Multicomponent graphene based catalysts for guaiacol upgrading in hydrothermal conditions: Exploring “H2-free” alternatives for bio-compounds hydrodeoxygenation


Catalytic hydrodeoxygenation (HDO) is a critical technique for upgrading biomass derivatives to deoxygenated fuels or other high-value compounds. Phenol, guaiacol, anisole, p-cresol, m-cresol and vanillin are all monomeric phenolics produced from lignin. Guaiacol is often utilised as a model lignin compound to deduce mechanistic information about the bio-oil upgrading process. Typically, a source of H2 is supplied as reactant for the HDO reaction. However, the H2 supply, due to the high cost of production and additional safety precautions needed for storage and transportation, imposes significant economic infeasibilities on the HDO process’s scaling up. We investigated a novel H2-free hydrodeoxygenation (HDO) reaction of guaiacol at low temperatures and pressures, using water as both a reaction medium and hydrogen source. A variety of Ni catalysts supported on zirconia/graphene/with/without nitrogen doping were synthesised and evaluated at 250 °C and 300 °C in a batch reactor, with the goal of performing a multi-step tandem reaction including water splitting followed by HDO. The catalysts were characterised using H2-TPR, XRD, TEM and XPS to better understand the physicochemical properties and their correlation with catalytic performance of the samples in the HDO process. Indeed, our NiZr2O/Gr-n present the best activity/selectivity balance and it is deemed as a promising catalyst to conduct the H2-free HDO reaction. The catalyst reached commendable conversion levels and selectivity to mono-oxygenated compounds considering the very challenging reaction conditions. This innovative HDO approach provides a new avenue for cost-effective biomass upgrading.

    H2-TPR and b-e) CO2-TPD spectra with deconvoluted sub-signals of the fresh supports and supported Ru catalysts up to 350 ℃. Numbers indicate the peak temperature of the sub-signals.

    Paper information


    Catalysis Today

    Volume 423, 1 November 2023, 114020


    Silvia Parrilla-Lahoz

    W. Jin

    L. Pastor-Pérez

    M.S. Duyar

    Laura Martínez-Quintana

    A.B. Dongil

    Tomas Ramirez Reina 



    H2-free HDO
    N-doped catalysts