Rotating Disk Electrode Studies of Benzaldehyde Oxidation on Group Ib Metals
Authors: Ramos Nathanael , Neyer Hudson , Medlin J. Will , Holewinski Adam 
Published: August 2024

Water electrolysis is a green means of producing hydrogen gas to be used as a fuel or reactant in key industrial processes such as ammonia production. The conventional system of oxygen evolution (OER) and hydrogen evolution (HER) suffers from slow kinetics at the anode and a high cell voltage limited by thermodynamics. One solution is to replace OER with another reaction such as an organic oxidation reaction that has a lower equilibrium potential and produces a valuable organic byproduct at the anode. Recent work has demonstrated that biomass-derived aldehydes such as furfural and 5-hydroxymethylfurfural can be selectively oxidized to their corresponding carboxylates and H2 on Cu-based anodes at low potentials (~0.1 VRHE) in alkaline media. In alkaline media, a hydroxide ion adds to the carbonyl carbon of an aldehyde molecule forming a gem diolate in solution phase. It is argued that dehydrogenation becomes more facile due to the weaker C-H bond of the gem diolate compared to the aldehyde form of the molecule. This may enable oxidation without the need for coadsorbed-OH. Additionally, aldehyde oxidation is only active on Au, Ag, and Cu electrodes at higher pHs.
The aim of this work is to identify the conditions under which low potential oxidation of aldehydes and high anodic Faradaic efficiency to H2 occurs, namely, electrode material and applied potential. To avoid polymerization side reactions of furans in alkaline media, we studied benzaldehyde as a model compound which has also been shown to exhibit low potential oxidation and anodic H2. The activity (rate of aldehyde consumption) and selectivity (to anodic H2 versus H2O) were compared for the group Ib metals (Au, Ag, Cu), each of which demonstrates a relatively early onset potential (<0.4 VRHE) and generates anodic H2 at certain potentials. Rotating disk electrode studies with Koutecky-Levich analysis were conducted to separate mass transfer effects from kinetic current to compare the intrinsic activity of each electrode. Additionally, the average number electrons transferred per aldehyde molecule consumed was estimated from Koutecky-Levich analysis; the one-electron pathway combines the aldehyde hydrogens to H2 while the two-electron pathway requires an additional electron per aldehyde molecule to oxidize the hydrogen from the surface to form H2O. Rotating ring disk electrode studies were used to further validate the anodic H2 generation as a Pt ring was still able to oxidize H2 despite the presence of benzaldehyde. This was used as an additional means of estimating the selectivity to H2 as a function of potential.
CVs for benzaldehyde oxidation on each metal are shown in Figure a. Peak current followed the order of Au > Ag >> Cu. Au reached a mass transfer limiting current, and Ag also showed an RPM dependence but did not reach full mass transfer limitations. Cu was the least active and did not show any mass transfer dependence. On the other hand, Cu has the earliest onset potential followed by Ag then Au. The average number of electrons transferred per aldehyde molecule according to RRDE measurements is shown in Figure b, where one electron represents H2 and two electrons represents H-oxidation to H2O. Cu had 100% selectivity to H2 over its entire potential window of activity (up to 0.45 VRHE). Au and Ag have high selectivity to H2 at low potentials but decreases to near zero H2 production in the range of 0.6-0.8 VRHE; the decrease in selectivity to H2 on Ag occurs slightly earlier than Au (~0.1 V). H2 selectivity is related to the inability of each metal to oxidize H to H2O at low potentials.

Figure 1