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Lee, Dongho

Publications and source records attributed to Lee, Dongho.

5 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Impact of Varying the Photoanode/Catalyst Interfacial Composition on Solar Water Oxidation: The Case of BiVO 4 (010)/FeOOH Photoanodes

Photoanodes used in a water-splitting photoelectrochemical cell are almost always paired with an oxygen evolution catalyst (OEC) to efficiently utilize photon-generated holes for water oxidation because the surfaces of photoanodes are typically not catalytic for the water oxidation reaction. Suppressing electron–hole recombination at the photoanode/OEC interface is critical for the OEC to maximally utilize the holes reaching the interface for water oxidation. Here, in order to explicitly demonstrate and investigate how the detailed features of the photoanode/OEC interface affect interfacial charge transfer and photocurrent generation for water oxidation, we prepared two BiVO 4 (010)/FeOOH photoanodes with different Bi:V ratios at the outermost layer of the BiVO 4 interface (close to stoichiometric vs Bi-rich) while keeping all other factors in the bulk BiVO 4 and FeOOH layers identical. The resulting two photoanodes show striking differences in the photocurrent onset potential and photocurrent density for water oxidation. The ambient pressure X-ray photoelectron spectroscopy results show that these two BiVO 4 (010)/FeOOH photoanodes show drastically different Fe 2+ :Fe 3+ ratios in FeOOH both in the dark and under illumination with water, demonstrating the immense impact of the interfacial composition and structure on interfacial charge transfer. Using computational studies, we reveal the effect of the surface Bi:V ratio on the hydration of the BiVO 4 surface and bonding with the FeOOH layer, which in turn affect the band alignments between BiVO 4 and FeOOH. These results explain the atomic origin of the experimentally observed differences in electron and hole transfer and solar water oxidation performance of the two photoanodes having different interfacial compositions.

14 SOLAR ENERGY↗
DOE OSTI2021

The impact of surface composition on the interfacial energetics and photoelectrochemical properties of BiVO{sub 4}.

The ability to engineer a photoelectrode surface is pivotal for optimizing the properties of any photoelectrode used for solar fuel production. Altering crystal facets exposed on the surface of photoelectrodes has been a major strategy to modify their surface structure. However, there exist numerous ways to terminate the surface even for the same facet, which can considerably alter the photoelectrode properties. Here we report tightly integrated experimental and computational investigations of epitaxial BiVO4 photoelectrodes with vanadium- and bismuth-rich (010) facets. Our study demonstrates that even for the same facet the surface Bi:V ratio has a remarkable impact on the interfacial energetics and photoelectrochemical properties. We also elucidate the microscopic origins of how the surface composition can affect the photoelectrochemical properties. This study opens an unexplored path for understanding and engineering surface energetics via tuning the surface termination/composition of multinary oxide photoelectrodes.

Lee, Dongho↗
DOE OSTI2020

Electrochemical Oxidation of Metal–Catechol Complexes as a New Synthesis Route to the High-Quality Ternary Photoelectrodes: A Case Study of Fe 2 TiO 5 Photoanodes

A new electrochemical, solution-based synthesis method to prepare uniform multinary oxide photoelectrodes was developed. This method involves solubilizing multiple metal ions as metal-catechol complexes in a pH condition where they are otherwise insoluble. When some of the catechol ligands are electrochemically oxidized, the remaining metal complexes become insoluble and are deposited as metal-catechol films on the working electrode. The resulting films are then annealed to form crystalline multinary oxide electrodes. Since catechol can serve as a complexing agent for a variety of metal ions, the newly developed method can be used to prepare a variety of multinary oxide films. In the present study, we used this method to prepare n-type Fe 2 TiO 5 photoanodes and investigated their photoelectrochemical properties for use in a photoelectrochemical water splitting cell. We also performed a computational investigation with two goals. The first goal was to investigate small electron polaron formation in Fe 2 TiO 5 . Charge transport in most oxide photoelectrodes involves small polaron hopping, but small polaron formation in Fe 2 TiO 5 has not been examined prior to this work. The second goal was to investigate the effect of substitutional Sn doping at the Fe site on the electronic band structure and the carrier concentration of Fe 2 TiO 5 . Here, the combined experimental and theoretical results presented in this study greatly improve our understanding of Fe 2 TiO 5 for use as a photoanode.

14 SOLAR ENERGY↗
DOE OSTI2020

The Role of Surface Oxygen Vacancies in BiVO 4

Bismuth vanadate (BiVO 4 ) is a widely studied oxide in solar water splitting, known for its ease of synthesis, high charge extraction yields, and advantageous band alignment with water. We present a combined first-principles and experimental study of the electronic structure of the (010) surface of BiVO 4 aimed at disentangling the impact of the surface and bulk oxygen vacancies on the electronic structure and transport properties. We found that oxygen vacancies are deep donors at the surface as they are in the bulk; our calculations on defect and polaron formation energies suggest that, while polarons formed from oxygen vacancies in the bulk can contribute to conductivity, those at the surface likely do not. Our results also show that out-of-plane structural relaxations at the surface contribute to the relatively immobile nature of electron polarons derived from surface oxygen vacancies. The structural model derived from first-principles calculation was validated by comparing computed results with experimental measurements of single-crystal and epitaxially grown single-crystalline BiVO 4 samples. Finally, we also found a reasonably good agreement between our calculated and measured work functions for BiVO 4 samples with and without oxygen vacancies.

36 MATERIALS SCIENCE↗