Redox-Switchable Single-Atom Catalyst Enables Efficient Aqueous Hydroxymethylfurfural Oxidation

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15640%2F25%3A73633283" target="_blank" >RIV/61989592:15640/25:73633283 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989100:27640/25:10259337

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acscatal.5c06280" target="_blank" >https://pubs.acs.org/doi/10.1021/acscatal.5c06280</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acscatal.5c06280" target="_blank" >10.1021/acscatal.5c06280</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Redox-Switchable Single-Atom Catalyst Enables Efficient Aqueous Hydroxymethylfurfural Oxidation

Popis výsledku v původním jazyce

The selective aerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is a pivotal step toward biobased polymers, pharmaceuticals, and fuels. Yet, most high-performance catalysts require noble metals and organic solvents and lose activity in water. Here, we report a robust and recyclable heterogeneous catalyst comprising mixed-valence single-atom iron dimers anchored on nitrogen-doped graphene acid (Fe-NGA), which mimics the powerful oxidation center in nonheme diiron oxidases. Spectroscopic and theoretical studies reveal a redox-flexible Fe2+/Fe3+ manifold that, under basic aqueous conditions, evolves into a Fe3+-Fe4+ ferryl species capable of highly selective proton-coupled two-electron oxidations. Fe-NGA achieves 97% HMF conversion with 95% DFF selectivity, a turnover frequency of 17.3 h-1, and a specific productivity of 12.5 mmolDFF gcat -1 h-1 in pure water, surpassing state-of-the-art homogeneous and heterogeneous catalysts. The catalyst is stable with very low performance loss for at least six reactions. By merging such functionalities within a stable and reusable heterogeneous framework, Fe-NGA provides a benchmark earth-abundant catalyst for the effective oxidation of renewable feedstocks.

Název v anglickém jazyce

Redox-Switchable Single-Atom Catalyst Enables Efficient Aqueous Hydroxymethylfurfural Oxidation

Popis výsledku anglicky

The selective aerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is a pivotal step toward biobased polymers, pharmaceuticals, and fuels. Yet, most high-performance catalysts require noble metals and organic solvents and lose activity in water. Here, we report a robust and recyclable heterogeneous catalyst comprising mixed-valence single-atom iron dimers anchored on nitrogen-doped graphene acid (Fe-NGA), which mimics the powerful oxidation center in nonheme diiron oxidases. Spectroscopic and theoretical studies reveal a redox-flexible Fe2+/Fe3+ manifold that, under basic aqueous conditions, evolves into a Fe3+-Fe4+ ferryl species capable of highly selective proton-coupled two-electron oxidations. Fe-NGA achieves 97% HMF conversion with 95% DFF selectivity, a turnover frequency of 17.3 h-1, and a specific productivity of 12.5 mmolDFF gcat -1 h-1 in pure water, surpassing state-of-the-art homogeneous and heterogeneous catalysts. The catalyst is stable with very low performance loss for at least six reactions. By merging such functionalities within a stable and reusable heterogeneous framework, Fe-NGA provides a benchmark earth-abundant catalyst for the effective oxidation of renewable feedstocks.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

ACS Catalysis

ISSN

2155-5435

e-ISSN

—

Svazek periodika

15

Číslo periodika v rámci svazku

24

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

"20997–21008"

Kód UT WoS článku

001632682000001

EID výsledku v databázi Scopus

2-s2.0-105024490414