Determining the Adsorption Energetics of 2,3-Butanediol on RuO<sub>2</sub>(110) [electronic resource] : Coupling First-Principles Calculations With Global Optimizers

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Tác giả:

Ngôn ngữ: eng

Ký hiệu phân loại: 662.12 Technology of explosives, fuels, related products

Thông tin xuất bản: Washington, D.C. : Oak Ridge, Tenn. : United States. Dept. of Energy. Office of Science ; Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2022

Mô tả vật lý: Size: Article No. 781001 : , digital, PDF file.

Bộ sưu tập: Metadata

ID: 262477

 As climate change continues to pose a threat to the Earth due to the disrupted carbon cycles and fossil fuel resources remain finite, new sources of sustainable hydrocarbons must be explored. 2,3-butanediol is a potential source to produce butene because of its sustainability as a biomass-derived sugar. Butene is an attractive product because it can be used as a precursor to jet fuel, categorizing this work in the alcohol-to-jet pathway. While studies have explored the conversion of 2,3-butanediol to butene, little is understood about the fundamental reaction itself. We quantify the energetics for three pathways that were reported in the literature in the absence of a catalyst. One of these pathways forms a 1,3-butadiene intermediate, which is a highly exothermic process and thus is unlikely to occur since 2,3-butanediol likely gets thermodynamically trapped at this intermediate. We further determined the corresponding energetics of 2,3-butanediol adsorption on an ensemble of predetermined binding sites when it interacts with a defect-free stoichiometric RuO<
 sub>
 2<
 /sub>
 (110) surface. Within this ensemble of adsorption sites, the most favorable site has 2,3-butanediol covering a Ru 5?coordinated cation. This approach is compared to that obtained using the global optimization algorithm as implemented in the Northwest Potential Energy Surface Search Engine. When using such a global optimization algorithm, we determined a more favorable ground-state structure that was missed during the manual adsorption site testing, with an adsorption energy of -2.61 eV as compared to -2.34 eV when using the ensemble-based approach. We hypothesize that the dehydration reaction requires a stronger chemical bond, which could necessitate the formation of oxygen vacancies. As such, this study has taken the first step toward the utilization of a global optimization algorithm for the rational design of Ru-based catalysts toward the formation of butene from sustainable resources.
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