Ni Single‐Atoms Supported on N‐Doped Carbon Prepared by Cation Exchange: Ultrafast Catalyst For The Reduction of Nitroarene Compounds Under Ambient Conditions

Author:

do Carmo Batista Walker Vinicius Ferreira1,de Oliveira Wanessa Lima1,de Oliveira Eduarda Ferreira1,Cruz Taís Santos1,Ferrari Jefferson Luis2,Archanjo Braulio Soares3,Grigoletto Sabrina4,da Costa Ferreira Dalva Ester4,Pereira Fabiano Vargas4,Diab Gabriel Ali Atta5,Mastelaro Valmor Roberto6,Teixeira Ivo Freitas6ORCID,de Mesquita Joao Paulo16

Affiliation:

1. Department of Chemistry – Universidade Federal dos Vales do Jequitinhonha e Mucuri Diamantina MG 39100–000 Brazil

2. Desenvolvimento de Materiais Inorgânicos com Terras Raras (DeMITeR) Laboratório de Materiais Fotoluminescentes (LAMAF) Universidade Federal de Uberlândia Instituto de Química Uberlândia MG, CEP: 38400–902 Brazil

3. Materials Metrology Division National Institute of Metrology Quality, and Technology (Inmetro) Duque de Caxias, RJ 25250-020 Brazil

4. Department of Chemistry – Federal University of Minas Gerais. Av. Antônio Carlos, 6627 – Pampulha Belo Horizonte – MG Brazil CEP 31270-901

5. Department of Chemistry – Federal University of São Carlos. Rod. Washington Luís km 235 – SP-310 São Carlos – SP Brazil CEP 13565–905

6. Instituto de Física de São Carlos Universidade de São Paulo Avenida Trabalhador São-Carlense, 400 13566-590 São Carlos, SP Brazil

Abstract

AbstractWe present a highly efficient single‐atom catalyst (SACs) tailored for nitroarene reduction using NaBH4 under ambient conditions. Employing an unique approach, we harnessed NaCl under high temperature to create host materials enriched with negatively charged nitrogenous and oxygenated functional groups, capable of anchoring and stabilizing Ni ions within the aromatic structure. The nickel single sites were prepared by a straightforward cation exchange method. STEM‐HAADF imaging confirmed the presence of nickel single‐atoms, while XPS, FTIR, and Raman spectra validated nickel coordination within the catalyst. Remarkably, the CN−Ni catalyst exhibited exceptional catalytic performance under ambient conditions, achieving a high catalytic activity with NaBH4 (TOF 2246 452 h−1 and 107 47 mmol g−1 min−1). It also demonstrated remarkable conversion exceeding 90 % and outstanding selectivity. Equally impressive was its ability to maintain full catalytic activity over multiple reaction cycles, highlighting its robustness. This work is a significant leap in SACs design, offering a versatile and highly effective preparation method for SACs based on N‐doped carbon with far‐reaching implications in industrial reduction reactions.

Funder

Fundação de Amparo à Pesquisa do Estado de São Paulo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Conselho Nacional de Desenvolvimento Científico e Tecnológico

Publisher

Wiley

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