Versatile Aerogel Fabrication by Freezing and Subsequent Freeze-Drying of Colloidal Nanoparticle Solutions.

A versatile method to fabricate self-supported aerogels of nanoparticle (NP) building blocks is presented. This approach is based on freezing colloidal NPs and subsequent freeze drying. This means that the colloidal NPs are directly transferred into dry aerogel-like monolithic superstructures without previous lyogelation as would be the case for conventional aerogel and cryogel fabrication methods. The assembly process, based on a physical concept, is highly versatile: cryogelation is applicable for noble metal, metal oxide, and semiconductor NPs, and no impact of the surface chemistry or NP shape on the resulting morphology is observed. Under optimized conditions the shape and volume of the liquid equal those of the resulting aerogels. Also, we show that thin and homogeneous films of the material can be obtained. Furthermore, the physical properties of the aerogels are discussed.

A Facile Surface Passivation of Hematite Photoanodes with TiO2 Overlayers for Efficient Solar Water Splitting.

The surface modification of semiconductor photoelectrodes with passivation overlayers has recently attracted great attention as an effective strategy to improve the charge-separation and charge-transfer processes across semiconductor-liquid interfaces. It is usually carried out by employing the sophisticated atomic layer deposition technique, which relies on reactive and expensive metalorganic compounds and vacuum processing, both of which are significant obstacles toward large-scale applications. In this paper, a facile water-based solution method has been developed for the modification of nanostructured hematite photoanode with TiO2 overlayers using a water-soluble titanium complex (i.e., titanium bis(ammonium lactate) dihydroxide, TALH). The thus-fabricated nanostructured hematite photoanodes have been characterized by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. Photoelectrochemical measurements indicated that a nanostructured hematite photoanodes modified with a TiO2 overlayer exhibited a photocurrent response ca. 4.5 times higher (i.e., 1.2 mA cm(-2) vs RHE) than that obtained on the bare hematite photoanode (i.e., 0.27 mA cm(-2) vs RHE) measured under standard illumination conditions. Moreover, a cathodic shift of ca. 190 mV in the water oxidation onset potential was achieved. These results are discussed and explored on the basis of steady-state polarization, transient photocurrent response, open-circuit potential, intensity-modulated photocurrent spectroscopy, and impedance spectroscopy measurements. It is concluded that the TiO2 overlayer passivates the surface states and suppresses the surface electron-hole recombination, thus increasing the generated photovoltage and the band bending. The present method for the hematite electrode modification with a TiO2 overlayer is effective and simple and might find broad applications in the development of stable and high-performance photoelectrodes.