Determining the Adsorption Energetics of 2,3-Butanediol on RuO2(110): Coupling First-Principles Calculations With Global Optimizers

Frontiers in Energy Research

Jean-Sabin McEwen¹  Carrington Moore⁴  Vassiliki-Alexandra Glezakou⁵  Difan Zhang⁵  Roger Rousseau⁵ 

[1] Department of Biological Systems Engineering, Washington State University, Pullman, WA, United States;Department of Chemistry, Washington State University, Pullman, WA, United States;Department of Physics and Astronomy, Washington State University, Pullman, WA, United States;Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University Pullman, Pullman, WA, United States;Pacific Northwest National Laboratory, Physical Sciences Division, Richland, WA, United States;

关键词: energy;    butene;    RuO2;    computational catalysis;    butanediol;    bio-jet fuel;   

DOI  :  10.3389/fenrg.2021.781001

来源: DOAJ

【 摘 要 】

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 RuO2(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.

【 授权许可】

Unknown