This study is concerned with the development of a modified sol-gel synthesis of Fe2O3 xerogels that would allow the design and control of the interfacial area between the oxidant iron oxide matrix and the metal reducing agent, thus optimizing the energetic yield of these highly energetic reactions. The modification consisted in the addition of a new class of di-functional template molecules, such as diamines or di-acids, as gelation agents. pH profile measurements indicated that the mechanism of reaction of propylene oxide and of succinic acid as the gelation agents was fundamentally different. Propylene oxide acts as a proton scavenger, reducing the hydrated iron species to Fe2O3, thus reducing the concentration of protons in the reaction mixture leading to an increase in pH. When succinic acid is used as the gelation agent, a decrease in pH versus time during the reaction indicates the formation of carboxylate ions, thus creating reactive molecules that are capable of stabilizing the Fe2O3 clusters during the growth process. Infrared spectra of the products in both reactions support presence of carboxylate groups in the Fe2O3 xerogels. X-ray diffraction analyses revealed low levels of crystallinity in both products, and the presence of different phases of Fe2O3.