Modification of Potassium Chabazites Derived from Fly Ash by Dosing Extra Cations: Promoted CO2 Adsorption Capacities and Fine‐Tuned Frameworks

Potassium chabazite (K‐CHA), a typical microporous zeolite with excellent CO₂ separating properties, was synthesized with waste fly ash and modified via cation dosing treatments using cesium and zinc cations, respectively. The resulting CHAs were analyzed by XRF, XRD, FT‐IR, SEM, and N₂ physisorption, whose CO₂ adsorption properties were then tested on the reorganized TGA apparatus. It showed from XRF data that cesium and zinc cations were successfully imported in the original K‐CHA by cation dosing, but the CHA microstructures and morphologies of K‐CHA were perfectly retained as confirmed by XRD, FT‐IR, SEM and N₂ physisorption. Since there were still over 9 potassium cations per unit cell in cation dosed Cs‐CHA and Zn‐CHA, they both maintained the favored properties of K‐CHA as “molecular trapdoors”. In the following adsorption experiments, the CO₂ uptakes of Cs‐CHA and Zn‐CHA at 333 K and 1 bar, compared with K‐CHA, elevated from 1.70 mmol · g^–1 to 2.34 and 2.03 mmol · g^–1, and the import of zinc cation also presented a positive effect on the adsorption kinetics. Detailed comparisons suggested modifications with cesium and zinc cations fine‐tune the CHA complying with different mechanisms, and CHAs modified via cation perform more approvingly than fully ion‐exchanged ones, providing us important insights into CHA modifications and applications in practice.     

Solvent‐Induced Cluster‐to‐Cluster Transformation of Homoleptic Gold(I) Thiolates between Catenane and Ring‐in‐Ring Structures

Supramolecular ensembles adopting ring‐in‐ring structures are less developed compared with catenanes featuring interlocked rings. While catenanes with inter‐ring closed‐shell metallophilic interactions, such as d¹⁰–d¹⁰ Au^I–Au^I interactions, have been well‐documented, the ring‐in‐ring complexes featuring such metallophilic interactions remain underdeveloped. Herein is described an unprecedented ring‐in‐ring structure of a Au^I‐thiolate Au₁₂ cluster formed by recrystallization of a Au^I‐thiolate Au₁₀ [2]catenane from alkane solvents such as hexane, with use of a bulky dibutylfluorene‐2‐thiolate ligand. The ring‐in‐ring Au^I‐thiolate Au₁₂ cluster features inter‐ring Au^I–Au^I interactions and underwent cluster core change to form the thermodynamically more stable Au₁₀ [2]catenane structure upon dissolving in, or recrystallization from, other solvents such as CH₂Cl₂, CHCl₃, and CH₂Cl₂/MeCN. The cluster‐to‐cluster transformation process was monitored by ¹H NMR and ESI‐MS measurements. Density functional theory (DFT) calculations were performed to provide insight into the mechanism of the “ring‐in‐ring? [2]catenane” interconversions.     

Topotactic Conversion of Alkali-Treated Intergrown Germanosilicate CIT-13 into Single-Crystalline ECNU-21 Zeolite as Shape-Selective Catalyst for Ethylene Oxide Hydration

The conversion of the alkali-treated intergrowth germanosilicate CIT-13 into the single-crystalline high-silica ECNU-21 (named after East China Normal University) zeolite, with a novel topology and a highly crystalline zeolite framework, has been realized through a creative top-down strategy involving a mild alkaline-induced multistep process consisting of structural degradation and reconstruction. Instead of acid treatment, hydrolysis in aqueous ammonia solution not only readily cleaved the chemically weak Ge(Si)−O−Ge bonds located within the interlayer double four ring (D4R) units of CIT-13, but also cleaved the metastable Si−O−Si bonds therein. This led to extensive removal of the D4R units, and also generated silanol groups on adjacent silica-rich layers, which then condensed to form a novel daughter structure upon calcination. Individual oxygen bridges in the reassembled ECNU-21 replaced the germanium-rich D4R units in CIT-13, thereby eliminating the original intergrowth phenomenon along the b axis. With an ordered crystalline structure of 10-ring (R) channels as well as suitable germanium-related Lewis acid sites, ECNU-21 serves as a stable solid Lewis acid catalyst for the shape-selective hydration of ethylene oxide (EO) to ethylene glycol (EG) at greatly reduced H₂O/EO ratios and reaction temperature in comparison with the noncatalytic industrial process.     

Intramolecular Nitrene Insertion into Saturated C−H-Bond-Mediated C−N Bond Cleavage of a Coordinated NHC Ligand

Ruthenium(II) complexes bearing a tridentate bis(N-heterocyclic carbene) ligand reacted with iminoiodanes (PhI=NR) resulting in the formation of isolable ruthenium(III)–amido intermediates, which underwent cleavage of a C−N bond of the tridentate ligand and formation of an N-substituted imine group. The Ru^III–amido intermediates have been characterized by ¹H NMR, UV/Vis, ESI-MS, and X-ray crystallography. DFT calculations were performed to provide insight into the reaction mechanism.     

大孔阳树脂催化合成苯乙酸酯

利用Ｄ７２，Ｄ６１大孔阳离子交换树脂为催化剂，催化合成苯乙酸异戊酯、苯乙酸丁酯、苯乙酸苄酸、苯乙酸苯乙酯、苯乙酸茴香酯。对影响反应的诸因素进行了讨论，酯收率为９０％左右。     

CHARACTERIZATION OF RADIATION GRAFT COPOLYMER OF INORGANIC COMPOUND ONTO ALKENE

ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＲＡＤＩＡＴＩＯＮＧＲＡＦＴＣＯＰＯＬＹＭＥＲＯＦＩＮＯＲＧＡＮＩＣＣＯＭＰＯＵＮＤＯＮＴＯＡＬＫＥＮＥＺｈａｎｇＷａｎｘｉ；ＣｈｅＪｉｔａｉ；ＹａｎＭｅｉｌａｎ（ＣｈａｎｇｃｈｕｎｉｎｓｔｉｔｕｔｅｏｆＡｐｐｌｉ...     

阴离子交换树脂催化醇的氰乙基化反应

利用阴离子交换树脂为催化剂，进行了醇的氰乙基化反应，对影响反应的诸因素进行了讨论。     

螯合型二甘醇钛酸酯的合成及其催化性能研究

报导了两种新的螯合型二甘醇钛酸酯的合成方法，进行了ＩＲ和ＵＶ鉴定，并作为酯化反应催化剂催化合成了邻苯二甲酸二辛酯。研究了酯化反应转化率与反应时间、反应温度及催化剂用量的关系，探讨了催化剂结构与催化性能的关系。     

X-ray analysis at 150?K, synthesis and theoretical calculations of 1-naphthaleneacrylic acid

The X-ray structure, synthesis, theoretical calculation and IR spectra of 1-naphthaleneacrylic acid are reported. The titled compound crystallizes in the monoclinic C 2/c space group with unit cell parameters: a = 14.556(3), b = 5.1332(10), c = 26.832(5) ?, β = 97.02(3)°, V = 1989.8(7) ?³, Z = 8 and form typical centrosymmetric hydrogen-bonded dimers. Theoretical calculations of 1-naphthylacrylic acid isolated molecule and hydrogen-bonded dimer have been carried out using density functional theory at the B3LYP level. For optimized structures the vibrational spectra have been then calculated and compared with experimental IR spectrum. The assignment and characterization of theoretical vibrational spectra were based on the potential energy distribution analysis. This comparison has shown that the theoretical spectrum for the dimer structure is in good agreement with the experimental one. Structural comparisons with naphthalene, and with some substituted 2-propenoic acids have shown influence of the substituent on conformation of the naphthalene ring or 2-propenoic moiety.     

Surface-relief-grating formation behavior of two hyperbranched azo polymers

In this work,surface-relief-grating formation behavior was studied by using two hyperbranched azo polymers.The hyperbranched polymers containing pseudo-stilbene type azo chromophores throughout the hyperbranched structure were synthesized by step-growth polycondensation of AB₂ type monomers.The AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）-phenylazo） benzoic acid（BAA）,was prepared through azo-coupling reaction between N,N’-bis（2-chloroethyl）aniline and 4- aminobenzenic acid.The another AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）phenylazo）-3-nitro-benzoic acid（BANA）, was prepared through azo-coupling reaction between N,N-bis（2-chloroethyl）aniline and 3-nitro-4-aminobenzcnic acid.The hyperbranched polymers（PBAA and PBANA） were prepared through nucleophilic substitution reaction of BAA and BANA, respectively.The polymers synthesized were characterized by using spectroscopic methods and thermal analysis.The photoinduced dichroism and photo-induced surface-relief-grating（SRG） formation of the hyperbranched polymers were investigated upon irradiation with Ar⁺ laser at 488 nm.PBAA shows typical photoinduced dichroism SRG formation behavior.On the contrary,PBANA does not show the photoresponsive properties.The results indicate that the nitro at the ortho position of azo group of PBANA shows the effect of inhibiting the photoinduced variations.The effect can be attributed to the blockage of the trans-cis isomerization of the azobenzene moieties by the steric hindrance.