Enhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalysts

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Июль 26, 2023

Oxidation of renewable polyol/sugar into formic acid using molecular O2 over heterogeneous catalysts is still challenging due to the insufficient activation both and organic substrates on coordination-saturated metal oxides. In this study, we develop a defective MnO2 catalyst through coordination number reduction strategy enhance aerobic oxidation various polyols/sugars acid. Compared common MnO2, tri-coordinated Mn in displays electronic reconstruction surface oxygen charge state rich vacancies. These vacancies create more Mnδ+ Lewis site together with nearby as base sites. This combined structure behaves much like Frustrated pairs, serving facilitate O2, well C-C C-H bonds. As result, shows high catalytic activity (turnover frequency: 113.5 h-1) yield (>80%) comparable noble for glycerol oxidation. The system further extended other excellent performance.

Язык: Английский

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Progress in design and preparation of multi-atom catalysts for photocatalytic CO2 reduction

Science China Materials, Год журнала: 2024, Номер 67(2), С. 397 - 423

Опубликована: Янв. 5, 2024

Язык: Английский

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Advances in CO₂ activation by frustrated Lewis pairs: from stoichiometric to catalytic reactions

Chemical Science, Год журнала: 2023, Номер 14(47), С. 13661 - 13695

Опубликована: Янв. 1, 2023

Frustrated Lewis pair systems have been explored efficiently in homogeneous and heterogeneous conditions for the activation reduction of CO 2 to various useful products stoichiometric as well catalytic reactions.

Язык: Английский

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Computational Evolution Of New Catalysts For The Morita–Baylis–Hillman Reaction**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(18)

Опубликована: Фев. 14, 2023

We present a de novo discovery of an efficient catalyst the Morita-Baylis-Hillman (MBH) reaction by searching chemical space for molecules that lower estimated barrier rate-determining step using genetic algorithm (GA) starting from randomly selected tertiary amines. identify 435 candidates, virtually all which contain azetidine N as catalytically active site, is discovered GA. Two are further study based on their predicted synthetic accessibility and have barriers than known catalyst. Azetidines not been used catalysts MBH reaction. One suggested successfully synthesized showed eightfold increase in activity over commonly believe this first experimentally verified generative model.

Язык: Английский

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Straightforward synthesis of functionalized γ-Lactams using impure CO2 stream as the carbon source

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 22, 2023

Abstract Direct utilization of CO 2 into organic synthesis finds enormous applications to synthesize pharmaceuticals and fine chemicals. However, pure gas is essential achieve these transformations, the purification highly cost energy intensive. Considering this, we describe a straightforward synthetic route for γ-lactams, pivotal core structure bioactive molecules, by using commercially available starting materials (alkenes amines) impure stream (exhaust collected from car) as carbon source. This blueprint features broad scope, excellent functional group compatibility application late-stage transformation existing natural products functionalized γ-lactams. We believe that our strategy will provide direct access γ-lactams in very sustainable way also enhance Carbon Capture Utilization (CCU) strategy.

Язык: Английский

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Creation of surface frustrated Lewis pairs on high-entropy spinel nanocrystals that boosts catalytic transfer hydrogenation reaction

Chemical Engineering Journal, Год журнала: 2023, Номер 470, С. 144291 - 144291

Опубликована: Июнь 22, 2023

Язык: Английский

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Mechanism-Guided Catalyst Design for CO₂ Hydrogenation to Formate and Methanol

Accounts of Materials Research, Год журнала: 2023, Номер 4(9), С. 746 - 757

Опубликована: Июль 26, 2023

ConspectusCO2 to formate/formic acid and methanol has emerged as a promising method for utilizing CO2 in chemical fuel synthesis, well reducing emissions when H2 is produced through renewable energy sources. This reaction requires the activation of two chemically distinct molecules, H2, along with selective formation desired product. Creating efficient catalysts that surpass limitations existing remains significant challenge. Historically, development largely depended on trial error until successful outcomes are achieved. However, recent advances material synthesis well-defined structures, kinetics analysis, situ characterization techniques, computational studies have facilitated systematic understanding catalytic reactions enabled mechanism-guided catalyst development. innovative approach empowered researchers strategically design effective optimize target reaction, particularly rate-determining step, while tackling other limitations, such selectivity stability.This Account provides an overview our efforts hydrogenation engineering, which primarily divided into sections: (i) formic acid/formate (ii) production. For acid, we first discuss structure–activity correlation various metal/support systems, including different metal particle sizes, types support, crystalline morphologies support. These highlight crucial role electron-rich sites splitting adequate number weak basic activation, inform improved unique architectures. Notably, encapsulated cluster enhance utilization species synergistic interaction between active support material. The encapsulation strategy can also be applied inexpensive elements Ni, facilitating highly catalysts.Our primary focus CO2-to-methanol durable oxide-based catalysts. We identify critical limitation oxide their poor capability, based comprehensive review classical state-of-the-art Consequently, principal concept involves coupling promoters, provide high functionality, enable adsorption synthesis. An essential synthetic doping promoters surface Specifically, atomically dispersed significantly improve yield by maximizing interfacial synergy catalyst. A remarkable incorporation hydrogen dispenser, conductive carbon, promoter multicomponent composite dramatically enhances delivery from via long-range spillover, resulting accelerated overcomes conventional metal/oxide constrain movement across conclude discussing underlying implications these observations offering perspectives future research opportunities.

Язык: Английский

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Structure–Reactivity Relationships in Borane-Based FLP-Catalyzed Hydrogenations, Dehydrogenations, and Cycloisomerizations

Accounts of Chemical Research, Год журнала: 2023, Номер 56(7), С. 821 - 834

Опубликована: Март 13, 2023

ConspectusThe activation of molecular hydrogen by main-group element catalysts is an extremely important approach to metal-free hydrogenations. These so-called frustrated Lewis pairs advanced within a short period time become alternative transition metal catalysis. However, deep understanding the structure–reactivity relationship far less developed compared that complexes, although it paramount for advancing pair chemistry.In this Account, we provide detailed insight into how acidity and basicity correlate reactivity. The reactivity will be systematically discussed in context with selected reactions. influence major electronic modifications correlated ability activate hydrogen, channel reaction kinetics pathways, or achieve C(sp3)–H activations.First, describe entered emerging field research after quickly realizing information was lacking on changes modification pair. This led us development qualitative quantitative imine hydrogenation utilized as model experimentally determine parameters FLP-mediated first time. kinetic study revealed autoinduced catalytic profiles when acids weaker than tris(pentafluorophenyl)borane were applied, opening up base dependency one system. With knowledge interplay between acid strength basicity, methods densely functionalized nitroolefins, acrylates, malonates. Here, reduced needed counterbalanced suitable ensure efficient activation. opposite measure necessary unactivated olefins. For these, comparably electron-releasing phosphanes required generate strong Brønsted systems displayed highly reversible even at temperatures low −60 °C. A systematic these enabled acceptorless dehydrocouplings amines silanes dehydrogenations aza-heterocycles activations. Furthermore, π-activation cycloisomerizations carbon–carbon carbon–nitrogen bond formations. Lastly, new featuring weak bases active components reductive deoxygenation phosphane oxides carboxylic amides.

Язык: Английский

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Carbon dioxide capture and functionalization by bis(N-heterocyclic carbene)-borylene complexes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 9, 2024

Derivatives of free monocoordinated borylenes have attracted considerable interest due to their ability exhibit transition-metal-like reactivity, in particular small molecules capture. However, such complexes are rare as the formation is either endergonic, or resulting adduct a transient intermediate that prone reaction. Here, we present synthesis two bis(N-heterocyclic carbene)-borylene capable capturing and functionalizing carbon dioxide. The capture subsequent functionalization CO2 by bis(NHC)-disilylamidoborylene 1 demonstrated bis(NHC)-isocyanatoborylene-carbon dioxide complex 3. Reversible observed using bis(NHC)-mesitylborylene 2, persistent bis(NHC)-mesitylborylene-carbon 4 can be stabilized hydrogen bonding with boric acid. reactions ammonia-borane aniline demonstrate captured further functionalized.

Язык: Английский

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Homogeneous and Heterogeneous Frustrated Lewis Pairs for the Activation and Transformation of CO2

Chemistry - An Asian Journal, Год журнала: 2024, Номер 19(12)

Опубликована: Апрель 12, 2024

Due to the serious ecological problems caused by high CO

Язык: Английский

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