Single-Atoms on Crystalline Carbon Nitrides for Selective C─H Photooxidation: A Bridge to Achieve Homogeneous Pathways in Heterogeneous Materials.

non-noble metals photocatalysis poly(heptazine imides) selective oxidation single-atom catalysis

Journal

Advanced materials (Deerfield Beach, Fla.)
ISSN: 1521-4095
Titre abrégé: Adv Mater
Pays: Germany
ID NLM: 9885358

Informations de publication

Date de publication:
20 Nov 2023
Historique:
revised: 15 09 2023
received: 04 05 2023
medline: 21 11 2023
pubmed: 21 11 2023
entrez: 21 11 2023
Statut: aheadofprint

Résumé

Single-atom catalysis is a field of paramount importance in contemporary science due to its exceptional ability to combine the domains of homogeneous and heterogeneous catalysis. Iron and manganese metalloenzymes are known to be effective in C─H oxidation reactions in nature, inspiring scientists to mimic their active sites in artificial catalytic systems. Herein, a simple and versatile cation exchange method is successfully employed to stabilize low-cost iron and manganese single-atoms in poly(heptazine imides) (PHI). The resulting materials are employed as photocatalysts for toluene oxidation, demonstrating remarkable selectivity toward benzaldehyde. The protocol is then extended to the selective oxidation of different substrates, including (substituted) alkylaromatics, benzyl alcohols, and sulfides. Detailed mechanistic investigations revealed that iron- and manganese-containing photocatalysts work through a similar mechanism via the formation of high-valent M═O species. Operando X-ray absorption spectroscopy (XAS) is employed to confirm the formation of high-valent iron- and manganese-oxo species, typically found in metalloenzymes involved in highly selective C─H oxidations.

Identifiants

pubmed: 37986204
doi: 10.1002/adma.202304152
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

e2304152

Subventions

Organisme : Brazilian funding agencies CAPES
Organisme : CNPq
ID : 423196/2018-9
Organisme : CNPq
ID : 403064/2021-0
Organisme : CNPq
ID : 405752/2022-9
Organisme : FAPESP
ID : 2020/14741-6
Organisme : FAPESP
ID : 2021/13271-9
Organisme : FAPESP
ID : 2022/16273-5
Organisme : FAPESP
ID : 2021/12394-0
Organisme : FAPESP
ID : 2021/13915-3
Organisme : FAPESP
ID : 2021/11162-8
Organisme : HORIZON EUROPE European Innovation Council - CATART
ID : 101046836

Informations de copyright

© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.

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Auteurs

Marcos A R da Silva (MAR)

Department of Chemistry, Federal University of São Carlos, São Carlos, São Paulo, 13565-905, Brazil.

Nadezda V Tarakina (NV)

Department of Colloid Chemistry, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, D-14476, Potsdam, Germany.

José B G Filho (JBG)

Department of Chemistry, ICEx, Federal University of Minas Gerais, Belo Horizonte, MG, 31270-901, Brazil.

Carla S Cunha (CS)

Department of Chemistry, Federal University of São Carlos, São Carlos, São Paulo, 13565-905, Brazil.

Guilherme F S R Rocha (GFSR)

Department of Chemistry, Federal University of São Carlos, São Carlos, São Paulo, 13565-905, Brazil.

Gabriel A A Diab (GAA)

Department of Chemistry, Federal University of São Carlos, São Carlos, São Paulo, 13565-905, Brazil.

Rômulo Augusto Ando (RA)

Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo, 05508-000, Brazil.

Oleksandr Savateev (O)

Department of Colloid Chemistry, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, D-14476, Potsdam, Germany.

Iker Agirrezabal-Telleria (I)

Department of Chemical and Environmental Engineering of the Bilbao Engineering School, University of Basque Country (UPV/EHU), Plaza Torres Quevedo 1, Bilbao, 48013, Spain.

Ingrid F Silva (IF)

Department of Colloid Chemistry, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, D-14476, Potsdam, Germany.

Sara Stolfi (S)

Department of Chemistry, University of Pavia, viale Taramelli 12, Pavia, 27100, Italy.

Paolo Ghigna (P)

Department of Chemistry, University of Pavia, viale Taramelli 12, Pavia, 27100, Italy.

Maurizio Fagnoni (M)

Department of Chemistry, University of Pavia, viale Taramelli 12, Pavia, 27100, Italy.

Davide Ravelli (D)

Department of Chemistry, University of Pavia, viale Taramelli 12, Pavia, 27100, Italy.

Piero Torelli (P)

TASC Laboratory, CNR-IOM, Istituto Officina dei Materiali, Trieste, 34149, Italy.

Luca Braglia (L)

TASC Laboratory, CNR-IOM, Istituto Officina dei Materiali, Trieste, 34149, Italy.

Ivo F Teixeira (IF)

Department of Chemistry, Federal University of São Carlos, São Carlos, São Paulo, 13565-905, Brazil.

Classifications MeSH