Highly Electrocatalytic Conversion and Separation of Organometallic Ions to Vapor on an Au-Modified Nickel Foam Cathode: A Classic Application for Mercury Speciation Analysis at the μg/L Level

Abstract

A simple, accurate, and sustainable electrocatalytic conversion strategy has been used for the speciation analysis of trace mercury. An Au- or Ag-modified nickel foam electrode (Au/NFE or Ag/NFE) prepared by cyclic voltammetry was used first as a cathode for the gaseous conversion of organomercury. The mechanism of improving the electrochemical inertness of methylmercury is considered to be the migration of charge centers and the weakening of C–Hg bonds caused by the formation of Au–Hg amalgam. A large specific surface area, high catalytic activity, and low transport resistance allow an effective conversion of 0.1 μg L–1 level organomercury on the Au/NFE surface. The difference of gaseous conversion behavior under current control also provides a green way for the analysis of mercury speciation. A lower limit of detection (4.9 pg g –1 for Hg2+ and 5.5 pg g –1 for CH3Hg+), stronger anti-interference ability, more than 180 sample analysis capacities, and less than 8% signal fluctuation, importantly, confirmed that the electrocatalytic conversion technology based on the gold/silver-modified NFE is very suitable for the analysis of ultratrace methylmercury in complex matrix samples, such as animal and plant samples.