Thermochemical Transformations Using Entropy-Stabilized Oxides

Abstract

Thermochemical Transformations Using Entropy-Stabilized OxidesAbstractEntropy-stabilized oxides (ESOs) are a recently discovered class of materials that offer tworemarkable attributes: (a) unprecedented ability to tune the enthalpy and entropy of bound oxygen in the solid phase; (b) possibly unique arrangements of co-located neighboring transition metal cations in metastable crystal str"uctures. The first attribute could potentially offer new pathways for thermochemical redox reactions. As an example, preliminary wor"k on watersplittingreactions using a four-cation ESO has produced a remarkable breakthrough in reducing the temperature of hydrogen" production to 1100 oC, which is beyond the reach of traditional oxides such as ceria and ferrites that operate >1300 oC. We propose"" leveraging this attribute to explore the possibility of CO2 reduction to form CO, a well-known precursor for chemical synthesis. Th"e second attribute offers the promising prospects of cooperative effects in catalysis using multiple neighboring transition-metal ca"tions. Here, one cation could be used to chemisorb a chemical species while the others in the neighborhood could be used to stabiliz""e a complex via physisorption or chemisorption. Such multi-cation catalysis is found in biological enzymes, butsimilar mimics in in"organic catalysts have remained largely elusive. We will explore whether ESOs could potentially offer this promise in both Fischer-T"ropsch hydrogenation of carbon as well as C-H bond activation, which remains as one of the most difficult reactions to control. We w""ill leverage collaborations with the computational group at Stanford to guide the choice ofmulti-cation combinatorics of ESOs, and"" then synthesize these materials to experimentally study their impact on chemical transformations. Furthermore, we will use X-ray ab"sorption spectroscopy at SLAC to determine the role of the oxygen and the metal cations in thesechemical transformations.

Document Details

Document Type
DoD Grant Award
Publication Date
Sep 29, 2017
Source ID
N000141712918

Entities

People

  • Arun Majumdar

Organizations

  • Office of Naval Research
  • Stanford University
  • United States Navy

Tags

Fields of Study

  • Chemistry

Readers

  • Electrochemical Engineering/ Fuel Cell Technologies
  • Quantum Chemistry
  • Systems Analysis and Design