Electrocatalytic Hydrogenation of Oxygenates using Earth-Abundant Transition-Metal Nanoparticles under Mild Conditions.

Electrocatalytic hydrogenation (ECH) is a sustainable pathway for the synthesis of value-added organic compounds, provided affordable catalysts with high activity, selectivity and durability are developed. Here, we synthesize Cu/C, Ni/C, and CuNi/C nanoparticles and compare their performance to Pt/C, Ru/C, PtRu/C for the ECH of hydroxyacetone, a bio-derived feedstock surrogate containing a carbonyl and a hydroxyl functional group. The non-precious metal electrocatalysts show promising conversion-time behavior, product selectivities, and Faradaic efficiencies. Ni/C forms propylene glycol with a selectivity of 89 % (at 80 % conversion), while Cu/C catalyzes ECH (52 % selectivity) and hydrodeoxygenation (HDO, 48 % selectivity, accounting for evaporation). CuNi/C shows increased turnover frequencies but reduced ECH selectivity (80 % at 80 % conversion) as compared to the Ni/C catalyst. Importantly, stability studies show that the non-precious metal catalysts do not leach at operating conditions.

[1]  R. Luque,et al.  Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels. , 2015, Bioresource technology.

[2]  S. Pang,et al.  Synergistic Effects of Alloying and Thiolate Modification in Furfural Hydrogenation over Cu-Based Catalysts. , 2014, The journal of physical chemistry letters.

[3]  J. Yi,et al.  Effect of nickel on catalytic behaviour of bimetallic Cu–Ni catalyst supported on mesoporous alumina for the hydrogenolysis of glycerol to 1,2-propanediol , 2014 .

[4]  A. Alivisatos,et al.  Dendritic assembly of gold nanoparticles during fuel-forming electrocatalysis. , 2014, Journal of the American Chemical Society.

[5]  Uwe Schröder,et al.  Electrochemistry for biofuel generation: production of furans by electrocatalytic hydrogenation of furfurals , 2013 .

[6]  D. Vlachos,et al.  Production of dimethylfuran from hydroxymethylfurfural through catalytic transfer hydrogenation with ruthenium supported on carbon. , 2013, ChemSusChem.

[7]  I. Melián-Cabrera,et al.  Catalytic hydrotreatment of fast pyrolysis oil using bimetallic Ni–Cu catalysts on various supports , 2012 .

[8]  Sudipta De,et al.  One-pot conversions of lignocellulosic and algal biomass into liquid fuels. , 2012, ChemSusChem.

[9]  Zhenglong Li,et al.  Mild electrocatalytic hydrogenation and hydrodeoxygenation of bio-oil derived phenolic compounds using ruthenium supported on activated carbon cloth , 2012 .

[10]  Dennis J. Miller,et al.  Aqueous electrocatalytic hydrogenation of furfural using a sacrificial anode , 2012 .

[11]  Lungang Chen,et al.  Aqueous-phase hydrodeoxygenation of carboxylic acids to alcohols or alkanes over supported Ru catalysts , 2011 .

[12]  P. Arias,et al.  Liquid-phase glycerol hydrogenolysis to 1,2-propanediol under nitrogen pressure using 2-propanol as hydrogen source , 2011 .

[13]  Yuriy Román‐Leshkov,et al.  Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates , 2007, Nature.

[14]  P. Gallezot,et al.  Deactivation of metal catalysts in liquid phase organic reactions , 2003 .

[15]  R. Sheldon,et al.  Activities and stabilities of heterogeneous catalysts in selective liquid phase oxidations: recent developments , 2001 .

[16]  L. Brossard,et al.  Electrocatalytic hydrogenolysis of lignin model dimers at Raney nickel electrodes , 1997 .

[17]  J. Lipkowski,et al.  The influence of surface crystallography on the rate of hydrogen evolution at Pt electrodes , 1987 .

[18]  R. Parsons The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen , 1958 .