Selective Catalytic Reduction of NO Using Phase-Pure Anatase, Rutile, and Brookite TiO2 Nanocrystals.

We demonstrate a facile selective synthesis of phase-pure anatase, rutile, and brookite nanocrystal polymorphs of titania (TiO2) using a benign hydrothermal treatment of an industrial grade TiOSO4 precursor. Acetic acid (CH3COOH) is used for the synthesis of anatase, glycolic acid (HOCH2COOH) is used for rutile, and both glycolic acid and ammonium hydroxide (NH4OH) are used for obtaining brookite. The detailed morphologies of the as-synthesized materials are determined from a combination of powder X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. The anatase nanocrystals are terminated by low-energy {101} facets and a small amount of high-energy {001} facets, whereas the rutile nanocrystals are terminated by low-energy {110} facets and a small amount of high-energy {111} facets. The brookite nanocrystals are terminated by low-energy {210} facets and {111} facets, and not the high-energy {101} and {201} facets erroneously reported in the literature. The activities of as-synthesized TiO2 nanocrystals as supports for vanadia-titania catalysts are investigated by measuring the selective catalytic reduction of NO using ammonia (NH3-SCR). The O2-activated samples show similar oxidovanadium(V) bands in their Raman spectra, and the relative activity relation is found to be anatase > brookite > rutile. In addition, the photocatalytic activity is evaluated by measuring the decomposition of Rhodamine B (RhB) under UV-light irradiation, and the relative activity order is found to be P25 > anatase ≈ rutile > brookite.

Autocatalytic Formation of High-Entropy Alloy Nanoparticles.

High-entropy alloy (HEA) nanoparticles hold great promise as tunable catalysts. Despite the fact that alloy formation is typically difficult in oxygen-rich environments, we found that Pt-Ir-Pd-Rh-Ru nanoparticles can be synthesized under benign low-temperature solvothermal conditions. In situ X-ray scattering and transmission electron microscopy reveal the solvothermal formation mechanism of Pt-Ir-Pd-Rh-Ru nanoparticles. For the individual metal acetylacetonate precursors, formation of single metal nanoparticles takes place at temperatures spanning from ca. 150 °C for Pd to ca. 350 °C for Ir. However, for the mixture, homogenous Pt-Ir-Pd-Rh-Ru HEA nanoparticles can be obtained around 200 °C due to autocatalyzed metal reduction at the (111) facets of the forming crystallites. The autocatalytic formation mechanism suggests that many types of HEA nanocatalysts should accessible with scalable solvothermal reactions, thereby providing broad availability and tunability.

Scrutinizing particle size related bond strengthening in anatase TiO2.

A series of small, middle, and large anatase TiO2 particles were synthesized through the hydrolysis of titanium tetraisopropoxide (TTIP) to investigate the size-related chemical bond length and strength variation. Unit cell volume contraction with decreasing particle size is identified from Rietveld refinement of high-resolution synchrotron powder X-ray diffraction (PXRD) patterns. More titanium vacancies are also found for smaller anatase particles. Contrary to the variation in unit cell volume, a larger Debye temperature ΘD(TiO2) derived from the linear and nonlinear fitting of atomic displacement parameters (Uiso(TiO2)) as a function of temperature is revealed for smaller anatase particles. The length of the Ti-O bond is also shorter for smaller anatase particles. Furthermore, optical phonon frequencies blue-shifting with the decrease in anatase particle size are determined by Raman spectroscopy. X-ray photoelectron spectroscopy (XPS) analysis rules out the presence of a large amount of Ti3+, while optical diffuse reflectance measurement eliminates the existence of a large number of oxygen vacancies in all particles. Combining the analysis results of PXRD, thermogravimetric analysis (TGA), and Fourier-transform infrared spectroscopy (FTIR), more structural and surface hydroxyls (-OH) appear to exist in smaller anatase particles. It is the structural and surface -OH that are responsible for the size-related chemical bond length and strength variation in the as-synthesized anatase particles.

Facile synthesis of brookite TiO2 nanoparticles.

Brookite is the most difficult TiO2 polymorph to obtain in phase pure form. Here we report on a facile synthesis method for phase-pure brookite nanoparticles using a broad range of titanium precursors. General availability of phase pure brookite opens up multiple research activities to explore both fundamental properties as well as applications. The synthesis method is scalable and thus it potentially allows for large-scale industrial production.

Continuous flow hydrothermal synthesis of phase pure rutile TiO2 nanoparticles with a rod-like morphology.

Titania nanocrystals are used in numerous applications but specific polymorphs (anatase, rutile, brookite) are typically required in specific applications making synthesis control over the crystal phase essential. Supercritical continuous flow reactors constitute fast, scalable alternatives to conventional autoclave hydrothermal synthesis. They provide outstanding control over nanoparticle characteristics such as size, crystallinity, and morphology but previous studies have always resulted in anatase products. Here we report, for the first time, a continuous hydrothermal flow method for obtaining phase pure rutile nanoparticles thereby significantly broadening the crystal design space for large scale titania applications. Through variation of the reactor temperature, the dimensions of the rod-like rutile crystallites are tunable in a range of 35 to 60 nm in length and 10 to 35 nm in width (maximum aspect ratio of ∼3.5) leading to a tunable band gap (3.2-3.5 eV) and high specific surface areas exceeding 200 m2 g-1.

Mapping the redox chemistry of common solvents in solvothermal synthesis through in situ X-ray diffraction.

Solvothermal technology shows great promise in "green" materials synthesis, processing, and recycling. The outcome of a specific solvothermal reaction depends strongly on the solvent properties, and the versatility of solvothermal synthesis hinges on the very large changes in solvent properties as a function of temperature and pressure. Here, six simple 3d transition metal nitrate salts (Cu(ii), Ni(ii), Co(ii), Fe(iii), Mn(ii), Cr(iii)) were dissolved in five common solvents (water, ethanol, ethylene glycol, glycerol, and 10% hydrogen peroxide solution) and heated stepwise up to 450 °C at a pressure of 250 bar using an in situ reactor while X-ray scattering data was recorded. A range of crystalline phases were observed in the form of metallic phases, metal oxides, and other ionic compounds. These data by themselves provide simple recipes for synthesis of many technologically important 3d transition metal nanomaterials. However, more generally the oxidation states of the metals in the synthesized materials can be used to map the solvent redox properties under solvothermal conditions. It is found that glycerol and ethylene glycol are strongly reducing, ethanol is moderately reducing, while water is weakly oxidizing. The behavior of the hydrogen peroxide solution is more complex including both oxidization and reduction. Furthermore, it is observed that the reducing powers of ethanol, ethylene glycol, and glycerol are enhanced with increasing temperature. The mapping of the redox properties of these common solvents provides a method for tailoring a given reaction through choice of solvent and reaction temperature. Solvothermal processes represent an environmentally benign alternative to the use of toxic reducing agents in chemical reactions, and quantification of the redox chemistry is a first step in rational materials design.

Three-dimensional morphology of anatase nanocrystals obtained from supercritical flow synthesis with industrial grade TiOSO4 precursor.

Anatase TiO2 (a-TiO2) nanocrystals are vital in catalytic applications both as catalysts (e.g. photodegradation) and as a carrier material (e.g. NOx removal from exhaust). The synthesis of a-TiO2 nanocrystals and their properties have been heavily scrutinized, but there exists a clear gap between the scientific literature, and the scale and price expectation of industrial application. Here it is demonstrated that the industrially most attractive Ti precursor, titanyl sulfate (TiOSO4), can be combined with the green, scalable and fast supercritical flow method to produce phase pure and highly crystalline a-TiO2 nanoparticles with high specific surface area. Control of the nanocrystal morphology is important since it is known that certain facets substantially promote catalytic activity. It is, however, in itself challenging to determine nanocrystal morphology to provide a rational basis for the synthesis control. Here we advocate the use of advanced Rietveld refinement of powder X-ray diffraction data including anisotropic size broadening models in aiding to establish the sample three-dimensional morphology. This relatively quick and robust method assists in overcoming the often encountered ambiguity inherent in two-dimensional to three-dimensional reconstruction of selected particle morphologies with transmission electron microscopy and tomography techniques.