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Stabilization of Catalytically Active Surface Defects on Ga-doped La–Sr–Mn Perovskites for Improved Solar Thermochemical Generation of Hydrogen

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Abstract

Solar thermochemical hydrogen (STCH) production from water splitting typically requires performing redox cycles at temperatures above 1200 °C to reduce and re-oxidize the bulk of a reversible material. Bulk processes such as oxygen vacancy formation and oxygen diffusion energies dictate the viability of a material for STCH. The surface plays an important role in the formation and destruction of vacancies and interacts with gas phase water and surface adsorbed species. These surface processes can lead to surface reconfigurations and even the formation of surface phases with stoichiometry and oxygen content very different from the bulk composition. Understanding in-situ the surface chemical state and its evolution under water splitting is important to design nonstoichiometric oxides capable of longer-lasting STCH generation at lower temperatures. In this work, we describe the water splitting active defect sites in LSM ((La0.65Sr0.35)0.95MnO3−δ) and Ga-doped LSM ((La0.6Sr0.4)0.95(Mn0.8Ga0.2)O3−δ) perovskites during Operando thermochemical water splitting conditions using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) experiments at 800 °C under steam. We show that sub-stoichiometric La+3 in the oxygen-vacancy rich surface at operating conditions can be used to correlate surface water splitting activity and the creation of surface hydroxide intermediates. The addition of Ga in LSM is shown to drastically stabilize the surface chemical composition by preventing Sr segregation and stabilizing catalytically active surface defects that promote the binding of adsorbed hydroxides. We use Operando AP-XPS quantification of metastable surface hydroxide intermediates (La(OH)3) to determine the amount of catalytically active surface sites in LSM (2.9%) and in LSMG (7.8–8.1%, depending on the bulk oxidation state).

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Data availability

The datasets generated during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

We gratefully acknowledge financial support from the U.S. Department of Energy Hydrogen and Fuel Cell Technologies Office (Award Number: DE-EE0008840). Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC (NTESS), a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration (DOE/NNSA) under contract DE-NA0003525. This written work is authored by an employee of NTESS. The employee, not NTESS, owns the right, title and interest in and to the written work and is responsible for its contents. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the written work do not necessarily represent the views of the U.S. Government. The publisher acknowledges that the U.S. Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this written work or allow others to do so, for U.S. Government purposes. The DOE will provide public access to results of federally sponsored research in accordance with the DOE Public Access Plan.

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Authors and Affiliations

  1. Sandia National Laboratories, Livermore, CA, 94550, USA

    Andre L. Fernandes Cauduro, Keith A. King, Antony H. McDaniel & Farid El Gabaly

  2. Department of Mechanical and Aerospace Engineering, University of Florida, Gainesville, 32611, USA

    Dylan McCord & Jonathan Scheffe

  3. Department of Materials Science and Engineering, University of Florida, Gainesville, 32611, USA

    Elizabeth Gager & Juan Claudio Nino

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  1. Andre L. Fernandes Cauduro
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Correspondence to Farid El Gabaly.

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Fernandes Cauduro, A.L., Gager, E., King, K.A. et al. Stabilization of Catalytically Active Surface Defects on Ga-doped La–Sr–Mn Perovskites for Improved Solar Thermochemical Generation of Hydrogen. Top Catal (2024). https://doi.org/10.1007/s11244-024-01940-w

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