Selective electrocatalytic hydrogenation of bio-oil to oxygenated chemicals via suppression of deoxygenation

Abstract

Catalytic hydrogenation of bio-oil provides an avenue to produce renewable chemicals. To this end, electrocatalytic hydrogenation is especially interesting when powered using low-carbon electricity; however, it has to date lacked the needed selectivity: when hydrogenating bio-oil to oxygenated hydrocarbons, for example, it reduces the desired oxygenated groups (-OH and -OCH3). Here we report that Rh and Au modulate electronic structure of Pt and steer intermediate energetics to favor the hydrogenation while suppressing deoxygenation using computational studies and in-situ spectroscopies. PtRhAu catalysts achieve a record 47% faradaic efficiency (FE) and a partial current density (Jp) of 28 mA·cm-2 toward oxygenated 2-methoxycyclohexanol from lignin-derived guaiacol under room temperature and ambient pressure, representing 1.5x FE and 3.5x Jp increases compared to the best prior reports. We further demonstrate an integrated lignin biorefinery where wood-derived lignin oils are selectively hydrogenated and funneled to the oxygenated 2-methoxy-4-propylcyclohexanol using PtRhAu catalysts.

In situ reconfiguration of plasma-engineered copper electrodes towards efficient electrocatalytic hydrogenation

“…This deduction allows for the correlation of ECH kinetics with binding energies, consistent with the recent identification of lignin electrochemical reduction. 39 Defect engineering is one of the most effective strategies to improve electrocatalysis via enhancing intermediate chemisorption on a vast amount of coordinatively unsaturated sites. [40][41][42] In this regard, BE H and BE FAL are examined on pristine and defective Cu (p-Cu and d-Cu) surfaces via DFT calculations.…”

Electrokinetic Analyses Uncover the Rate‐Determining Step of Biomass‐Derived Monosaccharide Electroreduction on Copper

“…[3,4] The past few years have witnessed a growing interest in the conversion of biomass-derived feedstock utilizing renewable-driven electricity, which allows operations under mild conditions. [5][6][7][8][9][10] In the prior studies, glycerol was electrochemically oxidized to dihydroxyacetone (DHA) on a bismuth (Bi) modified carbon-supported platinum (Pt) electrode with high selectivity. [11,12] As one of the simplest monosaccharides, DHA can function as a renewable building block in the production of high-demand commodities, such as acetol.…”