Carbon Supported Pd Nanostructures for Electrochemical Reduction of Carbon Dioxide – Effects of Ozonation
Authors: Suominen Milla , Moumaneix Lilian , Kobets Anna , Kallio Tanja 
Published: February 2024

Out of the transition metals capable of electrochemical carbon dioxide reduction, Pd is interesting as it can convert carbon dioxide electrochemically into formate or carbon monoxide depending on the applied potential. In fact, it is capable of producing formate at the most positive known potentials that are close to zero overpotentials although at an unfortunately low activity and at the cost of deactivation by carbon monoxide poisoning. One aim is to improve the activity and stability of Pd-based electrocatalysts towards formate production in low overpotentials. As Pd is a critical raw material, we also wish to decrease the amount of Pd required while maintaining high carbon dioxide electroreduction capability. These goals can be achieved by nanostructuring and supporting the Pd catalyst. Here, we have employed a simple wet impregnation synthesis approach to prepare small nanoparticles and nanowires of Pd supported on single walled carbon nanotubes and tested the optimum loading of Pd to obtain high formate yield with improved activity and stability. Reactive sites can be created on the carbon support by subjecting it to ozonation prior to supporting the metal, which may help certain interesting nanostructures, such as nanowires, to grow. Additionally, the oxygen functional groups on the carbon surface are expected to affect the wettability of the electrode which is important for achieving an efficient carbon dioxide electroreduction and a longer-term stability of the reaction. Therefore, we also studied the effects of ozonation of the carbon supports on the electrochemical reduction of carbon dioxide into both formate and syngas (mixture of hydrogen and carbon monoxide) on Pd. Carbon atoms inevitably participate in hydrogen evolution reaction and, thus, in syngas production on Pd-supported catalysts at higher overpotentials. Our results show that ozonation greatly enhances the activity of the catalyst material and improves its stability when applying low overpotentials for formate formation in comparison to the pristine carbon support. The current density on Pd supported ozone treated carbon nanotube material remains stable over 4h of carbon dioxide electrolysis at an applied potential of -0.45 V (vs. RHE) while Pd on pristine carbon support deactivates during the initial 30 min of the experiment. Longer electrolysis times do reveal slow changes in product distribution although activity on ozone-treated single walled carbon nanotube-supported catalyst is excellent. Additionally, the different support materials cause interesting changes in product selectivity upon applying higher overpotentials for the production of syngas. Pd supported on pristine nanotubes produces syngas with carbon monoxide-to-hydrogen ratios of 0.72 and 1.38 at applied potentials of -0.85 V (vs. RHE) and -0.95 V (vs. RHE), respectively, while ozone treated material produces less than 10% of carbon monoxide. Through physico-chemical characterizations of the materials we aim at understanding the observed changes in electrochemical reduction of carbon dioxide on carbon supported Pd nanostructures.