Design of novel catalysts by infusion of presynthesized nanocrystals into mesoporous supports

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Gupta, Gaurav, Ph. D.

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Traditionally, supported metal catalysts have been synthesized by reduction of precursors directly over the support. In these techniques, it is challenging to control the metal cluster size, composition and crystal structure. Herein, we have developed a novel approach to design catalysts with controlled morphologies by infusing presynthesized nanocrystals into the supports. High surface area mesoporous materials, including graphitic carbons, have been utilized for obtaining a high degree of metal dispersion to enhance catalyst stabilities and activities. Gold and iridium nanocrystals have been infused in mesoporous silica with loadings up to 2 wt % using supercritical CO₂ as an antisolvent in toluene to enhance the van der Waals interactions between nanocrystals and the silica. The iridium catalysts show high catalytic activity and do not require high temperature annealing for ligand removal, as ligands bind weakly to the iridium surface. To further enhance metal loadings to >10 % in the catalysts, short-ranged interactions between the metal nanocrystals and the support are further strengthened with weakly binding ligands to expose more of the metal surface to the support. For pre-synthesized FePt nanocrystals, coated with oleic acid and oleylamine ligands, high loadings >10 wt % in mesoporous silica are achieved, without using CO₂. The strong metal-support interactions favor FePt adsorption on the support and also enhance stability against sintering at high temperatures. High resistance to sintering favors formation of the FePt intermetallic crystal structure with <4 nm size upon thermal annealing at 700 °C. The fundamental understanding of the metal-support interactions gained from these studies is then utilized in the design of highly stable Pt and Pt-Cu electrocatalysts with controlled size, composition and alloy structure supported on graphitized mesoporous carbons for oxygen reduction. The resistance of the graphitic carbons to oxidation coupled with strong metal-support interactions mitigate nanoparticle isolation from the support, nanoparticle coalescence, Pt dissolution and subsequent Ostwald ripening and thus enhance catalyst stability. The control of the Pt nanocrystal morphology with high concentrations of highly active (111) surface leads to 25% higher activities than commercial Pt catalysts. Furthermore, the catalyst activities obtained for Pt-Cu catalysts are 4-fold higher than Pt catalysts due to strained Pt shell generated from electrochemical dealloying of copper from the nanoparticle surface.