Porosity of Rigid Dendrimers in Bulk: Interdendrimer Interactions and Functionality as Key Factors

The porous structure of second- and third-generation polyphenylene-type dendrimers was investigated by adsorption of N2, Ar, and CO2 gases, scanning electron microscopy and small-angle X-ray spectroscopy. Rigid dendrimers in bulk are microporous and demonstrate a molecular sieve effect. When using CO2 as an adsorbate gas, the pore size varies from 0.6 to 0.9 nm. This is most likely due to the distances between dendrimer macromolecules or branches of neighboring dendrimers, whose packing is mostly realized due to intermolecular interactions, in particular, π–π interactions of aromatic fragments. Intermolecular interactions prevent the manifestation of the porosity potential inherent to the molecular 3D structure of third-generation dendrimers, while for the second generation, much higher porosity is observed. The maximum specific surface area for the second-generation dendrimers was 467 m2/g when measured by CO2 adsorption, indicating that shorter branches of these dendrimers do not provide dense packing. This implies that the possible universal method to create porous materials for all kinds of rigid dendrimers is by a placement of bulky substituents in their outer layer.

Iron Dual-atom Catalyst combine with ″vicinal nonmetallic sites″ for efficient Ammonia Synthesis

Ammonia synthesis from N2 under mild conditions is a long-term pursuit and goal, which theoretically limited by the Brønsted–Evans–Polanyi (BEP) relation in industrial transformation via the N2 dissociation. Here we show that the Fe2 catalyst combined with the “vicinal nonmetallic sites” may break the BEP limitation to fulfill the efficient ammonia synthesis. The catalyst supported on boron doped graphitic carbon nitride (Fe2/B/mpg-C3N4) strongly favors hydrogenation of *N2 to form a *NHNH2 species, which leads to low energy barriers for N-H formation (0.57eV) and N-N dissociation (0.51eV). Constructed B-N “Lewis pairs” on the mpg-C3N4 serve as nonmetallic sites can activate and transfer hydrogen, which reduce the competitive adsorption of N2 and H2. Through co-activated H2 on the vicinal site, synergistic Fe2 catalyst shows a significant advantage among Fen/mpg-C3N4 (n=2, 3, 4) catalysts and thus can avoid harsh reaction condition for the thermal conversion of N2 to NH3.

Effects of removal of extractives on the chemical composition and mechanical properties of wood

Poplar and pine wood were extracted with water, 1% NaOH (wt%) solution, and benzene:ethanol solution (V1 : V2, 2 : 1) to investigate the governing factors and mechanism by which extractives affect wood structure and mechanical properties. The structure, pore distribution, crystal structure, and mechanical properties of samples were analyzed by Fourier transform infrared spectroscopy (FTIR), adsorption of N2 gas, X-ray diffraction (XRD), and mechanical testing, respectively. The results demonstrated that cellulose, hemicellulose, and lignin were degraded to some extent in the course of the dissolution of the extractives. This degradation had a great influence on the structure and quantity of pores. The extraction treatment did not change the crystallization type of the wood, but it increased the crystallinity of the wood, and the length and width of the crystallization area changed. In addition, the mechanical properties of wood were changed when the content of the extractives was reduced.

Effects of Basic Promoters on the Catalytic Performance of Cu/SiO2 in the Hydrogenation of Dimethyl Maleate

Continuous hydrogenation of dimethyl maleate (DMM) toγ-butyrolactone (GBL), 1,4-butanediol (BDO) and tetrahydrofuran (THF) is a promising process in industry. In this study, Cu-M/SiO2 catalysts modified by basic promoters (M = Mg, Ca, Sr, Ba, La) were prepared, and characterized by physical adsorption of N2, in situ XRD, H2-TPR, CO2-TPD. With the addition of basic promoters, the basicity of Cu-M/SiO2 catalysts was improved. The particle size of CuO on Cu-M/SiO2 catalyst was increased after modified by Mg, Ca, Sr, Ba. However, the CuO particle was decreased on the Cu-La/SiO2 catalyst. The series of Cu-M/SiO2 catalyst was applied to the hydrogenation of DMM. The addition of basic promoters increased the selectivity of GBL during the hydrogenation for the basic promoters improved the dehydrogenation of BDO to GBL in alkaline sites. Furthermore, Cu-La/SiO2 presented a higher activity in the hydrogenation of DMM, due to its higher dispersion of Cu.