat.2025.116433
Shengming Zhang, Xuerong Shi, Min Zhu, Xinlei Yu, Runlin Wang, Peijie Wang, Haichao Xiong, Shusheng Xu
{"title":"Atomic-scale hydrogen dynamics on (sub)nano-sized Ir/γ-Al2O3: chemisorption, spillover, and reverse spillover via combined theory-experiment","authors":"Shengming Zhang,&nbsp;Xuerong Shi,&nbsp;Min Zhu,&nbsp;Xinlei Yu,&nbsp;Runlin Wang,&nbsp;Peijie Wang,&nbsp;Haichao Xiong,&nbsp;Shusheng Xu","doi":"10.1016/j.jcat.2025.116433","DOIUrl":"10.1016/j.jcat.2025.116433","url":null,"abstract":"<div><div>Atomic-scale insights into hydrogen chemisorption, spillover, and reverse spillover on metal-oxide-supported metal (sub)nanoparticles are crucial for advancing hydrogen-related technologies. Using a combined calculations-experiments approach, we systematically studied these processes on hydrated γ-Al<sub>2</sub>O<sub>3</sub>(110) supported Ir<em><sub>n</sub></em> subnanoparticles (<em>n</em> = 1, 2, 4, 6, 22) and Ir<sub>91</sub> nanoparticle. A density-functional theory (DFT) investigation into the influence of Ir (sub)nanoparticles size on the processes of hydrogen chemisorption, spillover, and reverse spillover was initially performed. The maximum H/Ir(surf) adsorption ratio decreases with increasing cluster size (saturation ratios: 3 for Ir<sub>1</sub>, 2.11 for Ir<sub>22</sub>, and &lt;2 for Ir<sub>91</sub>), accompanied by significant (sub)nano-sized metal deformation under high H-loading. Most hydrogen spillover is thermodynamically unfavorable. Reverse spillover is favored for many supported Ir<em><sub>n</sub></em> clusters (<em>n</em> = 1, 2, 4, 6). Thermodynamic analysis indicates partial hydrogen retention on small Ir<em><sub>n</sub></em> clusters under moderate H<sub>2</sub> pressure (0.01 atm) and temperatures at 925 K, due to strong binding at undercoordinated Ir sites. H<sub>2</sub> temperature-programmed reduction/desorption (H<sub>2</sub>-TPR/TPD) experiments confirm computational insights. Peaks at ∼518, 709, and 809 K in H<sub>2</sub>-TPR curves are assigned to the reduction of surface IrO<sub>2</sub>, interfacial Ir-O-Al species, and Ir-induced oxygen-deficient Al<sub>2</sub>O<sub>3</sub>, respectively. This work elucidates the fundamental atomic-scale nature of hydrogen interactions on supported (sub)nanometer metal clusters.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116433"},"PeriodicalIF":6.5,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084274","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}
引用次数: 0
Cross-coupling catalysts for inactive substrates from a three-dimensional virtual screening 非活性底物交叉偶联催化剂的三维虚拟筛选
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-09-17 DOI: 10.1016/j.jcat.2025.116446
Arron L. Burnage, Hannes Kneiding, Ainara Nova, David Balcells
{"title":"Cross-coupling catalysts for inactive substrates from a three-dimensional virtual screening","authors":"Arron L. Burnage,&nbsp;Hannes Kneiding,&nbsp;Ainara Nova,&nbsp;David Balcells","doi":"10.1016/j.jcat.2025.116446","DOIUrl":"10.1016/j.jcat.2025.116446","url":null,"abstract":"<div><div>We report a three-dimensional virtual screening method to search a chemical space formed of ligands from the tmQMg-L library for Pd Suzuki–Miyaura cross-coupling catalysts that has future potential to be applied to a broader range of catalytic reactions. It utilises three criteria related to important steps in the catalytic cycle of the reaction to distinguish between candidate Pd(0) species, namely the oxidative addition and reductive elimination barriers and the binding energy of acetonitrile. This method ultimately leads to identifying a region of chemical space that provides a good compromise between the three search criteria, highlighting a smaller set of ligands that merits further exploration. After the screening, several candidates are confirmed as catalysts based on literature searches. We also found Pd(0) complexes with high potential in catalytic cross-couplings involving less reactive substrates that require the oxidative addition of strong C–O bonds.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116446"},"PeriodicalIF":6.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077911","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}
引用次数: 0
Transformations of tungstacyclopentane species in a WOx/SiO2 catalyst: Different pathways generating olefin metathesis active sites 钨环戊烷在WOx/SiO2催化剂中的转化:生成烯烃转化活性位点的不同途径
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-09-17 DOI: 10.1016/j.jcat.2025.116432
Jarosław Handzlik
{"title":"Transformations of tungstacyclopentane species in a WOx/SiO2 catalyst: Different pathways generating olefin metathesis active sites","authors":"Jarosław Handzlik","doi":"10.1016/j.jcat.2025.116432","DOIUrl":"10.1016/j.jcat.2025.116432","url":null,"abstract":"<div><div>Surface tungstacyclopentane species can be formed from alkenes and W(IV) oxide species in the industrial WO<sub>x</sub>/SiO<sub>2</sub> catalyst for large scale olefin metathesis. In this work, density functional theory (DFT) studies of various experimentally observed transformations of silica-supported unsubstituted tungstacyclopentane species, leading mainly to the formation of olefin metathesis active sites, have been performed. It is shown that the conversion of square pyramidal tungstacyclopentane to W(VI) butylidene species via 1,4-hydrogen transfer is slightly more kinetically favored than the ring contraction to α-methyl-substituted tungstacyclobutane through W(VI) butenyl hydride intermediate. In the case of tungstacyclopentane species with the trigonal bipyramidal geometry, the ring contraction can also occur in a single step. Ethene insertion into the secondary W-C bond of the α-methyl-substituted tungstacyclobutane, giving γ-methyl-substituted tungstacyclohexane species, has also been examined. The activation barriers of the tungstacyclopentane transformations can be reduced by about 50 kJ mol<sup>−1</sup> if a surface silanol group adjacent to the metal site takes part. Initially, W(VI) butyl species are formed, which can then convert to W(VI) butylidene species, α-methyl-substituted tungstacyclobutane or 1-butene together with the monooxo W(IV) species. The proposed silanol-assisted transformations of surface tungstacyclopentane species yielding olefin metathesis active sites may compete with other reported activation mechanisms involving a silanol group.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116432"},"PeriodicalIF":6.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077885","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}
引用次数: 0
Regioselective hydroformylation of sterically hindered olefins over single-atom Rh sites on porous organic polymer incorporating hybrid phosphine ligands 含杂化膦配体的多孔有机聚合物上单原子Rh位点上空间位阻烯烃的区域选择性氢甲酰化
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-09-17 DOI: 10.1016/j.jcat.2025.116439
Xin Zhou , Yuanjun Zhao , Pengzhen Yin , Zhaozhan Wang , Xingtao Zhao , Fengqi Zhang , Huibing Shi , Dmitry Gorbunov , Yong Yang
{"title":"Regioselective hydroformylation of sterically hindered olefins over single-atom Rh sites on porous organic polymer incorporating hybrid phosphine ligands","authors":"Xin Zhou ,&nbsp;Yuanjun Zhao ,&nbsp;Pengzhen Yin ,&nbsp;Zhaozhan Wang ,&nbsp;Xingtao Zhao ,&nbsp;Fengqi Zhang ,&nbsp;Huibing Shi ,&nbsp;Dmitry Gorbunov ,&nbsp;Yong Yang","doi":"10.1016/j.jcat.2025.116439","DOIUrl":"10.1016/j.jcat.2025.116439","url":null,"abstract":"<div><div>Developing heterogeneous catalysts capable of efficient and regioselective hydroformylation of sterically hindered alkenes remains a significant challenge. In this work, we develop a stable and active Rh single-atom catalyst (Rh@POP-X) anchored on a hybrid phosphine-functionalized porous organic polymer (POP) with tailored porosity and high specific surface area, allowing for hydroformylation of sterically hindered diisobutylene (DIB). Comprehensive characterizations including solid-state NMR, AC HAADF-STEM, XPS, in-situ CO-DRIFTS, XAS confirm the atomic dispersion of Rh sites coordinated by phosphine ligands within the crosslinked polymeric network. The optimal catalyst Rh@POP-2 exhibits exceptional performance, achieving &gt;98 % conversion with excellent regioselectivity toward linear isononanal. Remarkably, the Rh@POP-2 catalyst demonstrates high stability, maintaining its catalytic performance over 10 times successive reaction cycles without significant deactivation. The versatility of this catalytic system is further demonstrated by its broad substrate adaptability, enabling efficient hydroformylation of various olefins, including linear, terminal, aromatic, and sterically hindered olefins, to yield their corresponding C<sub>1+</sub> aldehydes. This work provides a general strategy for designing robust single-atom catalysts for challenging hydroformylation of sterically hindered olefins.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116439"},"PeriodicalIF":6.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077886","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}
引用次数: 0
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