Microenvironment Modulation for Electronic Structure of Atomically Dispersed Ir Species in Metal–Organic Frameworks Toward Boosting Catalytic DCPD Hydrogenation Performance

Carbon Neutralization, Journal Year: 2025, Volume and Issue: 4(2)

Published: March 1, 2025

ABSTRACT The fine‐tuning of the electronic structure and local environment surrounding atomically dispersed metal centers is crucial in catalysis but remains a grand challenge that requires in‐depth exploration. In this study, Ir species were incorporated into series UiO‐type metal−organic frameworks via strong metal–support interactions (SMSI), their state was precisely modulated by regulating metal‐oxo clusters (Ce, Zr, Hf) organic ligands (BDC‐X, where X = ‐H, ‐NH 2 , ‐Me, or ‐NO ) for enhancing catalytic performance dicyclopentadiene (DCPD) hydrogenation. optimized Ir@Ce‐UiO‐66‐NO effectively transforms DCPD tetrahydrodicyclopentadiene (THDCPD), giving 100% conversion over 99% THDCPD selectivity, far superior to corresponding counterparts. Experimental theoretical results jointly demonstrated Ce‐oxo with unique Ce III /Ce IV redox pairs can facilitate electron transfer species. Furthermore, electron‐withdrawing groups play role increasing ratio, promoting efficient uptake MOF support leading low density around species, which enhances stronger between substrate molecules active sites contributes excellent activity. findings presented work provide valuable insights rational design advanced heterogeneous catalysts leveraging properties modulation capabilities supports.

Language: Английский

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Aromatic compounds‐mediated synthesis of anatase‐free hierarchical TS‐1 zeolite: Exploring design strategies via machine learning and enhanced catalytic performance

Aggregate, Journal Year: 2023, Volume and Issue: 4(4)

Published: Jan. 28, 2023

Abstract Simultaneous achievement of constructing mesopores and eliminating anatase is a long‐term pursuit for enhancing the catalytic performance TS‐1. Here, we developed an aromatic compounds‐mediated synthesis method to prepare anatase‐free hierarchical TS‐1 olefin epoxidation. A series zeolites were prepared by introducing compounds containing different functional groups via crystallization process. The formation intercrystalline insertion titanium into framework facilitated at extent. synergistic coordination carboxyl hydroxyl in with Ti(OH) 4 realizes uniform distribution species eliminates generation anatase. Noteworthily, eight machine learning models trained reveal mechanism additive preparation conditions on microstructure optimization. prediction accuracy most can reach more than 80%. Benefiting from larger mesopore volumes (0.37 cm 3 ·g −1 ) higher content Ti species, TS‐DHBDC‐48h samples exhibit other zeolites, giving 1‐hexene conversion 49.3% 1,2‐epoxyhenane selectivity 99.9%. paper provides facile strategy promotes application toward design optimization new zeolites.

Language: Английский

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Recent advances in biomass-assisted synthesis of hierarchical porous zeolite

Materials Today Sustainability, Journal Year: 2024, Volume and Issue: 27, P. 100917 - 100917

Published: July 14, 2024

Language: Английский

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Comprehensive Theoretical Study of Cp*Ir^III-Catalyzed Intermolecular Enantioselective Allylic C–H Amidation: Reaction Mechanism, Electronic Processes, and Regioselectivity

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(4), P. 2493 - 2504

Published: Jan. 30, 2023

Density functional theory was used to elucidate the reaction mechanism of Cp*IrIII-catalyzed intermolecular regioselective C(sp3)-H amidation alkenes with methyl dioxazolones. All substrates, intermediates, and transition states were fully optimized at ωB97XD/6-31G(d,p) level (LANL2DZ(f) for Ir). The computational results revealed that this occurred through IrIII/IrV catalytic cycle, involving four important elementary steps: C-H bond activation, oxidative addition dioxazolone, reductive elimination, proto-demetalation, first rate-determining step. activation showed good α- branch-regioselectivity, decided by distortion energy 2-pentene interaction state, respectively. dioxazolone in one step CO2 disassociation. elimination branch-regioselectivity determined distorted allyl group. In hydrogen directly transferred from oxygen atom nitrogen atom. Moreover, clarify effect substituted groups, selected 12 substrates also discussed text.

Language: Английский

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Ir(iii)/Ag(i)-catalyzed directly C–H amidation of arenes with OH-free hydroxyamides as amidating agents

RSC Advances, Journal Year: 2024, Volume and Issue: 14(9), P. 5975 - 5980

Published: Jan. 1, 2024

A versatile Ir( iii )-catalyzed C–H amidation of arenes by employing readily available and stable OH-free hydroxyamides as a novel source.

Language: Английский

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Efficient Removal of Azine Directing Group Using Oxone in Acetone for Application in Protection-Deprotection and Ch Functionalization Chemistry

Published: Jan. 1, 2023

Azine derivatives of carbonyl compounds have been used as protecting groups in the past and directing CH activation recently. Stability azine functional limits its application areas where removal group is desirable. We hereby report a mild efficient using green oxidant oxone presence acetone water solvent system. The regeneration has afforded high yields from range aldazine ketazine to demonstrate substrate scope. Gram scale synthesis DG activated performed extend methodology.

Language: Английский

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