Juan D. Jiménez¹, Pablo G. Lustemberg^2*, Maila Danielis³, Estefanía Fernández-Villanueva^2,4, Sooyeon Hwang⁵, Iradwikanari Waluyo⁶, Adrian Hunt⁶, Dominik Wierzbicki⁶, Jie Zhang⁷, Long Qi⁷, Alessandro Trovarelli³, Jose A. Rodriguez^1,8, Sara Colussi³, M. Verónica Ganduglia-Pirovano², Sanjaya D. Senanayake¹

1 Chemistry Division, Brookhaven National Laboratory, Upton, NY, 11973, USA

2 Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain

3 Polytechnic Department, University of Udine and INSTM, Via del Cotonificio 108, 33100 Udine

4 Universitat Politècnica de València, Camí de Vera s/n, 46022, València, Spain

5 Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, 11973, USA

6 National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, New York 11973, USA

7 Ames National Laboratory, Iowa State University, Ames, Iowa, 50011, USA

8 Department of Chemistry, State University of New York Stony Brook, Stony Brook, NY 11794, USA

* Corresponding authors emails: p.lustemberg@csic.es

DOI10.24435/materialscloud:dz-zz [version v1]

Publication date: Aug 06, 2024

How to cite this record

Juan D. Jiménez, Pablo G. Lustemberg, Maila Danielis, Estefanía Fernández-Villanueva, Sooyeon Hwang, Iradwikanari Waluyo, Adrian Hunt, Dominik Wierzbicki, Jie Zhang, Long Qi, Alessandro Trovarelli, Jose A. Rodriguez, Sara Colussi, M. Verónica Ganduglia-Pirovano, Sanjaya D. Senanayake, From Methane to Methanol: Pd-iC-CeO2 Catalysts Engineered for High Selectivity via Mechano-Chemical Synthesis, Materials Cloud Archive 2024.117 (2024), https://doi.org/10.24435/materialscloud:dz-zz

Description

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-CeO2 catalysts, modified by carbon, created by a simple mechanochemical synthesis method exhibit 100% selectivity towards methanol at 75°C, using hydrogen peroxide as oxidizing agent. The solvent-free synthesis yields a distinctive Pd-iC-CeO2 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 rate of 117 µmol/gcat at 75°C. Notably, solvent interactions of H2O2 (aq) were found to be critical for methanol selectivity through a DFT-simulated Eley-Rideal-like mechanism. This mechanism uniquely enables the direct conversion of methane into methanol via a solid-liquid-gas process.

Materials Cloud sections using this data

Files

File name	Size	Description
references.zip MD5md5:a4d3b68b3d8fd790c1e10abc2a1b2ce4	6.1 MiB	This file includes the DFT calculations for two catalysts, Pd.CeO2 and PdiC.CeO2, as well as the molecules CH4, H2O2, and CH3OH in the gas phase.
CH4_activation.zip MD5md5:83f66b825abb8454938d7a25257afb59	54.9 MiB	Contains the adsorbed molecular state of CH4 and the dissociated state of CH3+H on each catalyst
H2O2_activation.zip MD5md5:f8afeaf5fc418bc9ef8cbebc24c883ff	43.3 MiB	Includes the adsorbed molecular state of H2O2 and the dissociated state of OOH+H on each catalyst
Langmuir-Hinshelwood_mechanism.zip MD5md5:cc80cccc71c96bc73f35841b2e180f57	222.8 MiB	Features the stable states considered through the Langmuir-Hinshelwood mechanism on each catalyst, corresponding to the two mechanisms shown in Figure 8. There are six states for PdiC.CeO2 with folders named A to F, and nine states for Pd.CeO2 with folders named a to i.
Eley-Rideal_mechanism.zip MD5md5:90dadc7c978402096dbfbdfdc34b6ad4	196.5 MiB	Contains the stable states considered through the Langmuir-Hinshelwood mechanism for each catalyst, corresponding to the two mechanisms in Figure 9. There are three states, a, b, and c for PdiC.CeO2, and A, B, and C for Pd.CeO2.
README.txt MD5md5:b226dd0785c5267c8dcb48b48d0f0b59	1.8 KiB	Readme file, includes tge description of the uploaded data

License

Files and data are licensed under the terms of the following license: Creative Commons Attribution 4.0 International.
Metadata, except for email addresses, are licensed under the Creative Commons Attribution Share-Alike 4.0 International license.

External references

Keywords

Pd.CeO2 PdC.CeO2 CH4 CH3OH H2O2 Eley-Rideal mechanism