Abstract
Non-stoichiometric perovskite oxides have been studied as a new family of redox oxides for solar thermochemical hydrogen (STCH) production owing to their favourable thermodynamic properties. However, conventional perovskite oxides suffer from limited phase stability and kinetic properties, and poor cyclability. Here, we report a strategy of introducing A-site multi-principal-component mixing to develop a high-entropy perovskite oxide, (La1/6Pr1/6Nd1/6Gd1/6Sr1/6Ba1/6)MnO3 (LPNGSB_Mn), which shows desirable thermodynamic and kinetics properties as well as excellent phase stability and cycling durability. LPNGSB_Mn exhibits enhanced hydrogen production (?77.5 mmol moloxide?1) compared to (La2/3Sr1/3)MnO3 (?53.5 mmol moloxide?1) in a short 1 hour redox duration and high STCH and phase stability for 50 cycles. LPNGSB_Mn possesses a moderate enthalpy of reduction (252.51-296.32 kJ (mol O)?1), a high entropy of reduction (126.95-168.85 J (mol O)?1 K?1), and fast surface oxygen exchange kinetics. All A-site cations do not show observable valence changes during the reduction and oxidation processes. This research preliminarily explores the use of one A-site high-entropy perovskite oxide for STCH.
| Original language | English |
|---|---|
| Pages (from-to) | 3910-3922 |
| Number of pages | 13 |
| Journal | Journal of Materials Chemistry A |
| Volume | 12 |
| Issue number | 7 |
| DOIs | |
| State | Published - Dec 18 2023 |
Funding
This work is supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy (EERE), under the Agreement Number DE-EE0008839, managed by the Hydrogen and Fuel Cell Technologies Office in the Fiscal Year 2019 H2@SCALE program. The UCSD team also acknowledges partial support from the NSF (DMR-2026193) after July 2023. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. This article has been authored by an employee of National Technology & Engineering Solutions of Sandia, LLC under Contract No. DE-NA0003525 with the U.S. Department of Energy (DOE). The employee owns all right, title and interest in and to the article and is solely responsible for its contents. The publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this article or allow others to do so, for United States Government purposes. The DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. The Alliance for Sustainable Energy, LLC, operates and manages the National Renewable Energy Laboratory (NREL) for DOE under contract no. DE-AC36-08GO28308. A part of this research used resources at the Spallation Neutron Source (SNS), a Department of Energy Office of Science User Facility operated by the Oak Ridge National Laboratory. The use of the WVU Shared Research Facilities is acknowledged. We thank Dr Xin Qian at Northwestern University for the technical discussion of direct water thermolysis, Dr J. Madhusudhan Naik at University of Zurich for the technical discussion of thermodynamics and configurational entropy, and Dr Yue Qi and Boyuan Xu at Brown University for the theoretical computation discussion.
| Funders | Funder number |
|---|---|
| U.S. Department of Energy | |
| Office of Energy Efficiency and Renewable Energy | DE-EE0008839 |
| Hydrogen and Fuel Cell Technologies Office |
