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In this work, plasmonic metal nanoparticles (MNPs) are utilized to improve the photoelectrochemical (PEC) response of strontium titanate (STO). These MNPs were introduced by either direct exsolution, i.e., nickel (Ni), copper (Cu), iron (Fe), ruthenium (Ru), and silver (Ag), or by galvanically replacing exsolved less noble MNPs, i.e., Ni by Gold (Au), or Cu for Ag. Au, Ag, and Cu were the materials chosen with significant plasmonic activity; Fe, Ru, Pt, and Ni were used to make MNPs with minimal plasmonic response. Two different stoichiometries of STO were synthesized. One, La-doped A-site deficient STO (La0.6Sr0.2Ti0.9Ni0.1O3–x), was exclusively doped with Ni and utilized as powder samples. The other stoichiometry was A-site excess STO (Sr1.07Ti0.93M0.07O3±δ, where M is the dopant) was doped with various metals. These excess perovskites were studied in thin film and powder forms. A-site excess STO thin films were deposited by pulsed laser deposition on silicon substrates. The as-deposited thin films appeared nanocrystalline or amorphous until the exsolution process was engaged. The exsolution step was studied explicitly for these A-site excess STO thin films where the formation of MNPs occurred not only at or near the thin film surface but also on grain interfaces and in bulk. Moreover, the dopant diffused significantly during the process. While the size of the template particles depended on the exsolution conditions, the galvanic replacement reaction determined the shapes and sizes of the newly formed MNPs. The replacement time and the form (thin film/powder) of STO influenced the results, both completely replaced particles and partially replaced particles with complex structures were obtained. Additionally, more prolonged galvanic replacement reactions lead to larger particles. In turn, the specific shape of the plasmonic MNPs determined the localized surface plasmon resonance band shape and peak position. Overall, exsolution leads to well-socketed MNPs, a property seemingly inherited by the MNPs created by galvanic replacement. Well-socketed MNPs are extremely difficult to obtain by any other technique and have a favorable localized surface plasmon resonance peak shift. The PEC response revealed that reducing STO first decreases the material’s response. Reducing it further, however, increases the PEC response significantly. Au MNPs increase the PEC performance until the MNPs reach a specific size and subsequently decrease the PEC performance when growing more prominent. This work highlights the ease by which well-socketed plasmonic MNPs can be created, some impossible to synthesize by another technique, and how different reaction conditions can change the shape and size of the MNPs, ultimately tuning the localized surface plasmon resonance band shape and peak position. The method of exsolution and galvanic replacement reaction was generalized by utilizing different elements, implying that the tuning of catalytic activity depends on the choice of elements and reaction conditions.
