Realizing the Direct Synthesis of High Silica IWS Zeolite with Improved Hydrothermal Stability.

Direct synthesis of germanosilicate zeolites with low Ge content and improved hydrothermal stability is a great challenge. Herein, we successfully achieve the direct synthesis of IWS zeolite with a Si/Ge ratio higher than 4 for the first time. High silica IWS zeolites can be prepared in a wide range of Si/Ge ratios (4-16) by utilizing bulky 1,3-bis(1-adamantyl)-imidazolium (BAdaI+) as an efficient organic structure-directing agent from the concentrated synthesis gel under fluoride conditions. It is proven by a series of characterizations that Ge atoms preferentially occupy the double-four-ring (D4R) units. Theoretical calculations reveal the preferential interactions of guest organic structure-directing agents (OSDAs) and host IWS zeolites with different Si/Ge ratios. The introduction of more Ge atoms cannot improve the host-guest interaction when the BAdaI+ molecule is accommodated within the nanopores of IWS zeolite compared to other OSDAs. The obtained IWS zeolite shows an extremely high specific surface area (905 m2/g) and pore volume (1.31 cm3/g). Due to the low Ge content, IWS zeolite exhibits outstanding hydrothermal stability and experiences high temperature steam heating with no loss of crystallinity and only a slight loss of microporosity.

Direct Propylene Epoxidation with Molecular Oxygen over Cobalt-Containing Zeolites.

Direct propylene epoxidation with molecular oxygen is a dream reaction with 100% atom economy, but aerobic epoxidation is challenging because of the undesired over-oxidation and isomerization of epoxide products. Herein, we report the construction of uniform cobalt ions confined in faujasite zeolite, namely, Co@Y, which exhibits unprecedented catalytic performance in the aerobic epoxidation of propylene. Propylene conversion of 24.6% is achieved at propylene oxide selectivity of 57% at 773 K, giving a state-of-the-art propylene oxide production rate of 4.7 mmol/gcat/h. The catalytic performance of Co@Y is very stable, and no activity loss can be observed for over 200 h. Spectroscopic analyses reveal the details of molecular oxygen activation on isolated cobalt ions, followed by interaction with propylene to produce epoxide, in which the Co2+-Coδ+-Co2+ (2 < δ < 3) redox cycle is involved. The reaction pathway of propylene oxide and byproduct acrolein formation from propylene epoxidation is investigated by density functional theory calculations, and the unique catalytic performance of Co@Y is interpreted. This work presents an explicit example of constructing specific transition-metal ions within the zeolite matrix toward selective catalytic oxidations.

White-light emission from a single organic compound with unique self-folded conformation and multistimuli responsiveness.

White-light emitting organic materials attract broad attention which are ascribed to their potential for applications in lighting devices and display media. Most reported organic white-light emitters rely on the combination of several components that emit different colors of light (red/green/blue or orange/blue), which may cause problems to stability, reproducibility and device fabrication. By contrast, white-light emission from single-molecule systems offers opportunities to overcome these disadvantages, meanwhile engendering white-light with high quality. Nevertheless, limited cases of white-light emission at the molecular scale reported principally concentrate on organic solvents. Herein, we designed and synthesized new bi-functional organic molecules with a symmetric donor-acceptor-donor (D-A-D) type structure with the aim to construct a single-molecule white-light emitting system in aqueous solution. Further experiments and calculations demonstrate the possibility of stacking between the pyridinium-naphthalene (PN) core and coumarin groups in the designed molecules, ascribed to hydrophobic effects, π-π stacking and donor-acceptor interactions, which could dramatically enhance the intramolecular charge transfer (ICT) efficiency along with remarkable charge transfer (CT) emission. Based on this, multicolor photoluminescence including white-light can be finely tuned in various modes including excitation wavelength, solvent polarity, temperature, and host-guest interactions. A white-light emitting (WLE) hydrogel was also facilely prepared through the dispersion of one of the compounds in a commercial agarose gelator. This innovative study helps enrich the strategies to construct single-molecule organic white-light emitting materials in aqueous medium using the self-folding behavior.

Amorphous Metal-Free Room-Temperature Phosphorescent Small Molecules with Multicolor Photoluminescence via a Host-Guest and Dual-Emission Strategy.

Metal-free room-temperature phosphorescence (RTP) materials offer unprecedented potentials for photoelectric and biochemical materials due to their unique advantages of long lifetime and low toxicity. However, the achievements of phosphorescence at ambient condition so far have been mainly focused on ordered crystal lattice or on embedding into rigid matrices, where the preparation process might bring out poor repeatability and limited application. In this research, a series of amorphous organic small molecular compounds were developed with efficient RTP emission through conveniently modifying phosphor moieties to ß-cyclodextrin (ß-CD). The hydrogen bonding between the cyclodextrin derivatives immobilizes the phosphors to suppress the nonradiative relaxation and shields phosphors from quenchers, which enables such molecules to emit efficient RTP emission with decent quantum yields. Furthermore, one such cyclodextrin derivative was utilized to construct a host-guest system incorporating a fluorescent guest molecule, exhibiting excellent RTP-fluorescence dual-emission properties and multicolor emission with a wide range from yellow to purple including white-light emission. This innovative and universal strategy opens up new research paths to construct amorphous metal-free small molecular RTP materials and to design organic white-light-emitting materials using a single supramolecular platform.