All-solid-state reference electrodes based on colloid-imprinted mesoporous carbon and their application in disposable paper-based potentiometric sensing devices

Reference electrodes are used in almost every electroanalytical measurement. Here, all-solid-state reference electrodes are described that employ colloid-imprinted mesoporous (CIM) carbon as solid contact and a poly(vinyl chloride) reference membrane to contact the sample. Such a reference membrane is doped with a moderately hydrophilic ionic liquid and a hydrophobic redox couple, leading to well-defined constant potentials at the interfaces of this membrane to the sample and to the solid contact, respectively. Due to the intrinsic properties of CIM carbon, reference electrodes with a CIM carbon solid contact exhibit excellent resistance to common interfering agents such as light and O₂, with outstanding potential stability in continuous potentiometric measurements. The potential drift of CIM carbon-based reference electrodes without redox couple is as low as 1.7 μV/h over 110 h, making them the most stable all-solid-state reference electrodes reported so far. To demonstrate the compatibility of CIM carbon-based reference electrodes with miniaturized potentiometric systems, these reference electrodes were integrated into paper-based potentiometric sensing devices, successfully replacing the conventional reference electrode with its reference electrolyte solution. As a proof of concept, disposable paper-based Cl^- sensing devices that contain stencil-printed Ag/AgCl-based Cl^- selective electrodes and CIM carbon-based reference electrodes were constructed. These sensing devices are inexpensive, easy to use, and offer highly reproducible Cl^- measurements with sample volumes as low as 10 μL.