The energetics of the TiO2 polymorphs (rutile, anatase, and brookite) were studied by high temperature oxide melt drop solution calorimetry. Relative to bulk rutile, bulk brookite is 0.71 ؎ 0.38 kJ͞mol (6) and bulk anatase is 2.61 ؎ 0.41 kJ͞mol higher in enthalpy. The surface enthalpies of rutile, brookite, and anatase are 2.2 ؎ 0.2 J͞m 2 , 1.0 ؎ 0.2 J͞m 2 , and 0.4 ؎ 0.1 J͞m 2 , respectively. The closely balanced energetics directly confirm the crossover in stability of nanophase polymorphs inferred by Zhang and Banfield (7). An amorphous sample with surface area of 34,600 m 2 ͞mol is 24.25 ؎ 0.88 kJ͞mol higher in enthalpy than bulk rutile.

With controlled nanometre-sized pores and surface areas of thousands of square metres per gram, metal-organic frameworks (MOFs) may have an integral role in future catalysis, filtration and sensing applications. In general, for MOF-based device fabrication, well-organized or patterned MOF growth is required, and thus conventional synthetic routes are not suitable. Moreover, to expand their applicability, the introduction of additional functionality into MOFs is desirable. Here, we explore the use of nanostructured poly-hydrate zinc phosphate (α-hopeite) microparticles as nucleation seeds for MOFs that simultaneously address all these issues. Affording spatial control of nucleation and significantly accelerating MOF growth, these α-hopeite microparticles are found to act as nucleation agents both in solution and on solid surfaces. In addition, the introduction of functional nanoparticles (metallic, semiconducting, polymeric) into these nucleating seeds translates directly to the fabrication of functional MOFs suitable for molecular size-selective applications.