We report the application of low-voltage direct current (dc) electric fields to self-assemble close-packed colloidal crystals in nonaqueous solvents from colloidal spheres that vary in size from as large as 1.2 μm to as small as 0.1 μm. The assemblies are created rapidly (∼2 min) from an initially low volume fraction colloidal particle suspension using a simple capacitor-like electric field device that applies a steady dc electric voltage. Confocal microscopy is used to observe the ordering that is produced by the assembly method. This spatial evidence for ordering is consistent with the 6-fold diffraction patterns identified by light scattering. Red, green, and blue structural color is observed for the ordered assemblies of colloids with diameters of 0.50, 0.40, and 0.29 μm, respectively, consistent with spectroscopic measurements of reflectance. The diffraction and spectrophotometry results were found to be consistent with the theoretical Bragg's scattering expected for closed-packed crystals. By switching the dc electric field from on to off, we demonstrate reversibility of the structural color response on times scales ∼60 s. The dc electric field assembly method therefore represents a simple method to produce reversible structural color in colloidal soft matter.

Ceria–zirconia-supported Ni catalysts (Ni/Ce0.83Zr0.17O2 or Ni/CZ) are prepared by dry impregnation, strong electrostatic adsorption, coprecipitation (CP), and combustion synthesis (CS). The nature and abundance of Ni species in these samples are characterized by X-ray adsorption spectroscopy, temperature-programmed reduction, and CO chemisorption. The bulk synthesis methods (i.e., CP and CS) produce Ni cations that are incorporated into the CZ lattice forming mixed-metal oxides with Ni3+ species at low Ni content. The formation of mixed-metal oxides increases the reducibility of CZ and increases the abundance of active surface oxygen. All NiO/CZ catalysts are active for methane dry reforming and retain some of their activity at a steady state. The initial methane conversion correlates linearly with the fraction of accessible Ni after reduction. The predominant path of catalyst deactivation strongly depends on the structure of the catalyst and, thus, on the synthesis method used. All catalysts experience agglomeration of Ni particles under reaction conditions. Improving the Ni dispersion to isolated species embedded in a support does not improve resistance to Ni particle growth. Coke formation is inversely related to the concentration of active surface oxygen. The dominant deactivation mechanism for catalysts made by CS is the encapsulation of Ni particles by the support.

Hydrothermal solutions are important media for the conversion of biomass-derived species to useful chemicals and the destruction of environmental pollutants. These solutions are aggressive and can degrade heterogeneous catalysts. This article describes a framework for understanding the hydrothermal stability of heterogeneous catalyst materials with respect to oxidation and dissolution. We applied the revised Helgeson–Kirkham–Flowers thermodynamic equation of state to determine the oxidation states and solubilities of metals and oxides in water at 150–550 °C and 22–50 MPa. Design criteria for catalyst compositions were determined through correlations between metal solubility and electronegativity and between oxide solubility and cation electronegativity, ionic–covalent parameter, and polarizing power. Design criteria for aqueous solution compositions were determined by constructing oxygen fugacity–pH diagrams, which illustrate material phase changes in response to changes in pH and the oxidative or reductive strength of the solution. Combined, these criteria facilitate design of stable catalytic materials for hydrothermal reactions.

Several ceria‐zirconia supported mono and bi‐metallic transition metal oxide clusters containing Fe, Cu, and Ni are synthesized by dry impregnation. Through XRD, H2‐TPR, NH3‐TPD, pyridine adsorption followed by FTIR spectroscopy and XAS, the well‐dispersed nature of the transition metal oxide clusters is revealed, and the Lewis acidity of the catalysts is assessed. In‐situ FTIR spectroscopy is used to monitor the methane activation on catalyst surfaces. All catalysts activate methane at 250 °C forming methyl, alkyl, and methoxy species on the catalyst surface. By co‐feeding steam and oxygen together with methane, continuous direct oxidation of methane to methanol can be achieved, with the complete oxidation to CO2 as the other reaction path. Methoxy species are found to be a key intermediate for methanol production. Lowering the methane conversion improves the methanol selectivity. By extrapolation, it is estimated that methanol selectivity close to unity can be achieved below a threshold of methane conversion at about 0.002 %. The formation of CuO and NiO mixed metal oxides produces stronger Lewis acid sites and yields higher methanol selectivity.

Current efforts to overcome the challenges of direct methane to methanol processes have focused on designing heterogeneous catalysts that perform methane partial oxidation using cheap and abundant oxidants such as molecular oxygen and water. An evaluation of the thermodynamic limitations of methanol production with the use of these oxidants is required to understand the maximum possible conversion and selectivity for a given feed composition and temperature. When O2 is present, the formation of the most thermodynamically stable product, carbon dioxide, must be inhibited. At practical temperatures for moderate scale processes, water as the sole oxidant results in extremely low steady‐state methane conversion, but higher yields can be achieved with coupled surface reactions. This work evaluates these thermodynamic challenges and opportunities for catalysts that can selectively oxidize methane to methanol with oxygen and water and discusses routes for achieving high methanol yields.