Nanofluids (NFs) are colloidal suspensions of nanoparticles (NPs) within a base fluid. Unlike conventional mixtures, NFs exhibit dramatically enhanced properties, such as an abnormal increase in heat capacity at low concentration of NPs (e.g., Cp values 30% higher than the base material value). Understanding the thermo-physical behavior of NFs is essential for their application as thermal energy storage systems. In this study, we analyze a sodium nitrate ionic system containing 1 wt%, 3 wt% and 7 wt% of SiO2 NPs with different techniques like infrared thermography, infrared spectroscopy and differential scanning calorimetry (DSC) in order to shed light on the mechanism behind the increase of Cp. The themographies reveal the presence of a colder layer on top of the NF with 1 wt% of NPs whereas this layer does not appear at higher concentrations of NPs. The IR spectrum of this foamy top layer evidences the high amount of SiO2 bonds suggesting the clustering of the NPs into this layer linked by the nitrate ions. The linking is enhanced by the presence of hydroxyls in the NPs' surface (i.e., hydroxilated NPs) that once mixed in the NF suffer ionic exchange between OH- and NO3- species, leading to O2-Si-O-NO2 species at the interface where a thermal boundary resistance or Kapitza resistance appears (RT = 2.2 m2 K kW-1). Moreover, the presence of an exothermic reactive processes in the calorimetry of the mixture with 1 wt% of NPs evidences a reactive process (ionic exchange). These factors contribute to the heat capacity increase and thus, they explain the anomalous behavior of the heat capacity in nanofluids.