On-line mass spectrometry system for measurements at single-crystal electrodes in hanging meniscus configuration

We present the construction and some first applications of an On-line electrochemical mass spectrometry system for detecting volatile products formed during electrochemical reactions at a single-crystal electrode in hanging meniscus configuration. The system is based on a small inlet tip made of porous Teflon and a Peek holder, which is brought in close proximity (ca. 10–20 μm) to the electrode surface. The tip is connected to the mass spectrometer by glass and metal tubing. Because of the small amount of gas entering the mass spectrometer, no differential pumping is needed during the measurement. The tip construction and preparation introduced here leads to reproducible voltammetry with very good cleanliness characteristics. The presence of the tip has no significant influence on the blank voltammetry of a Pt(111) in sulfuric acid, and on voltammetric responses for CO adlayer oxidation, methanol oxidation, and hydroxylamine electrochemistry on Pt(111). The formation of gaseous products in these reactions can be followed accurately and is in good agreement with earlier results obtained by other mass spectrometric or spectroscopic techniques. The time response and tailing of the setup is on the order of seconds and mainly determined by the distance between the tip and the electrode.