Solid-contact electrodes include a molecular redox buffer that is covalently attached to one of the components of the electrodes. These electrodes can be incorporated into electrochemical sensor systems. The electrode components are an electron conductor, a membrane and optionally, an interlayer. The electrode includes covalent attachment of the molecular redox buffer to the interlayer, to the electron conductor or the membrane. The interlayer includes nanoporous carbon such as CIM-carbon. The molecular redox buffer includes a well-defined redox pair, e.g., a complex of Co(II)/Co(III). The electrodes are ion-selective electrodes (ISEs) or reference electrodes. Methods include constructing solid contact electrodes and using the electrodes in electrochemical sensor systems to determine the quantity of an analyte in a sample. The electrochemical sensor systems include disposable paper-based devices and/or wearable devices for measuring analytes in a sample.