From Methane to Methanol: Pd-iC-CeO <sub>2</sub> Catalysts Engineered for High Selectivity via Mechanochemical Synthesis
In the pursuit of selective conversion of methane directly to methanol in the liquid-phase, a common challenge is the concurrent formation of undesirable liquid oxygenates or combustion byproducts. However, we demonstrate that monometallic Pd-CeO<sub>2</sub> catalysts, modified by carbon, created by a simple mechanochemical synthesis method exhibit 100% selectivity toward methanol at 75 °C, using hydrogen peroxide as oxidizing agent. The solvent free synthesis yields a distinctive Pd-iC-CeO<sub>2</sub> interface, where interfacial carbon (iC) modulates metal-oxide interactions and facilitates tandem methane activation and peroxide decomposition, thus resulting in an exclusive methanol selectivity of 100% with a yield of 117 μmol/g<sub>cat</sub> at 75 °C. Notably, solvent interactions of H<sub>2</sub>O<sub>2</sub> (aq) were found to be critical for methanol selectivity through a density functional theory (DFT)-simulated Eley-Rideal-like mechanism. This mechanism uniquely enables the direct conversion of methane into methanol via a solid-liquid-gas process.
Authors
- Sara Colussi (ORCID: https://orcid.org/0000-0001-5316-1746)
- M. V. Ganduglia-Pirovano (ORCID: https://orcid.org/0000-0003-2408-8898)
- Long Hao Qi (ORCID: https://orcid.org/0000-0002-1213-2946)
- Estefanía Fernández-Villanueva (ORCID: https://orcid.org/0000-0002-9419-0786)
- Maila Danielis (ORCID: https://orcid.org/0000-0001-8469-9282)
- Juan D. Jiménez (ORCID: https://orcid.org/0000-0003-4710-1047)
- Dominik Wierzbicki (ORCID: https://orcid.org/0000-0003-0558-7405)
- Sanjaya D. Senanayake (ORCID: https://orcid.org/0000-0003-3991-4232)
- Alessandro Trovarelli (ORCID: https://orcid.org/0000-0002-1396-4031)
- Iradwikanari Waluyo (ORCID: https://orcid.org/0000-0002-4046-9722)
- Sooyeon Hwang (ORCID: https://orcid.org/0000-0001-5606-6728)
- Adrian Hunt (ORCID: https://orcid.org/0000-0002-5283-9647)
- Pablo G. Lustemberg (ORCID: https://orcid.org/0000-0003-4058-4023)
- José A. Rodríguez (ORCID: https://orcid.org/0000-0002-5680-4214)
- Jie Zhang (ORCID: https://orcid.org/0000-0002-9976-3942)
Institutions
- University of Udine (IT)
- State University of New York (US)
- Iowa State University (US)
- Brookhaven National Laboratory (US)
- Instituto de Catálisis y Petroleoquímica (ES)
- National Interuniversity Consortium of Materials Science and Technology (IT)
- Stony Brook University (US)
- Universitat Politècnica de València (ES)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2024-08-15
- DOI
- https://doi.org/10.1021/jacs.4c04815
- Citations
- 22
- Primary Topic
- Catalytic Processes in Materials Science
- Type
- article
- Field-Weighted Citation Impact
- 2.58
Funders
- U.S. Department of Energy
- Iowa State University
- European Commission
- Universidad Autónoma de Madrid
- Ministerio de Ciencia e Innovación
- Office of Science
- Universitat Politècnica de València
- European Regional Development Fund
- Agencia Estatal de Investigación
- Basic Energy Sciences
- Chemical Sciences, Geosciences, and Biosciences Division
- Brookhaven National Laboratory
- Ames Laboratory