Mesocrystals (MCs) are superstructures with a crystallographically ordered alignment of nanoparticles. Owing to their organized structures, MCs posses some unique characteristics such as a high surface area, pore accessibility, and good electronic conductivity and thermal stability; thus, MCs could be beneficial for many areas of research and application. This review begins with a description of the common synthesis strategies for, and characterization and fundamental properties of metal oxide MCs. Newly developed analytical methods (that is, photoconductive atomic force microscopy and single-molecule, single-particle fluorescence microscopy) for unraveling the charge transport and photocatalytic properties of individual MCs are then introduced. Further, recent developments in the applications of various metal oxide MCs, especially in the fields of energy conversion and storage, are also reviewed. Finally, several perspectives in terms of future research on MCs are highlighted. NPG Asia Materials (2014) 6, e100; doi:10.1038/am.2014.21; published online 16 May 2014 Keywords: energy storage; mesocrystal; metal oxide; photocatalysis; solar energy conversion; superstructure
INTRODUCTIONThe self-assembly of nanoparticle building blocks into highly ordered superstructures is one of the actively pursued research topics in materials science and technology. 1-4 Such hierarchical architectures have potentially tunable electronic, optical and magnetic properties, which promise various applications ranging from catalysis to optoelectronics. A mesocrystal (MC), which was first introduced by Cölfen in the early years of 2000s, is defined as a superstructure consisting of nanoparticles on the scale of several hundred nanometers to micrometers. [5][6][7][8][9][10][11] In contrast to the classical mechanism of atom/ ion-mediated growth of a single crystal, the particle-mediated growth mechanisms of MCs are termed as non-classical crystallization (Figure 1). This definition has been developed in recent years, where MCs are defined entirely according to their structures rather than their formation mechanism. 12 In this decade, a variety of MCs of metal oxides (for example, TiO 2 , 13-23 ZnO, [24][25][26][27][28][29][30][31][32][33][34] Among metal oxides, TiO 2 is used in many applications that deal with environmental and energy problems (for example, photodegradation of pollutants, 67 water splitting for H 2 evolution, 68 dyesensitized solar cells 68 and lithium-ion batteries 69 ) owing to its