Many polyols are abundant and cheap molecules highly spread in the biomass. These molecules have an enormous potential to be used in electrochemical devices to generate energy and/or value-added molecules. The electrooxidation of polyols can produce different substances of interest in the chemical industry concomitantly to high purity hydrogen in electrolyzers. The cost in the production of all these chemicals depends, among other factors, on the develop of more active and selective catalysts. However, in order to search for these materials using computational experiments, it is mandatory to have a better understanding of the fundamental aspect of the reactions, which permit to base the search on the adsorption energies of one or more key reaction intermediates. To contribute to this task, we performed (spectro)electrochemical and computational experiments to study the electrooxidation of C 4 polyols. We show that the electrooxidation of polyols does not depend on the relative orientation of their OH groups. Besides, using Pt single crystals, we demonstrate that the trend for the oxidation of the primary carbon (relative to the secondary) increases in the order Pt(111) < Pt(100) < Pt(110) and that this result can be extended to polyols with longer carbon chains. Finally, computational experiments permit us to rationalize these trends looking at the relative stability of double dehydrogenated intermediates on the Pt basal planes.
Herein we show that Pt(111) and Pt(100) can produce the ketone through the oxidation of the secondary carbon of the polyols. After the Bi modification, the selectivity for the ketone formation increases. On the other hand, we observe that pure and Bi‐modified Pt(110) only produced the C3 molecules oxidized in the primary carbon, and it is the only facet that shows an enhancement in the activity due to the modification. In line with these findings, small Pt nanoparticles are not selective for ketone formation. Finally, based on data obtained through DFT calculations, we suggest that positively charged Bi adatoms interact with the OH‐ groups of the enediol‐like intermediate (believed to be the precursor for the ketone/aldehyde production), facilitating the oxidation of the secondary carbon to produce DHA.
Ao meu pai, Vinicius, pelo apoio, tanto financeiro, como emocional, durante todos estes anos. À minha mãe, por estar sempre ao meu lado e sempre me receber de braços abertos para qualquer problema. Também a minha irmã, Giovanna, por todo companheirismo e conselhos dados. Obrigada a todos por acreditarem em mim! Ao Professor Dr. Miguel Angel San Miguel Barrera, por toda orientação e aprendizado que obtive durante estes dois anos. Aos colegas do grupo Unicamp Materials Simulation Lab e agregados, Carlos, Otto, André, Douglas, Heitor, Manoel, Felipe e Lucas pela convivência e solicitude. Em especial, ao Bruno, que desde o começo foi muito presente no desenvolvimento do meu projeto; obrigada pela ajuda, pelas conversas e pela amizade. Às amigas que conquistei durante a graduação, Tamaira, Mari, Camila, Paola, Laís, Marina e Mi pela parceria durante os momentos felizes e difíceis que passamos dentro da Unicamp e também pelas missões fora dela. Também ao Humanas, por todas as conversas e ajuda. Aos meus amigos que fui encontrar há 10000 km do Brasil, Luíza, Anna, Lucia, Asta e Igor, por todos os papos, refeições, conselhos e consultas médicas. Levo vocês sempre comigo! Aos meus amigos de Limeira, Nate, Carol, Pedro e Gui, que me acompanham há mais de 10 anos. Sei que posso contar com vocês! Ao Professor Dr. Pablo Fernandéz pelo desenvolvimento do projeto, o acolhimento e disponibilidade. Ao Prof. Dr. Edison Zacarias, por toda a assistência oferecida durante o projeto. Aos docentes, cujas disciplinas ministradas por eles contribuiram à minha formação, Prof.
Nitrate and nitrite reduction reactions (NO3RR and NO2RR, respectively) are important processes in water treatment as well as model processes in surface science. The sluggish kinetics observed for the NO3RR...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.