Prediction of Feasibility of Polaronic OER on (110) Surface of Rutile TiO 2 .

Autor: Pada Sarker H; Liquid Sunlight Alliance (LiSA), California Institute of Technology, Pasadena, CA, 91125, USA.; Department of Chemical Engineering, Stanford University, 43 Via Ortega, Stanford, CA, 94305, USA.; SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA., Abild-Pedersen F; Liquid Sunlight Alliance (LiSA), California Institute of Technology, Pasadena, CA, 91125, USA.; SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA., Bajdich M; Liquid Sunlight Alliance (LiSA), California Institute of Technology, Pasadena, CA, 91125, USA.; SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA.
Jazyk: angličtina
Zdroj: Chemphyschem : a European journal of chemical physics and physical chemistry [Chemphyschem] 2024 Jun 03; Vol. 25 (11), pp. e202400060. Date of Electronic Publication: 2024 Apr 14.
DOI: 10.1002/cphc.202400060
Abstrakt: The polaronic effects at the atomic level hold paramount significance for advancing the efficacy of transition metal oxides in applications pertinent to renewable energy. The lattice-distortion mediated localization of photoexcited carriers in the form of polarons plays a pivotal role in the photocatalysis. This investigation focuses on rutile TiO 2 , an important material extensively explored for solar energy conversion in artificial photosynthesis, specifically targeting the generation of green H 2 through photoelectrochemical (PEC) H 2 O splitting. By employing Hubbard-U corrected and hybrid density functional theory (DFT) methods, we systematically probe the polaronic effects in the catalysis of oxygen evolution reaction (OER) on the (110) surface of rutile TiO 2 . Theoretical understanding of polarons within the surface, coupled with simulations of OER at distinct titanium (Ti) and oxygen (O) active sites, reveals diverse polaron formation energies within the lattice sites with strong preference for bulk and surface bridge (O b ) oxygen sites. Moreover, we provide the evidence for the facilitative role of polarons in OER. We find that hole polarons situated at the equatorial oxygen sites near the Ti-active site, along with bridge site hole polarons distal from the O b active site yield a small reduction in OER overpotential by ~0.06 eV and ~0.12 eV, respectively. However, subsurface, equatorial, and bridge site hole polarons significantly reduce the Ti-active site OER overpotential by ~0.4 eV through the peroxo-type oxygen pathway. We also observe that the presence of hole polarons stabilizes the *OH, *O, and *OOH intermediate species compared to the scenario without hole polarons. Overall, this study provides a detailed mechanistic insight into polaron-mediated OER, offering a promising avenue for improving the catalytic activity of transition metal oxide-based photocatalysts catering to renewable energy requisites.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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