Partial Thermal Condensation Mediated Synthesis of High-Density Nickel Single Atom Sites on Carbon Nitride for Selective Photooxidation of Methane into Methanol

Pawan Kumar, Peter Antal, Xiyang Wang, Jiu Wang, Dhwanil Trivedi, Ondřej František Fellner, Yimin A. Wu, Ivan Nemec, Vinicius Tadeu Santana, Josef Kopp, Petr Neugebauer, Jinguang Hu, Md Golam Kibria, Subodh Kumar

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

Direct selective transformation of greenhouse methane (CH4) to liquid oxygenates (methanol) can substitute energy-intensive two-step (reforming/Fischer–Tropsch) synthesis while creating environmental benefits. The development of inexpensive, selective, and robust catalysts that enable room temperature conversion will decide the future of this technology. Single-atom catalysts (SACs) with isolated active centers embedded in support have displayed significant promises in catalysis to drive challenging reactions. Herein, high-density Ni single atoms are developed and stabilized on carbon nitride (NiCN) via thermal condensation of preorganized Ni-coordinated melem units. The physicochemical characterization of NiCN with various analytical techniques including HAADF-STEM and X-ray absorption fine structure (XAFS) validate the successful formation of Ni single atoms coordinated to the heptazine-constituted CN network. The presence of uniform catalytic sites improved visible absorption and carrier separation in densely populated NiCN SAC resulting in 100% selective photoconversion of (CH4) to methanol using H2O2 as an oxidant. The superior catalytic activity can be attributed to the generation of high oxidation (NiIII═O) sites and selective C─H bond cleavage to generate •CH3 radicals on Ni centers, which can combine with •OH radicals to generate CH3OH.

Original languageEnglish
Article number2304574
JournalSmall
Volume20
Issue number15
Early online date27 Nov 2023
DOIs
StatePublished - 11 Apr 2024
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2023 The Authors. Small published by Wiley-VCH GmbH.

Funding

P.A., I.N. and S.K. acknowledges financial support from institutional sources of the Department of Inorganic Chemistry, Palacký University Olomouc, Czech Republic. Ondrej Tomanec, Ms. J. Stráská, and Martin Petr are acknowledged for the measurement of HRTEM, TEM, and XPS, respectively. J. Michalička and CzechNanoLab Research Infrastructure supported by MEYS CR (LM2023051) are also acknowledged for the TEM results. D. Milde is acknowledged for ICP‐MS analysis. P.K., J.H. and M.G.K. would like to thank the University of Calgary's Canada First Research Excellence Fund (CFREF) for financial assistance. The authors also acknowledge Canadian Light Source (project: 35G12344), a national research facility of the University of Saskatchewan, which is supported by the Canada Foundation for Innovation (CFI), the Natural Sciences and Engineering Research Council (NSERC), the National Research Council (NRC), the Canadian Institutes of Health Research (CIHR), the Government of Saskatchewan, and the University of Saskatchewan. Drs. Ning Chen, Adam Leontowich, Beatriz Diaz‐Moreno, Jay Dynes, Tom Regier, and Zachary Arthur are kindly acknowledged for XANES/EXAFS, WAXS, and soft X‐ray analysis on the samples.

FundersFunder number
Department of Inorganic Chemistry
University of Calgary's Canada First Research Excellence Fund
Canadian Light Source35G12344
University of Saskatchewan
National Research Council
Government of Saskatchewan
Canadian Institutes of Health Research
Natural Sciences and Engineering Research Council of Canada
Canada Foundation for Innovation
Ministerstvo Školství, Mládeže a TělovýchovyLM2023051
Univerzita Palackého v Olomouci
Canada First Research Excellence Fund

    Keywords

    • Ni single atom catalysts
    • carbon nitride
    • heterogeneous catalysts
    • methane oxidation
    • photocatalysis

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