Water-stable, hydroxamate anchors for functionalization of TiO2 surfaces with ultrafast interfacial electron transfer
نویسندگان
چکیده
A novel class of derivatized hydroxamic acid linkages for robust sensitization of TiO2 nanoparticles (NPs) under various aqueous conditions is described. The stability of linkages bound to metal oxides under various conditions is important in developing photocatalytic cells which incorporate transition metal complexes for solar energy conversion. In order to compare the standard carboxylate anchor to hydroxamates, two organic dyes differing only in anchoring groups were synthesized and attached to TiO2 NPs. At acidic, basic, and close to neutral pH, hydroxamic acid linkages resist detachment compared to the labile carboxylic acids. THz spectroscopy was used to compare ultrafast interfacial electron transfer (IET) into the conduction band of TiO2 for both linkages and found similar IET characteristics. Observable electron injection and stronger binding suggest that hydroxamates are a suitable class of anchors for designing water stable molecules for functionalizing TiO2.
منابع مشابه
Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes.
A novel class of derivatized acetylacetonate (acac) linkers for robust functionalization of TiO2 nanoparticles (NPs) under aqueous and oxidative conditions is reported. The resulting surface adsorbate anchors are particularly relevant to engineering photocatalytic and photovoltaic devices since they can be applied to attach a broad range of photosensitizers and photocatalytic complexes and are ...
متن کاملHydroxamate anchors for improved photoconversion in dye-sensitized solar cells.
We present the first analysis of performance of hydroxamate linkers as compared to carboxylate and phosphonate groups when anchoring ruthenium-polypyridyl dyes to TiO2 surfaces in dye-sensitized solar cells (DSSCs). The study provides fundamental insight into structure/function relationships that are critical for cell performance. Our DSSCs have been produced by using newly synthesized dye mole...
متن کامل“ Hydroxamates as Robust , Conductive Anchors for Semiconductor Oxide Surfaces
Working in the Yale Solar Group (YSG PIs: Batista, Brudvig, Crabtree, Schmuttenmaer) in the Chemistry Dept., we have introduced a more robust anchor to attach molecular components to semiconductor oxide surfaces such as to TiO2 nanoparticles (n-TiO2). The goal of the YSG, generation of fuels from solar-driven water splitting, required that the dye and catalyst components be attached to the n-Ti...
متن کاملOrdered water structure at hydrophobic graphite interfaces observed by 4D, ultrafast electron crystallography.
Interfacial water has unique properties in various functions. Here, using 4-dimensional (4D), ultrafast electron crystallography with atomic-scale spatial and temporal resolution, we report study of structure and dynamics of interfacial water assembly on a hydrophobic surface. Structurally, vertically stacked bilayers on highly oriented pyrolytic graphite surface were determined to be ordered, ...
متن کاملModel study of coherent quantum dynamics of hole states in functionalized semiconductor nanostructures.
Functionalization of semiconductor nanocrystals can be achieved by anchoring organic ligands to the surface dangling bonds. The resulting surface complexes often introduce electronic states in the semiconductor band gap. These interband states sensitize the host material for photoabsorption at frequencies characteristic of the molecular adsorbates, leading to the well-known process of photoexci...
متن کامل