A. Walcarius et al., Amperometric detection of nonelectroactive cations in electrolyte-free flow systems at zeolite modified electrodes, ELECTROANAL, 11(6), 1999, pp. 393-400
An electrochemical detector was designed and constructed, based upon a thin
-layer cell with a working electrode prepared from carbon paste modified wi
th copper- (or silver-) exchanged zeolite particles. This electrode was the
n evaluated as a sensor for nonelectroactive cations in an electrolyte-free
flow injection system and as an amperometric detector for suppressed ion c
hromatography. In the absence of supporting electrolyte, a higher signal-to
-background ratio enhanced by about two order of magnitude the response obt
ained in electrolytic medium. Peak currents resulted from an important fara
dic component which was due to the electrochemical activity of the mediator
-containing zeolites, while the capacitive counterpart was much lower. When
applied to the analysis of alkali, alkaline earth metal and ammonium ions,
in combination with a suppressed ion chromatography system, the zeolite-mo
dified detector gave rise to reproducible amperometric responses. This resu
lted in chromatograms comparable to those obtained simultaneously by using
a conductivity detector in series, and any extra-column effects were never
observed. The most sensitive responses were achieved when using zeolites di
splaying the largest pore size, the highest ion exchange capacity, and the
most mobile mediator, to ensure the highest exchange rates for the analytes
within the zeolite framework.