165753 20260113234335.0 doi 10.1021/acsami.5c11895 sideral 147368 ART-2025-147368 eng Mollar-Cuni, Andrés Mechanistic Insights in Acceptorless Dehydrogenation of N-Heterocycles Using Graphenes as Carbocatalysts 2025 Catalytic dehydrogenation is a critical transformation in the chemical and energy sectors, particularly for reversible hydrogen storage systems. One of the most promising systems for hydrogen storage is the development of liquid organic hydrogen carriers (LOHCs), which have the potential capacity of storing and releasing hydrogen gas on demand. Catalytic direct dehydrogenation represents a greener, promising method to generate hydrogen in situ from these hydrogen-dense carriers. The catalytic activity of graphene materials as metal-free carbocatalysts in the acceptorless dehydrogenation of N-heterocycles has been explored. Herein, a detailed mechanistic investigation has been conducted through both experimental (stoichiometric and masking experiments) and DFT calculations on the reaction mechanism. The proposed mechanism identifies o-quinone groups as the active sites responsible for catalysis, involving the transformation of o-quinone groups into epoxide intermediates, which release molecular hydrogen and regenerate the o-quinone groups, completing the catalytic cycle. This work provides insight into the design of efficient metal-free catalysts for their use in LOHCs storage systems, paving the way for sustainable energy solutions. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/AEI/PID2021-126071OB-C21 info:eu-repo/grantAgreement/ES/AEI/PID2021-126071OB-C22 info:eu-repo/grantAgreement/ES/AEI/PID2022-141433OB-I00 info:eu-repo/grantAgreement/ES/DGA/E31-23R info:eu-repo/semantics/openAccess by https://creativecommons.org/licenses/by/4.0/deed.es info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion García-Aznar, Pablo Martín, Santiago Universidad de Zaragoza (orcid)0000-0001-9193-3874 Sastre, German García, Hermenegildo Mata, Jose A. 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 17, 51 (2025), 69234-69244 ACS appl. mater. interfaces ACS applied materials & interfaces 1944-8244 5123269 http://zaguan.unizar.es/record/165753/files/texto_completo.pdf Versión publicada 3295394 http://zaguan.unizar.es/record/165753/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:165753 articulos driver 2026-01-13-22:07:37 ARTICLE