Described herein are substrates, sensors and systems related to measuring the concentration of an analyte such as hydrogen ion in a sample. Redox active moieties whose reduction and/or oxidation potentials are sensitive to the presence of an analyte are immobilized onto a silicon surface. Immobilized redox active moieties whose reduction and/or oxidation potential are insensitive to the analyte can be used for reference. Voltammetric measurements made using such modified silicon surfaces can accurately determine the presence and/or concentrations of analytes in a sample of interest. The silicon electrochemical sensors of the invention are robust and can be made so as not to require calibration or re-calibration.