Bioinspired Framework Catalysts: From Enzyme Immobilization to Biomimetic Catalysis

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5347 - 5420

Published: April 12, 2023

Enzymatic catalysis has fueled considerable interest from chemists due to its high efficiency and selectivity. However, the structural complexity vulnerability hamper application potentials of enzymes. Driven by practical demand for chemical conversion, there is a long-sought quest bioinspired catalysts reproducing even surpassing functions natural As nanoporous materials with surface areas crystallinity, metal-organic frameworks (MOFs) represent an exquisite case how enzymes their active sites are integrated into porous solids, affording heterogeneous superior stability customizable structures. In this review, we comprehensively summarize advances MOFs catalysis, discuss design principle various MOF-based catalysts, such as MOF-enzyme composites embedded sites, explore utility these in different reactions. The advantages enzyme mimetics also highlighted, including confinement, templating effects, functionality, comparison homogeneous supramolecular catalysts. A perspective provided potential solutions addressing current challenges MOF catalysis.

Language: Английский

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Nitrogen Fixation via Splitting into Nitrido Complexes

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(11), P. 6522 - 6587

Published: May 11, 2021

The large carbon footprint of the Haber–Bosch process, which provides ammonia for fertilizers but also feedstock all nitrogenous commercial products, has fueled quest alternative synthetic strategies to nitrogen fixation. Owing extraordinarily strong N≡N triple bond, key step reaction, i.e., dissociative adsorption N2, requires high temperatures. Since first report in 1995, a wide variety molecular transition metal and f-block compounds have been reported that can fully cleave N2 at ambient conditions form well-defined nitrido complexes. We here provide comprehensive survey current state splitting reactions solution follow-up transfer reactivity. Particular emphasis is put on electronic structure requirements formation suitable precursors their N–N scission prospects synthesis containing products will be discussed, ranging from heterocumulenes organic amines, amides or nitriles via proton coupled electron transfer, carbonylation, electrophilic functionalization derived Accomplishments challenges fixation are presented offer guidelines development catalytic platforms.

Language: Английский

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Second and Outer Coordination Sphere Effects in Nitrogenase, Hydrogenase, Formate Dehydrogenase, and CO Dehydrogenase

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(14), P. 11900 - 11973

Published: July 18, 2022

Gases like H

Language: Английский

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Comprehensive insights into synthetic nitrogen fixation assisted by molecular catalysts under ambient or mild conditions

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(8), P. 5201 - 5242

Published: Jan. 1, 2021

N₂is fixed as NH₃industrially by the Haber–Bosch process under harsh conditions, whereas biological nitrogen fixation is achieved ambient which has prompted development of alternative methods to fix N₂catalyzed transition metal molecular complexes.

Language: Английский

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Nitrogen reduction by the Fe sites of synthetic [Mo3S4Fe] cubes

Nature, Journal Year: 2022, Volume and Issue: 607(7917), P. 86 - 90

Published: July 6, 2022

Language: Английский

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Exploration of the bio-analogous asymmetric C–C coupling mechanism in tandem CO2 electroreduction

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(10), P. 878 - 887

Published: Sept. 29, 2022

Language: Английский

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Near ambient N2 fixation on solid electrodes versus enzymes and homogeneous catalysts

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(3), P. 184 - 201

Published: Feb. 1, 2023

Language: Английский

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Inspiration from Nature: Influence of Engineered Ligand Scaffolds and Auxiliary Factors on the Reactivity of Biomimetic Oxidants

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(15), P. 9761 - 9797

Published: July 19, 2021

Enzymes are highly efficient catalysts in Nature that often react with high stereo-, chemo-, and regioselectivity. Usually, enzymes achieve this selectivity through substrate binding positioning the active site. The second-coordination sphere effects (also called noncovalent interactions) position oxidant close vicinity, their include electrostatic interactions, hydrogen-bonding salt-bridges, also long-range charge-effects from bound cations anions. Each of these environmental perturbations can affect kinetics reactions differently. Over past couple years, a variety biomimetic model complexes have been developed designed similar first-coordination to mononuclear iron-containing enzymes. However, sometimes reactivity patterns models solution different analogous enzymatic systems, reaction is lost. To understand functional differences between models, large catalytic clusters incorporate influence spectroscopic features as well patterns. In Review, we summarize highlight recent advances chemistry on creation design iron insights obtained when elaborate ligand added, which approach center. We start axial distal metal centers how be perturbed by hydrogen bonding steric restraints. syntheses oxidants addition proton-donating or -accepting groups structure discussed detail article. As shown work, useful not only trap characterize short-lived intermediates but enable specificity chemical analogy systems. These appear for biotechnological engineering applications reasonable turnover numbers consequently great potential future stereo- chemoselective synthetic reactions.

Language: Английский

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Evidence of substrate binding and product release via belt-sulfur mobilization of the nitrogenase cofactor

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(5), P. 443 - 454

Published: May 16, 2022

Language: Английский

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Recent advances in catalytic nitrogen fixation using transition metal–dinitrogen complexes under mild reaction conditions

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 472, P. 214783 - 214783

Published: Aug. 26, 2022

Language: Английский

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