Essential analysis of cyclic voltammetry of methanol electrooxidation using the differential electrochemical mass spectrometry

Abstract

Using the cyclic voltammetry to test the performance of methanol electrooxidation is the most popular method to seek anodic catalysts for direct methanol fuel cells. A cyclic voltammetry of methanol electrooxidation typically has two peaks on Pt-based catalysts: one peak of P f with the current of j f in the forward scan, the other peak of P b with the current of j b in the backward scan. The ratio of j f / j b is an intensively used criterion to evaluate the ability of CO tolerance of Pt-based catalysts. In this study, however, it is demonstrated that both peak currents are ascribed to the consumption of methanol at the surface of the electrode using the differential electrochemical mass spectrometry (DEMS). In addition, our results reveal that the peak area ratio should be a criterion linking to the overlapping region between the potentials of methanol oxidation and the potentials of the reduction of the oxidized surface generated in the forward scan. Based on our analysis, the ratio of the integrated current of P f and P b can be a new descriptor to describe the reducibility of the oxidized Pt surface formed at high potential instead of CO anti-poisoning of the catalyst. • Differential electrochemical mass spectrometry is used to monitor methanol oxidation. • The characteristic of cyclic voltammetry (CV) of methanol oxidation is revealed. • A new descriptor in evaluating the anti-oxidizing of catalyst is proposed. • The electrode surface changes during CV process are elucidated precisely.