Surface engineering of crystals at nanoscale level by precisely and rationally exposing specific facets proved to be highly effective in enhancing the performance of inorganic functional nanocrystals. To do so, a comprehensive understanding of the growth mechanism was of great importance. By using hematite (α-Fe2O3) as an example, in this paper we demonstrated high effectiveness of controlling supersaturation of growth monomers in engineering the exposed facets of nanocrystals. Under surfactant-free hydrothermal conditions, a series of morphology evolution of α-Fe2O3 nanocrystals from {012} faceted pseudocubes to {113} faceted hexagonal bipyramids and {001} faceted nanoplates were successfully activated through concentration-, reaction time-, and solvent-dependent hydrolysis of ferric acetylacetonate. High supersaturation was eventually proven to be conducive to the formation of facets with high surface energy. Furthermore, the α-Fe2O3 nanocrystals enclosed with facets of high surface energy exhibited excellent catalytic activity and gas-sensing ability. The present work will deepen our understanding of thermodynamics and kinetic control over the morphology of nanocrystals as well as our understanding of surface-related performance of inorganic functional nanocrystals.

No abstract

The amount of energy in the form of natural gas hydrates is huge and likely substantially more than twice the amount of worldwide conventional fossil fuel. Various ways to produce these hydrates have been proposed over the latest five decades. Most of these hydrate production methods have been based on evaluation of hydrate stability limits rather than thermodynamic consideration and calculations. Typical examples are pressure reduction and thermal stimulation. In this work we discuss some of these proposed methods and use residual thermodynamics for all phases, including the hydrate phase, to evaluate free energy changes related to the changes in independent thermodynamic variables. Pressures, temperatures and composition of all relevant phases which participate in hydrate phase transitions are independent thermodynamic variables. Chemical potential and free energies are thermodynamic responses that determine whether the desired phase transitions are feasible or not. The associated heat needed is related to the first law of thermodynamics and enthalpies. It is argued that the pressure reduction method may not be feasible since the possible thermal gradients from the surroundings are basically low temperature heat that is unable to break water hydrogen bonds in the hydrate–water interface efficiently. Injecting carbon dioxide, on the other hand, leads to formation of new hydrate which generates excess heat compared to the enthalpy needed to dissociate the in situ CH4 hydrate. But the rapid formation of new CO2 hydrate that can block the pores, and also the low permeability of pure CO2 in aquifers, are motivations for adding N2. Optimum mole fractions of N2 based on thermodynamic considerations are discussed. On average, less than 30 mole% N2 can be efficient and feasible. Thermal stimulation using steam or hot water is not economically feasible. Adding massive amounts of methanol or other thermodynamic inhibitors is also technically efficient but far from economically feasible.