Size/shape-controlled colloidal CdSe quantum disks with zinc-blende (cubic) crystal structure were synthesized using air-stable and generic starting materials. The colloidal CdSe quantum disks were approximately square, and their lateral dimensions were varied between 20 and 100 nm with the thickness controlled between 1 and 3 nm, which resulted in sharp and blue-shifted UV-vis and PL peaks due to one-dimensional quantum confinement. The quantum disks were grown with either <001> or <111> direction, polar directions in the single crystalline disks, as the short axis, and both basal planes were terminated with Cd ions. These surface Cd ions were passivated with negatively charged fatty acid ligands to neutralize the net positive charges caused by the excess monolayer of Cd ions. The coordination of the Cd ions and carboxylate groups further enabled the close-packing monolayer of fatty acid ligands on each basal plane. The close packing of the hydrocarbon chains of fatty acids dictated the up temperature limit for synthesis of the colloidal quantum disks, and the low temperature limit was found to be related to the reactivity of the starting materials. Overall, a high Cd to Se precursor ratio, negative-charged fatty acid ligands with a long hydrocarbon chain, and a proper temperature range (approximately between 140 and 250 °C) were found to be needed for successful synthesis of the colloidal CdSe quantum disks.

The initial formation of semiconductor nanocrystals/nanoclusters, that is, nucleation in the classic literature, was examined both theoretically and experimentally. An experimental method based on determining the initial reaction rate for the formation of nanocrystals/nanoclusters with fixed size and size distribution was developed using InP and CdS nanocrystals/nanoclusters systems, especially the InP one. This experimental strategy relies on the size-dependent absorption spectra of these semiconductor nanoparticles as quantitative probes. The experimental results along with theoretical analysis indicate that the classic nucleation model was unlikely relevant for such crystallization systems, whose bulk crystal solubility in a solution is extremely low. Instead, the formation process was found to match a reaction-controlled kinetics model. The results further imply that understanding of crystallization and development of controlled synthesis of high quality colloidal nanocrystals are both closely related to identifying the molecular mechanism and chemical kinetics.

With the rapid development of materials science, porous organic polymers (POPs) have received remarkable attentions because of their unique properties such as the exceptionally high surface area and flexible molecular design. The ability to incorporate specific functions in a precise manner makes POPs promising platforms for a myriad of applications in molecular adsorption, separation, and catalysis. Therefore, many different types of POPs have been rationally designed and synthesized to expand the scope of advanced materials, endowing them with distinct structures and properties. Recently, supramolecular macrocycles with excellent host–guest complexation abilities are emerging as powerful crosslinkers for developing novel POPs with hierarchical structures and improved performance, which can be well‐organized at different spatial scales. Macrocycle‐based POPs could have unusual porous, adsorptive, and optical properties when compared to their nonmacrocycle‐incorporated counterparts. This cooperation provides valuable insights for the molecular‐level understanding of skeletal complexity and diversity. Here, the research advances of macrocycle‐based POPs are aptly summarized by showing their syntheses, properties, and applications in terms of separation, sensing, and catalysis. Finally, the current challenging issues in this exciting research field are delineated and a comprehensive outlook is offered for their future directions.

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Formation of CdS nanocrystals in the classic approach (with octadecene (ODE) as the solvent and elemental sulfur and cadmium carboxylate as the precursors) was found to be kinetically dependent on reduction of elemental sulfur by ODE, which possessed a critical temperature (~180 °C). After elemental sulfur was activated by ODE, the formation reaction of CdS followed closely. 2-tetradecylthiophene from the activation of S by ODE and fatty acids from the formation reaction of CdS were found to be the only soluble side products. The overall reaction stoichiometry further suggested that oxidation of each ODE molecule generated two molecules of H(2)S, which in turn reacted with two molecules of cadmium carboxylate molecules to yield two CdS molecular units and four molecules of fatty acids. In comparison to alkanes, octadecene was found to be substantially more active as a reductant for elemental sulfur. To the best of our knowledge, this is the first example of quantitative correlation between chemical reactions and formation of high-quality nanocrystals under synthetic conditions. To demonstrate the importance of such discovery, we designed two independent and simplified synthetic approaches for synthesis of CdS nanocrystals. One approach with its reaction temperature at the critical temperature of S activation (180 °C) used the same reactant composition as the classic approach but without any hot injection. The other approach performed at an ordinary laboratory temperature (≤100 °C) and in a common organic solvent (toluene) was achieved by addition of fatty amine as activation reagent of elemental sulfur.

Formation of CdSe nanocrystals with two-dimensional quantum confinement (CdSe 2D nanocrystals) was studied with preformed CdSe nanocrystals in the size range between 1.7 and 2.2 nm as seeds. Specifically, the 2D CdSe nanocrystals were encased with six {100} facets of the zinc-blende (face-center-cubic) structure, that is, 1.5 nm in thickness with quite large atomically flat {100} basal planes (∼8 nm width and X ≈ 45 nm length). Symmetry breaking between the thickness and lateral directions occurred in the early stage by rapid formation of single-dot intermediates with flat yet polar {100} basal planes and the desired thickness from the seeds through intraparticle ripening. Two single-dot intermediates fused together through their reactive side facets-mostly the nonpolar {110} ones-to form 2D embryos with the same thickness. Such oriented attachment continued selectively onto the reactive side facets of the 2D embryos. Simultaneously, intraparticle ripening occurred slowly on the side facets of the 2D nanocrystals, which converted unstable side facets gradually to four stable {100} ones. When ∼3 stable {100} side facets were developed, oriented attachment would continue on the remaining active one, which would result in the second symmetry breaking between two lateral directions. Cadmium acetate assisted both formation of single-dot intermediates and oriented attachment. Cadmium alkanoates with a long hydrocarbon chain selectively stabilized polar {100} facets on the nanocrystals including single-dot intermediates and shuttled insoluble acetate to the reactive surface of the nanocrystals.

Mesoporous silica with Ia3̄d structure has been successfully prepared by using mixed surfactants of commercially available nonionic block copolymer P123 (EO20PO70EO20) and anionic sodium dodecyl sulfate (SDS) as structure-directing agents through an acid-catalyzed silica sol−gel process. XRD, TEM, and N2 sorption measurements show that the products have highly ordered bicontinuous cubic mesostructure with high surface area (∼770 m2/g), large pore volume (∼1.5 cm3/g), and uniform pore size (∼10 nm). Effects of preparation parameters on the formation of the mesostructure have been extensively investigated. It is found that the molar ratios of SDS/P123 between 2.1 and 2.5 and that of silicic species to P123 in the range from 40 to 75 are favorable for the formation of highly ordered Ia3̄d mesostructure. Prolonging hydrothermal treatment time leads to almost unchanged cell parameters of the products, whereas there is obvious increase of the pore sizes and pore volume. The results show that resultant template-free mesoporous silica products have excellent thermal stability, and they are more stable in N2 atmosphere than in air. Morphologies of the resultant materials can be further controlled by adding inorganic salt (such as Na2SO4) into the mixed surfactants system. Coral- and petaline-like mesoporous silica with continuous skeletons can be obtained. Understanding this synthesis system might be useful for economical and large-scale production of mesoporous materials with controllable structures.

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