Elucidation of Titanium Dioxide Nucleation and Growth on a Polydopamine-Modified Nanoporous Polyvinylidene Fluoride Substrate via Low-Temperature Atomic Layer Deposition.

Interfaces combining polydopamine (PDA) and nanoparticles have been widely utilized for fabricating hybrid colloidal particles, thin films, and membranes for applications spanning biosensing, drug delivery, heavy metal detection, antifouling membranes, and lithium ion batteries. However, fundamental understanding of the interaction between PDA and nanoparticles is still limited, especially the impact of PDA on nanoparticle nucleation and growth. In this work, PDA is used to generate functional bonding sites for depositing titanium dioxide (TiO2) via atomic layer deposition (ALD) onto a nanoporous polymer substrate for a range of ALD cycles (<100). The resulting hybrid membranes are systematically characterized using water contact angle, scanning electron microscopy, atomic force microscopy, nitrogen adsorption and desorption, and X-ray photoelectron spectroscopy (XPS). An intriguing nonlinear relationship was observed between the number of ALD cycles and changes in surface properties (water contact angle and surface roughness). Together with XPS study, those changes in surface properties were exploited to probe the nanoparticle nucleation and growth process on complex PDA-coated porous polymer substrates. Molecular level understanding of inorganic and polymer material interfaces will shed light on fine-tuning nanoparticle-modified polymeric membrane materials.

Synthesis of metastable chromium carbide nanomaterials and their electrocatalytic activity for the hydrogen evolution reaction.

Transition metal carbides including chromium, molybdenum, and tungsten are of particular interest as renewable energy catalysts due to their low cost and abundance. While several single metal carbide systems form multiple phases with different compositions and crystal structures, most of these materials are not as well studied due to their limited synthetic approaches and instability. By taking advantage of a low temperature salt flux synthetic method, these unique phases can be more easily synthesized and separated as phase pure materials. As an example, Chromium carbide forms five different crystal structures including three common phases, Cr3C2, Cr7C3, and Cr23C6, and two less studied phases, Cr2C and CrC. All five compounds were synthesized using the salt flux method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and electrocatalytic testing for the hydrogen evolution reaction (HER). This low temperature method allows for routine access to multiple compounds in complex phase diagrams and separation of each phase synthetically. This represents a significant step forward in synthesizing rare phases like rocksalt CrC and hexagonal Cr2C and allows for investigation into their potential catalytic properties and future applications.

Templated homoepitaxial growth with atomic layer deposition of single-crystal anatase (101) and rutile (110) TiO2.

Homoepitaxial growth of highly ordered and pure layers of rutile on rutile crystal substrates and anatase on anatase crystal substrates using atomic layer deposition (ALD) is reported. The epilayers grow in a layer-by-layer fashion at low deposition temperatures but are still not well ordered on rutile. Subsequent annealing at higher temperatures produces highly ordered, terraced rutile surfaces that in many cases have fewer electrically active defects than the substrate crystal. The anatase epitaxial layers, grown at 250 °C, have much fewer electrically active defects than the rather impure bulk crystals. Annealing the epilayers at higher temperatures increased band gap photocurrents in both anatase and rutile.