Electrocatalytic hydrogenation of furfural on metal surfaces has become an important research subject due to the potential of the reaction product 2‐methylfuran as a renewable energy resource. Identifying effective determinants in this reaction process requires a thorough investigation of the complex electrode‐electrolyte interactions, which considers a variety of the influential components. In this work, in operando electrochemical Raman Spectroscopy and Molecular Dynamics simulations were utilized to investigate different characteristics of the interface layer in the electrocatalytic hydrogenation of furfural. Hereby, the influence of applied potentials, electrode material, and electrolyte composition were investigated in detail. The studied parameters give an insight into furfural's binding situation, molecular orientation, and reaction mechanism.

Electrocatalytic hydrogenation (ECH) of biomass derived compounds is an emerging technology for the production of biofuels. Herein, the ECH of furfural was investigated systematically on femtosecond laser-structured copper electrodes, amending the work on commonly used bulk copper electrodes or electrodeposits. Laser-structuring was used to vary the amount of active sites and the crystallographic orientation on the copper electrodes (evidenced with scanning electron microscopy and X-ray diffraction), and to achieve nickel alloying with the structured copper surface. We showed that the production rate and the Faradaic efficiency for furfural ECH on both Cu (111) and Ni-alloyed Cu were substantially increased. This improvement was ascribed to more catalytic sites offered for hydrogen and interactions of furanic intermediates. Moreover, the Ni-alloyed Cu electrode enabled the stable production of 2methylfuran even at large overpotentials. The mechanistic insights gained could open up new pathways to produce sustainable biofuel candidates with more stable electrodes.

The electrochemical ring hydrogenation of aromatic compounds is an important synthetic tool, though scarcely described in the literature. This research paper investigates the utilization of different Pd- and Pt-containing electrocatalyst...

Electrochemical Raman spectroscopy can provide valuable insights into electrochemical reaction mechanisms. However, it also shows various pitfalls and challenges. This paper gives an overview of the necessary theoretical background, crucial practical considerations for successful measurement, and guidance for in situ/in operando electrochemical Raman spectroscopy. Several parameters must be optimized for suitable reaction and measurement conditions. From the experimental side, considerations for the setup, suitable signal enhancement methods, choice of material, laser, and objective lens are discussed. Different interface phenomena are reviewed in the context of data interpretation and evaluation. Graphical Abstract