It has been over twenty years since the linear scaling of reaction intermediate adsorption energies started to coin the fields of heterogeneous and electrocatalysis as a blessing and a curse at the same time. It has established the possibility to construct activity volcano plots as a function of a single or two readily accessible adsorption energies as descriptors, but also limited the maximal catalytic conversion rate. In this work, it is found that these established adsorption energy-based descriptor spaces are not applicable to electrochemistry, because they are lacking an important additional dimension, the potential of zero charge. This extra dimension arises from the interaction of the electric double layer with reaction intermediates which does not scale with adsorption energies. At the example of the electrochemical reduction of CO2 it is shown that the addition of this descriptor breaks the scaling relations, opening up a huge chemical space that is readily accessible via potential of zero charge-based material design. The potential of zero charge also explains product selectivity trends of electrochemical CO2 reduction in close agreement with reported experimental data highlighting its importance for electrocatalyst design.
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