A Binuclear Cerium-Based Metal–Organic Framework as an Artificial Monooxygenase for the Saturated Hydrocarbon Aerobic Oxidation with High Efficiency and High Selectivity DOI
Guanfeng Ji, Liang Zhao, Wang Ye

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(13), P. 7821 - 7832

Published: June 17, 2022

Artificial enzymatic systems have emerged in the field of biomimetic catalysis by constructing specific catalytic centers enzymes. Inspired high activity natural monooxygenase for oxidation transformation, several binuclear Cu/Fe-based metal–organic frameworks (MOFs) been frequently used as catalysts, yet rarely reports MOFs with other metals nodes reported to date. In this work, ingenious decoration Ce–O–Ce moieties and anthraquinone groups good oxygen activation ability one framework, an MOF-supported artificial cerium was obtained highly selective inert C(sp3)–H bonds. The single-crystal structural study reveals that molecule-level modularity a moiety design MOF creates confined microenvironment offer ordered distribution dense substrate-accessible active sites throughout architecture. After photoexcitation, trigger ligand-to-metal charge-transfer (LMCT) event form bridge radical, which abstracts hydrogen atom from bond generate carbon-centered radical through typical transfer (HAT) process. These radicals rapidly combine reactive species (ROS) produced via energy (EnT) process alkyl peroxy intermediates, are easily trapped another unsaturated coordinated ions further facilitate their hydrolysis formation carbonyl products. This anthraquinone-functionalized framework containing resembling exhibits unique selectivity (>97%) activity, represent first example constructed different applying alkanes, expanding selection range metal monooxygenase. Taking advantage heterogeneity MOF, Ce–MOF recycled five times without decrease its possessed broader applicability substrate C–H bonds, providing blueprint designing new alkane oxidation.

Language: Английский

A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation DOI Creative Commons
Yitao Dai, Corentin Poidevin, Cristina Ochoa‐Hernández

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(14), P. 5788 - 5796

Published: Dec. 18, 2019

Direct selective oxidation of hydrocarbons to oxygenates by O2 is challenging. Catalysts are limited the low activity and narrow application scope, main focus on active C-H bonds at benzylic positions. In this work, stable, lead-free, Cs3 Bi2 Br9 halide perovskites integrated within pore channels mesoporous SBA-15 silica demonstrate their photocatalytic potentials for bond activation. The composite photocatalysts can effectively oxidize (C5 C16 including aromatic aliphatic alkanes) with a conversion rate up 32900 μmol gcat-1 h-1 excellent selectivity (>99 %) towards aldehydes ketones under visible-light irradiation. Isotopic labeling, in situ spectroscopic studies, DFT calculations reveal that well-dispersed small perovskite nanoparticles (2-5 nm) possess enhanced electron-hole separation close contact facilitates C(sp3 )-H activation photoinduced charges.

Language: Английский

Citations

212
Boosted Photocatalytic Oxidation of Toluene into Benzaldehyde on CdIn2S4-CdS: Synergetic Effect of Compact Heterojunction and S-Vacancy DOI
Yuxuan Tan,

Zhao-Ming Chai,

Binghao Wang

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(5), P. 2492 - 2503

Published: Feb. 10, 2021

The enhancement of electron-and-hole separation efficiency and facile generation reactive oxygen species are significant factors for performance improvement photocatalysts in selective toluene photocatalytic oxidation. Heterojunction defect construction have been regarded as valid methods to boost activity semiconductors. Herein, the CdIn2S4-CdS composite with compact heterojunctions defect-induced sulfur vacancies was fabricated by a one-step hydrothermal process. sheet-to-sheet abundant facilitate migration photoinduced charge carriers. Benefited from compositional structural synergy, prepared CdIn2S4-CdS-140 boosted oxidation conversion into benzaldehyde (remarkable 80.3% selectivity 99% 6 h) under visible light irradiation. It is noteworthy that can perform well when pure O2 replaced air.

Language: Английский

Citations

198
Radical C(sp3)–H functionalization and cross-coupling reactions DOI
Dung L. Golden, Sung‐Eun Suh, Shannon S. Stahl

et al.

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(6), P. 405 - 427

Published: May 17, 2022

Language: Английский

Citations

186
Engineering Lattice Disorder on a Photocatalyst: Photochromic BiOBr Nanosheets Enhance Activation of Aromatic C–H Bonds via Water Oxidation DOI
Xing Cao, Aijian Huang, Chao Liang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(8), P. 3386 - 3397

Published: Feb. 15, 2022

Solar-driven photocatalytic reactions can mildly activate hydrocarbon C-H bonds to produce value-added chemicals. However, the inefficient utilization of photogenerated carriers hinders application. Here, we report reversible photochromic BiOBr (denoted as p-BiOBr) nanosheets that were colored by trapping holes upon visible light irradiation and bleached water oxidation generate hydroxyl radicals, demonstrating enhanced carrier separation oxidation. The coupling ethylbenzene efficiently realized p-BiOBr in a water-based medium under ambient temperature pressure (apparent quantum yield is 14 times pristine BiOBr). feature lattice disordered defects on surface, providing rich uncoordinated catalytic sites inducing structural distortions strain, which further leads an altered band structure significantly performances. These hole-trapping materials open up possibility substantially elevating efficiency for high-efficiency activation various saturated bonds.

Language: Английский

Citations

178
Recent development in transition metal-catalysed C–H olefination DOI Creative Commons
Wajid Ali, Gaurav Prakash, Debabrata Maiti

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(8), P. 2735 - 2759

Published: Jan. 1, 2021

Transition metal-catalysed functionalizations of inert C-H bonds to construct C-C represent an ideal route in the synthesis valuable organic molecules. Fine tuning directing groups, catalysts and ligands has played a crucial role selective bond (sp2 or sp3) activation. Recent developments these areas have assured high level regioselectivity olefination reactions. In this review, we summarized recent progress oxidative sp2 sp3 with special emphasis on distal, atroposelective, non-directed directed olefination. The scope, limitation, mechanism various transition reactions been described briefly.

Language: Английский

Citations

176
Thiosulfonates as Emerging Reactants: Synthesis and Applications DOI
Pieter Mampuys, Con Robert McElroy, James H. Clark

et al.

Advanced Synthesis & Catalysis, Journal Year: 2019, Volume and Issue: 362(1), P. 3 - 64

Published: Oct. 15, 2019

Abstract The synthetic strategies towards thiosulfonates (RSO 2 SR 1 ) are comprehensively reviewed from their original discovery to recent advances. Incorporation of the green credentials procedures allows one judge merits state art, beyond typical yield a product and availability reactants. As reactant for organic transformations, particularly interesting given possibility react with nucleophiles, electrophiles radicals. This review aims give researchers, not familiar field, good understanding general applications thiosulfonates, while skipping important related, but less explored, selenosulfonates SeR also covered. magnified image

Language: Английский

Citations

163
N-Rich 2D Heptazine Covalent Organic Frameworks as Efficient Metal-Free Photocatalysts DOI

Dan Chen,

Weiben Chen,

Guang Zhang

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 12(1), P. 616 - 623

Published: Dec. 22, 2021

Heptazine serves as the solely repetitive unit of graphitic carbon nitride (g-C3N4), which represents a progressive metal-free photocatalyst. However, synthesizing high-quality 2D heptazine-based covalent organic frameworks (COFs) remains formidable challenge, probably due to scarcity suitable and ample reactive building blocks. Herein, we designed synthesized 4-(methylene diacetate)phenyl-substituted heptazine monomer (HEP-OAc) by oxidation tris(4-tolyl)heptazine. Accordingly, two highly ordered N-rich COFs (HEP-TAPT-COF HEP-TAPB-COF) were readily prepared direct condensation HEP-OAc with C3-symmetric aromatic amines under solvothermal conditions. In comparison pristine g-C3N4, HEP-TAPT-COF exhibited greatly enhanced photocatalytic performance for benzylic C–H selective sulfoxidation mild This work provides meaningful insights into developing crystalline better capacities.

Language: Английский

Citations

105
Lewis Acid Sites in (110) Facet-Exposed BiOBr Promote C–H Activation and Selective Photocatalytic Toluene Oxidation DOI

Gaofeng Zhou,

Ben Lei,

Fan Dong

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4791 - 4798

Published: March 14, 2024

Solar photocatalytic technology has exhibited significant potential for upgrading the value-added chemicals industry through efficient C–H bond activation, such as selective toluene oxidation. However, improvement in activation of is still a challenge. Herein, (110) facet-exposed BiOBr (EC-BiOBr) synthesized via facile crystal facet control strategy an increasing exposure Lewis acid sites, confirmed by situ Fourier-transform infrared spectroscopy (FT-IR) using ammonia probe molecule. In FT-IR results substantiated improved absorption capacity EC-BiOBr toluene. Density functional theory (DFT) calculations indicated that acid–base pairs formed Bi sites and O can adsorb directionally, precisely matching orbit spaces conduction band (Bi 6p state) valence (O 2p Br 4p states). Benefiting from oriented adsorption toluene, electron could transfer to photogenerated hole precisely, thus achieving activation. Compared (001) (H–BiOBr), 11-fold conversion rate (from 233 2460 μmol g–1 h–1) was observed group, benzaldehyde formation increased 1623 h–1. Active species identification DFT revealed superoxide radicals were involved primary reactive subsequent oxidation benzyl generated This work highlights importance surface regulated strategy, which conducive rational design photocatalysts with high performance

Language: Английский

Citations

41
Photocatalytic aerobic oxidation of C(sp3)-H bonds DOI Creative Commons
Lei Zhang, Run‐Han Li, Xiaoxin Li

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 15, 2024

Abstract In modern industries, the aerobic oxidation of C(sp 3 )-H bonds to achieve value-added conversion hydrocarbons requires high temperatures and pressures, which significantly increases energy consumption capital investment. The development a light-driven strategy, even under natural sunlight ambient air, is therefore great significance. Here we develop series hetero-motif molecular junction photocatalysts containing two bifunctional motifs. With these materials, reduction O 2 can be effectively accomplished, thus realizing efficient in e.g., toluene ethylbenzene. Especially for ethylbenzene reactions, excellent catalytic capacity (861 mmol g cat −1 ) observed. addition direct bonds, CeBTTD-A also applied other types reactions highlighting their potential industrial applications.

Language: Английский

Citations

33
Triazine Frameworks for the Photocatalytic Selective Oxidation of Toluene DOI Creative Commons
Sizhe Li,

Niklas Huber,

Wei Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 26, 2024

Investigations into the selective oxidation of inert sp

Language: Английский

Citations

22