Electrochemical devices for converting carbon dioxide to useful reaction products include a solid or a liquid with a specific pH and/or water content. Chemical processes using the devices are also disclosed, including processes to produce CO, HCO−, H2CO, (HCO2), H2CO2, CH3OH, CH4, C2H4, CH3CH2OH, CH3COO−, CH3COOH, C2H6, (COOH)2, (COO−)2, acrylic acid, diphenyl carbonate, other carbonates, other organic acids and synthetic fuels. The electrochemical device can be a CO2 sensor.