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From Methane to Methanol: Pd-iC-CeO2 Catalysts Engineered for High Selectivity via Mechanochemical Synthesis

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.4c04815· OSTI ID:2429737
 [1];  [2];  [3];  [4];  [1];  [1];  [1];  [1];  [5];  [5];  [3];  [6];  [3];  [2];  [1]
  1. Brookhaven National Laboratory (BNL), Upton, NY (United States)
  2. CSIC, Instituto de Catálisis y Petroleoquímica, Madrid (Spain)
  3. University of Udine and INSTM (Italy)
  4. CSIC, Instituto de Catálisis y Petroleoquímica, Madrid (Spain); Universitat Politècnica de València (Spain)
  5. Ames Laboratory, and Iowa State University, Ames, IA (United States)
  6. Brookhaven National Laboratory (BNL), Upton, NY (United States); State University of New York Stony Brook, NY (United States)
+ Show Author Affiliations

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 toward 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 metaloxide interactions and facilitates tandem methane activation and peroxide decomposition, thus resulting in an exclusive methanol selectivity of 100% with a yield of 117 μmol/gcat at 75 °C. Notably, solvent interactions of H2O2 (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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-07CH11358; SC0012704; DEAC02-07CH11358; CUP G29C20000830001
OSTI ID:
2429737
Alternate ID(s):
OSTI ID: 2438331; OSTI ID: 2440528; OSTI ID: 2447900
Report Number(s):
IS-J-11,413; BNL-226055-2024-JAAM
Journal Information:
Journal of the American Chemical Society, Vol. 146, Issue 38; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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