Unscrambling illusionary catalysis in three-dimensional particle-modified electrodes: Reversible reactions at conducting particles

Abstract We present a comprehensive theoretical analysis of electrochemically-reversible voltammetry at three-dimensional electrodes modified with conducting particles. For common experimental conditions, our model is independent of the particle size, -shape, and the exact structure of the porous layer formed by the immobilized particles, and only requires the layer density and -thickness to be known. Presented findings are hence directly applicable to a wide range of experimental systems. Depending on various experimental parameters, the voltammetric peak heights and positions may vary substantially and independently of the electrode kinetics. These observations may falsely suggest a catalytic activity of the deposited particles in the absence of the theoretical analysis introduced in this paper. Our findings are therefore of importance to a broad range of experimental studies in nano-electrocatalysis.