A well-ordered porous three-phase boundary (TPB) was prepared with a polystyrene sphere as template and examined to improve the sensitivity of yttria-stabilized zirconia (YSZ)-based mixed-potential-type NO2 sensor due to the increase of the electrochemical reaction active sites. The shape of pore array on the YSZ substrate surface can be controlled through changing the concentration of the precursor solution (Zr4+/Y3+ = 23 mol/L/4 mol/L) and treatment conditions. An ordered hemispherical array was obtained when CZr 4+ = 0.2 mol/L. The processed YSZ substrates were used
to fabricate the sensors, and different sensitivities caused by different morphologies were tested. The sensor with well-ordered porous TPB exhibited the highest sensitivity to NO2 with a response value of 105 mV to 100 ppm of NO2, which is approximately twice as much as the smooth one. In addition, the sensor also showed good stability and speedy response kinetics. All these enhanced sensing properties might be due to the structure and morphology of the enlarged TPB.