Rhodium nanoparticles supported on silanol-rich zeolites beyond the homogeneous Wilkinson's catalyst for hydroformylation of olefins.

Hydroformylation is one of the largest industrially homogeneous processes that strongly relies on catalysts with phosphine ligands such as the Wilkinson's catalyst (triphenylphosphine coordinated Rh). Heterogeneous catalysts for olefin hydroformylation are highly desired but suffer from poor activity compared with homogeneous catalysts. Herein, we demonstrate that rhodium nanoparticles supported on siliceous MFI zeolite with abundant silanol nests are very active for hydroformylation, giving a turnover frequency as high as ~50,000 h-1 that even outperforms the classical Wilkinson's catalyst. Mechanism study reveals that the siliceous zeolite with silanol nests could efficiently enrich olefin molecules to adjacent rhodium nanoparticles, enhancing the hydroformylation reaction.

Insights into the Effect of the Adsorption Preference of Additives on the Anisotropic Growth of ZSM-5 Zeolite.

Invited for the cover of this issue are Zaiku Xie, Jiawei Teng, Chuanming Wang, and co-workers at the SINOPEC Shanghai Research Institute of Petrochemical Technology, Liaoning Petrochemical University and University of Science and Technology of China. The image depicts the effect of eight organic additives on the anisotropic growth of classical ZSM-5 zeolite at the molecular level. Read the full text of the article at 10.1002/chem.202201781.

Structural and Acidic Characteristics of Multiple Zr Defect Sites in UiO-66 Metal-Organic Frameworks.

Although defects are prevalent in metal-organic frameworks (MOFs) and usually play a crucial role in modulating their performance in various applications, detailed structural characterizations of various defects remain a challenging task mainly due to their disordered, heterogeneous, and local nature. In this work, by using solid-state nuclear magnetic resonance spectroscopy (SSNMR) techniques in conjunction with density functional theory (DFT) calculations, it is clearly elucidated that the trimethylphosphine (TMP)-assisted 31P NMR strategy is capable of greatly facilitating the qualitative and quantitative description of the detailed structural and acidic characteristics as well as the evolution process of various Zr defects with subtle distinctions in UiO-66 upon moderate thermal treatment, hence surpassing most conventional analytical techniques. These results offer a fundamental understanding of the defect chemistry in MOFs.

Insights into the Effect of the Adsorption Preference of Additives on the Anisotropic Growth of ZSM-5 Zeolite.

Zeolite morphology plays a crucial role in affecting catalytic performance, while is persistently challenging to tailor through crystal anisotropic growth. It has been recognized that specific additives can be introduced into the synthesis of zeolites to achieve anisotropic growth, however their role and the underlying mechanism are not well understood. Herein, the effect of eight specific additives on the anisotropic growth of the ZSM-5 zeolite is unveiled within the framework of crystallization engineering. Either an inhibition effect or a promotion effect is revealed for each additive according to the crystallization kinetics. The adsorption preference of typical additives on different surfaces was demonstrated by total internal reflection fluorescence microscopy (TIRFM) and transmission X-ray microscopy (TXM) together with 3D reconstruction. The calculated adsorption energy difference between MFI [100]/[101] and [010] surfaces was proposed as a key descriptor to estimate the possible morphology induced by additive. ZSM-5 zeolites varying from sphere-like, plate-like to noodle-like morphology could be synthesized by employing specific additives with increasing adsorption strength difference on distinct surfaces.

Isolated boron in zeolite for oxidative dehydrogenation of propane.

Oxidative dehydrogenation of propane (ODHP) is a key technology for producing propene from shale gas, but conventional metal oxide catalysts are prone to overoxidation to form valueless CO x Boron-based catalysts were recently found to be selective for this reaction, and B-O-B oligomers are generally regarded as active centers. We show here that the isolated boron in a zeolite framework without such oligomers exhibits high activity and selectivity for ODHP, which also hinders full hydrolysis for boron leaching in a humid atmosphere because of the B-O-SiO x linkage, achieving superior durability in a long-period test. Furthermore, we demonstrate an isolated boron with a -B[OH…O(H)-Si]2 structure in borosilicate zeolite as the active center, which enables the activation of oxygen and a carbon-hydrogen bond to catalyze the ODHP.

Merohedral icosahedral M48 (M = CoII, NiII) cage clusters supported by thiacalix[4]arene.

Cage clusters are a discrete chemically and topologically diverse family of molecule-based functional materials. Presented here are two isostructural M48 (M = CoII for LSHU01, NiII for LSHU02) cage clusters with a merohedral icosahedral cage structure featuring 12 M4-TC4A (H4TC4A, p-tert-butylthiacalix[4]arene) second building units as vertices and 18 asymmetric 5-(1H-tetrazol-1-yl)isophthalate ligands as faces. They are the highest-nuclearity cage compounds of CoII and NiII. The activated Co48 cage exhibited high selectivity in the sorption of C3H8 over CH4 under ambient conditions. Frequency response experiments indicated that the extrinsic voids and matrix interface of the activated crystalline samples are primarily responsible for the observed gas adsorption performance.

A 2D metal-thiacalix[4]arene porous coordination polymer with 1D channels: gas absorption/separation and frequency response.

A 2D layered structure {[Co4(TC4A)Cl](L)2][(CH3CH2)4N]}n (+solvent)(1) has been solvothermally synthesized by assembly of Co4-TC4A (H4TC4A = p-tert-butylthiacalix[4]arene) subunits and L (H2L = 4-(1H-tetrazol-5-yl)benzoic acid) ligands. The layers arranged in an edge-to-edge (AAAA) manner, which represented the only example of 2D porous coordination polymers (PCPs) with 1D uniform channels of metal-thiacalix[4]arene. The activated PCP 1 exhibited high selectivity for C3H8/C2H6, C3H6/C2H4, and C3H8/C2H4, which makes it a competitive porous material for C3/C2 alkane and/or olefin separations. Frequency response investigations for C3H8 and C2H6 indicated that the 1D channels and inter-layer voids of the activated crystalline samples are primarily responsible for the observed gas adsorption and separation performances.

Surface acidity effects of Al-SBA-15 mesoporous materials on adsorptive desulfurization.

SBA-15 and Aluminum-substituted SBA-15 with Si/Al molar ratio 10 (Al-SBA-15(10)) mesoporous materials were directly synthesized by a hydrolysis approach and characterized by a powder X-ray diffraction (XRD), N2 physisorption analysis and Fourier transform infrared (FTIR) etc. The relative number of hydroxyl groups was investigated by in situ FTIR systematically. The acid type and acid strength of the adsorbents were monitord by FTIR at 423 K and 673 K, respectively, utilizing pyridine as a probe. Desulfurization performances of the adsorbents were investigated via static adsorption experiment. Gas chromatography-sulfur chemiluminescence detector (GC-SCD) was employed to detect the sulfur compounds in model fuels before and after treated by the adsorbents. The calcined Al-SBA-15(10) material shows well-ordered hexagonal mesostructure and strong Lewis acid sites (L acid) and weak Brönsted acid sites (B acid). The number of hydroxy on the surface of the Al-SBA-15(10) is more than that of SBA-15, which is beneficial to further modifications such as spontaneous monolayer dispersion. Desulfurization performance of the adsorbents is affected by surface acidity of adsorbents and the constituent of model fuels (olefins, arene, etc.). The thiophene and olefins adsorbed on the B acid site of the adsorbent may occur subsequently alkylation reactions, which may block the pores of the adsorbents and thus cause the reduction of desulfurization capacity.