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Understanding the factors influencing nanocrystal formation is a challenge yet to be realized. In comparison to the large number of studies on nanocrystal synthesis and their applications, the number of studies on the effect of the precursor chemistry on nanocrystal composition and shape remains low. Although photochemical fabrication of metalsemiconductor nano-heterostructures is reported in literature, control over the free particle formation and the site of metal deposition have not been achieved. Moreover, utilization of metal- semiconductor nano-heterostructures in photocatalytic reactions other than water splitting is hardly explored. In this thesis, we studied the effect of chalcogenide precursor reactivity on the composition, morphology and the axial anisotropy of cadmiumchalcogenide nanocrystals. We also investigated the influence of the irradiation wavelength in synthesizing metal-semiconductor nano-heterostructures. Finally, we showed that metal semiconductor nano-heterostructures can be used as a photocatalyst for alcohol dehydrogenation reactions. We explored the pathways for the formation of Pt and Pd nanoparticles on CdS and CdS{sub 0.4}Se{sub 0.6} nanorods. This study revealed that the wavelength of irradiation is critical to control free-standing vs. bound metal (Pt and Pd) nanoparticles to semiconductor. Additionally, we observed that metal photodeposition occurs on specific segments of axially anisotropic, compositionally graded CdS0.4Se0.6 nanorods due to themore » band-gap differential between their nano-domains. We used semiconductor-metal heterostructures for sunlightdriven dehydrogenation and hydrogenolysis of benzyl alcohol. Heterostructure composition dictates activity (turnovers) and product distribution. A few metal (Pt, Pd) islands on the semiconductor surface significantly enhance activity and selectivity and also greatly stabilize the semiconductor against photoinduced etching and degradation.« less

Molecular level control of nanoscale composition and morphology: Toward photocatalytic nanocomposites for solar-to-chemical energy conversion of biomass