Electrochemical multisensor system for monitoring hydrogen peroxide, hydrogen and oxygen in direct synthesis microreactors

We present an electrochemical microsensor system for the monitoring of hydrogen peroxide, dissolved hydrogen and dissolved oxygen inside a direct synthesis microreactor. The setup allows the online, in situ measurement of high reactant concentrations by amperometric detection of all three reactants in aqueous solution using chronoamperometric protocols. Hydrogen peroxide is a key chemical for industrial oxidation applications, and its catalyzed direct synthesis is an attractive process route. For the first time, we integrated an electrochemical cell into a high pressure stainless steel microreactor environment (pressures up to 100 bar, pH of 3-4 and presence of bromide) by fabricating sensor plugs with 300 pm platinum microelectrodes encapsulated into a robust epoxy housing. The first microfabricated silver/silver bromide pseudo-reference electrode, integrated by electrodeposition, allowed to obtain a stable measurement potential directly from the electrolyte containing bromide. The investigation of platinum electrochemistry in the presence of bromide by cyclic voltammetry led to the development of chronoamperometric protocols for the stable, precise and reproducible measurement in this environment. Hydrogen peroxide was detected under reaction conditions showing linear behaviour up to 20 mM with high sensitivity of 55 mu A cm(-2) mM(-1) and excellent stability by application of a diffusion limiting hydrogel layer to the electrode surface. This linear range surpasses most micro- and nanostructured platinum approaches. Oxygen and hydrogen were both measured at elevated pressures up to 70 bar and high dissolved concentrations up to 52 mM and 40 mM with measured sensitivities of 26 mu A cm(-2) mM(-1) and 356 mu A cm(-2) mM(-1), respectively. We have successfully shown the application of electrochemical sensors for online, in situ monitoring of analyze concentrations under conditions found in direct synthesis microreactors.