The production of chemicals and fuels via transformation of biomass-derived feedstock requires the hydrodeoxygenation of oxygenated intermediates (e.g. carboxylic acids, aldehydes or phenolic compounds).[1] Usually, this step is done by thermal hydrogenation at elevated temperatures and high pressures, in which the reacting hydrogen is still supplied from reforming of non-sustainable fossil resources. These drawbacks make the hydrogenation of oxygen-containing intermediates the most energy- and capital-intensive step during the biomass upgrading process.[2] Electrocatalytic hydrogenation, in contrary, is a promising, sustainable technology for the ambient reduction of organic molecules. The required hydrogen is produced in situ from reduction of hydronium ions or electrolysis of water that is driven by renewable resources.[3] Especially, the selective hydrogenation of α,β-unsaturated aldehydes towards their corresponding unsaturated alcohols has proven difficult in the past, even under thermal conditions (ΔpH2, ΔT).[4] When using common hydrogenation catalysts that are based on noble metals, e.g. Pd, Rh, Ru, hydrogenation of the double bond towards saturated aldehydes is by far more likely than conversion of the carbonyl moiety.[5] Therefore, researchers have put lots of efforts in developing new catalysts that are capable of selectively converting α,β-unsaturated aldehydes towards unsaturated alcohols under thermal conditions. The addition of promotors specifically activating the CO-bond, e.g. metal oxide species, oxophilic metals, is one approach that has proven beneficial in tuning the reaction selectivity.[6] Another approach towards selective hydrogenation of the carbonyl group is the repulsion of the double bond away from the catalyst surface either electrostatically via changing the charge density on the catalyst surface or sterically via particle size effects.[7] The present study investigates the electrocatalytic hydrogenation of trans-pent-2-en-1-al and trans-cinnamaldehyde on transition metal catalysts supported on carbon nanotubes in aqueous phase (Scheme 1). The influence of different noble metals as well as promotor species on the reaction selectivity, especially concerning the formation of α,β-unsaturated alcohols, is analyzed. Furthermore, the impact of an external electric potential on product distribution and reaction kinetics is evaluated. The effect of different metals, promotors as well as the presence of an external electric potential on the kinetic data shall be related to adsorption measurements of organic species on the catalyst surface both via cyclic voltammetry (CV) and UV/VIS-spectroscopy.In a recent study, we have shown that adding phenol to an aqueous electrolyte gradually blocks sites for H adsorption and hence, diminishes the Hupd peaks in CV curves recorded on Pt.[8] Now, we are seeking to correlate these findings with adsorption isotherms measured via UV/VIS absorption spectroscopy in order to answer the question whether different moieties, e.g. double bond, carbonyl group, lead to changes in the adsorption and activation of organic molecules on the electrode surface that can explain the differences in reaction kinetics and product distribution. Furthermore, we want to shed light on the influence of increasing the negative charge density on the electrode during ECH on electrostatic repulsion of electron-rich moieties away from the catalyst surface. First results on the hydrogenation of trans-pent-2-en-1-al showed that in case of ECH the yield of alcohol was increased by two orders of magnitude compared to thermal hydrogenation.[1] Y. Song, O. Y. Gutiérrez, J. Herranz, J. A. Lercher, Applied Catalysis B: Environmental 2016, 182, 236-246.[2] Y. Song, U. Sanyal, D. Pangotra, J. D. Holladay, D. M. Camaioni, O. Y. Gutiérrez, J. A. Lercher, Journal of Catalysis 2018, 359, 68-75.[3] U. Sanyal, J. Lopez-Ruiz, A. B. Padmaperuma, J. D. Holladay, O. Y. Gutiérrez, Organic Process Research & Development 2018, 22, 1590-1598.[4] a) P. Gallezot, D. Richard, Catalysis Reviews 1998, 40, 81-126; b) P. Claus, Topics in Catalysis 1998, 5, 51-62.[5] a) X. Lan, T. Wang, ACS Catalysis 2020, 10, 2764-2790; b) C. Louis, L. Delannoy, in Advances in Catalysis, Vol. 64 (Ed.: C. Song), Academic Press, 2019, pp. 1-88.[6] a) M. Tamura, K. Tokonami, Y. Nakagawa, K. Tomishige, ACS Catalysis 2016, 6, 3600-3609; b) Y. Dai, X. Gao, X. Chu, C. Jiang, Y. Yao, Z. Guo, C. Zhou, C. Wang, H. Wang, Y. Yang, Journal of Catalysis 2018, 364, 192-203; c) N. Mahata, F. Gonçalves, M. F. R. Pereira, J. L. Figueiredo, Applied Catalysis A: General 2008, 339, 159-168.[7] E. Bailón-García, F. J. Maldonado-Hódar, A. F. Pérez-Cadenas, F. Carrasco-Marín, Catalysts 2013, 3.[8] N. Singh, U. Sanyal, J. L. Fulton, O. Y. Gutiérrez, J. A. Lercher, C. T. Campbell, ACS Catalysis 2019. Figure 1
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