Tuning the Sensitivity of Photonic Sensors Toward Alkanes Through the Textural Properties of Hybrid Xerogel Coatings

Abstract This work exemplifies how incorporating organosilane modifiers into silica matrices allows for tuning the optical response of reflection photonic sensors through customizing the textural properties of hybrid xerogel sensing films. Xerogels with propyl molar percentages 0, 5, and 10% are used to construct photonic probes (OFS0pTEOS, OFS5pTEOS and OFS10pTEOS, respectively) by dip‐coating upon optimizing film deposition parameters. The time response of these probes toward a battery of volatile organic compounds (VOCs) comprising species with different functionality, size‐shape, and polarity is systematically analyzed through ON/OFF experiments, revealing that a low propyl content makes the poor‐responding OFS0pTEOS film highly sensitive toward non‐aromatic, large molecules with low‐polar or non‐polar character in OFS5pTEOS. This sensor is particularly sensitive toward alkanes, with globular cyclohexane (cyHex) outperforming elongated n ‐hexane. Variable‐temperature calibration curves obtained from step‐by‐step experiments and adsorption–desorption cycles corroborate these observations and allow hysteresis to be quantified. The response to cyHex closely follows VOC concentration changes with the most stable signal among analytes, leading to well‐defined curves with low‐to‐negligible hysteresis. The isosteric enthalpies of cyHex adsorption are obtained for both the bulk material and the sensor, demonstrating labile adsorbate‐adsorbent interactions ruling the sensor response and becoming more exothermic for larger VOC concentrations.