Self‐Standing Metal Foam Catalysts for Cathodic Electro‐Organic Synthesis

Although electro‐organic synthesis is currently receiving renewed interest because of its potential to enable sustainability in chemical processes to value‐added products, challenges in process development persist: For reductive transformations performed in protic media, an inherent issue is the limited choice of metallic cathode materials that can effectively suppress the parasitic hydrogen evolution reaction (HER) while maintaining a high activity toward the targeted electro‐organic reaction. Current development trends are aimed at avoiding the previously used HER‐suppressing elements (Cd, Hg, and Pb) because of their toxicity. Here, this work reports the rational design of highly porous foam‐type binary and ternary electrocatalysts with reduced Pb content. Optimized cathodes are tested in electro‐organic reductions using an oxime to nitrile transformation as a model reaction relevant for the synthesis of fine chemicals. Their electrocatalytic performance is compared with that of the model CuSn7Pb15 bronze alloy that has recently been endorsed as the best cathode replacement for bare Pb electrodes. All developed metal foam catalysts outperform both bare Pb and the CuSn7Pb15 benchmark in terms of chemical yield and energetic efficiency. Moreover, post‐electrolysis analysis of the crude electrolyte mixture and the cathode's surfaces through inductively coupled plasma mass spectrometry (ICP‐MS) and scanning electron microscopy (SEM), respectively, reveal the foam catalysts’ elevated resistance to cathodic corrosion. This work develops leaded foam‐type electrodes through the dynamic hydrogen bubble template (DHBT) method and tests them in electro‐organic reductions using an oxime to nitrile transformation for synthesis of fine chemicals. All developed catalysts outperformed both Pb and CuSn7Pb15 in terms of chemical yields and energy efficiency. The latter material is deemed the best replacement for Pb in reductive organo‐electrosynthesis.