Heterogeneous acylation of phenol with acetic anhydride over hydrotalcite-like compounds

Liquid phase acylation of phenol with acetic anhydride was studied over the mixed oxides obtained from Mg-Al, Ni-Al, and Cu-Al hydrotalcites (HTs). The mixed oxides were characterized by XRD and SEM. The main acylation products of phenol over these oxide catalysts are phenylacetate and o-hydroxyacetophenone.     

K改性NiAl类水滑石衍生复合氧化物催化分解N2O

制备了Ni/Al=4.1(原子比)的NiAl类水滑石,焙烧获得NiAl复合氧化物,浸渍K2CO3溶液制备了K改性NiAl复合氧化物催化剂,其中K/Ni=0.05~0.2(原子比),用于N2O催化分解反应.通过元素分析、XRD、BET、H2-TPR、XPS等技术表征了催化剂的组成结构,考察了NiAl类水滑石的预处理方式、...     

Structural and thermal properties of Co-Cu-Fe hydrotalcite-like compounds

The structural properties and thermal decomposition processes of Co-Cu-Fe ternary hydrotalcites (HT) have been studied through X-ray diffraction, thermogravimetric measurements, Fourier-transform infrared and Mössbauer spectroscopies. Due to the strong Jahn-Teller effect, the Cu-Fe layered system is stabilized only in the presence of Co²⁺. At low Co²⁺ contents, additional phases are segregated in the solids. X-ray patterns show the presence of Cu(OH)₂ and CuO. The decomposition process was investigated by in situ X-ray, in situ Mössbauer and FTIR experiments. By increasing the temperature from 25 °C up to 180 °C we observed that the structural disorder increases. This effect has been likely attributed to the Co²⁺→Co³⁺ oxidation since thermal decomposition was carried out under static air atmosphere. Part of the Co³⁺ cations could migrate to the interlayer region, thus forming a metastable compound that still has a layered structure. Collapse of the layered structure was observed at about 200 °C. By further increasing the temperature the system becomes more crystalline and the formation of Co₃O₄ is observed in the X-ray patterns. In Cu-rich HT, some of the carbonate anions are released at temperatures higher than 550 °C and this phenomenon is attributed to the formation of a carbonate-rich phase. The specific surface area data present its highest values in the temperature range where the collapse of the layered structure takes place.     

钴铬水滑石的合成及表征

采用共沉淀法合成了一系列不同Co/Cr物质的量比的碳酸根型水滑石。用X－衍射、红外光谱、差热、热重、分光光度等方法对其组成和结构进行了研究。结果表明Co/Cr投料比为2到3时能形成结晶度好、纯度高的水滑石。初步推测了部分产物的组成及所含水滑石的化学式。     

Microwave-assisted reconstruction of Ni,Al hydrotalcite-like compounds

The microwave-assisted reconstruction of Ni,Al hydrotalcite-like compounds (HTlcs) with Ni/Al molar ratios 2/1 and 3/1 has been studied. Mixed oxides obtained after calcination of the HTlcs are immersed in three different solutions containing carbonate, distilled water and an aqueous NH₃ solution, and then heated at different temperatures for increasing periods of time under microwave radiation. The evolution of the structure during the treatment is followed by powder X-ray diffraction, FT-IR and vis-UV spectroscopies and SEM and TEM microscopies. Full recovery of the original layered structure is achieved in short periods of time for the 2/1 samples when the calcined HTlcs are rehydrated in the Na₂CO₃ solution, but more drastic conditions are necessary for the 3/1 samples and the reconstruction seems not to be complete. Finally, only a partial reconstruction is observed in distilled water or NH₃ aqueous solution.     

Shape-selective ethylation of biphenyl over a highly dealuminated H-mordenite

The shape-selective ethylation of biphenyl over a highly dealuminated mordenite was examined. The ethylation, occurring stepwise, resulted in the formation of ethylbiphenyls (EBP), diethylbiphenyls (DEBP) and tri- and tetraethylbiphenyls (polyethylbiphenyls, PEBP). In the first step, the ethylation was non-shape-selective and gave 17% 4-EBP, with large amounts of the bulkier 2-EBP and 3-EBP isomers. In the second step, the pores of H-mordenite differentiated the diffusion of the EBP isomers, leading to a preferential ethylation of 4-EBP; 4-EBP was consumed rapidly. 3-EBP gradually and 2-EBP did not participate in the further ethylation. Moreover, the transition state of the ethylation of 4-EBP underwent steric restriction by H-mordenite pores, leading to an increase of the selectivity of 4,4′-DEBP up to 30%. The lack of shape selectivity in the first step and the low selectivity for 4,4′-DEBP over HM220 indicate that the space of a H-mordenite pore is too large for highly shape-selective ethylation.     

Studies on intrinsic ionization constants of Fe-Al-Mg hydrotalcite-like compounds

The theoretical analysis of the intrinsic ionization constant (K(a2)(int)) of Fe-Al-Mg hydrotalcite-like compounds (HTlc) possessing permanent charges was first performed using the double extrapolation method proposed by James et al. The theoretical permanent charge density (sigma(p,T)) of the HTlc sample was calculated from the crystal structure of HTlc, and the influence of sigma(p,T) on the K(a2)(int) was also examined. From the experimental results, these conclusions can be obtained: the zero point of the charge (pH(ZPC)) of Fe-Al-Mg HTlc increases with decreased Fe3+ content and increases with increased Mg2+ in the HTlc. The pK(a2)(int) of Fe-Al-Mg HTlc also increases with decreased Fe3+ and increased Mg2+ content in the sample; furthermore, the pK(a2)(int) of Fe-Al-Mg HTlc increases with decreased sigma(p,T).     

Surface complexation reactions of inorganic anions on hydrotalcite-like compounds

In Qiao's previous report, only star polymers with T(g) (glass transition temperature) below 48°C were found forming homogeneous honeycomb coatings on the nonplanar substrates. The polymers with high T(g) are believed not able to duplicate nonplanar substrate due to their brittleness. This article presents a comprehensive study on the construction of macroporous polymeric films on various nonplanar substrates with static breath figure (BF) technique, using linear polymers with high T(g). Two kinds of linear polymers with high T(g), polystyrene-b-poly(acrylic acid) and polystyrene without polar end groups, are employed to prepare 3-dimensional macroporous films on different nonplanar substrates. Scanning electronic microscopy views on the side wall in addition to views in-plane prove that polymer films with BF array perfectly replicated the surface features of these substrates. The formation processes of macropores on these substrates are analyzed in detail, and it demonstrates that neither molecular topography nor T(g) of polymers is the critical factor contouring nonplanar substrate. A new hypothesis involving polymer plasticization and conformation during the solvent evaporation is formulated.     

Preparation and characterization of Mg-Al hydrotalcite-like compounds containing cerium

Hydrotalcite-like compounds (HTlcs) containing Mg(2+), Al(3+), and Ce(3+) in the hydroxide layer and with carbonate as charge-balancing anion have been prepared by a co-precipitation (at constant pH) method. The Al/Ce ratio in the final product depends on the concentration in the initial solution. The crystallinity of the layered materials decreases with the increase in cerium content, probably, due to the distortions introduced by the large difference in the ionic radii of the cations. All the synthesized materials were characterized by XRD, FT-IR spectroscopy and TG/DTA. The textural properties were determined from low-temperature nitrogen adsorption-desorption measurements.     

Side chain engineering investigation of non-fullerene acceptors for photovoltaic device with efficiency over 15%

Science China Chemistry - Side chain engineering plays a substantial role for high-performance organic solar cells (OSCs). Herein, a series of non-fullerene acceptor (NFA) molecules with A-D-A...     

反气相色谱法测定锌镁铝类水滑石的表面性能

采用水热合成法制备了锌镁铝类水滑石(ZnMgAl-HTLC),利用X射线衍射仪(XRD)对ZnMgAl-HTLC的晶体结构进行了表征,并以一系列非极性和极性分子为探针分子,采用反气相色谱法(IGC)研究了ZnMgAl-HTLC的表面性能.结果表明:XRD特征衍射峰窄、尖、高,水热合成法能够制得纯度较高的ZnMgAl-HTLC; ZnMgAl-HTLC表面吸附自由能小于零,表面色散自由能最大为6.02 mJ/m²,酸碱作用自由能最大为5.33 kJ/mol,吸附焓为43.6 kJ/mol,吸附熵为0.15 kJ/mol.本文的反气相色谱方法对研究锌镁铝类水滑石的表面性能具有重要的指导意义.     

Electrochemical characterization of carbon paste electrodes modified with MgZnGa and ZnGaAl hydrotalcite-like compounds

Two hydrotalcite-like compounds (HTs) were synthesized by coprecipitation. The electrochemical behavior of MgZnGa ([Mg_0.58 Zn_0.17Ga_0.25 (OH)₂] (CO₃)^2? _0.125 1.5 H₂O) and ZnGaAl ([Zn_0.75Ga_0.19 Al_0.06 (OH)₂] (CO₃)^2? _0.125·1.5 H₂O) Hydrotalcite-like compounds (HTs) was studied in NaOH at different concentrations. Voltammetric and chronoamperometric studies were performed to identify oxidation and reduction processes and the effect of the cations in total reactivity. Electrocatalytic effect of HTs on hydroxide electrochemical oxidation shows better performance of MgZnGa; this is apparently due to the presence of Mg and a greater amount of Ga³⁺ in the lattice of this HT. As far as reduction is concerned, Zn(II) reduction process is observed within the lattices of both HTs and is influenced by both the amount of OH^? in the solution and the potential which the previous oxidation has been performed.     

Transalkylation of toluene with diisopropylbenzene over rey zeolite

Production of cymenes and cumene through transalkylation of toluene with diisopropylbenzene has been studied over REY zeolite. Variation of different reaction parameters and their effects on the conversion of DIPB and selectivity to cymenes and cumene are described. Concentration of cymenes are more than cumene due to successive and simultaneous reactions.     

ortho-Selective ethylation of phenol with ethanol catalyzed by bimetallic mesoporous catalyst, CoAl-MCM-41

CoAl-MCM-41 (X) catalysts with X = n_Si/(n_Co + n_Al) various ratios were synthesized and ethylation of phenol with ethanol was studied in vapor-phase at temperatures between 250 and 450 °C. The products obtained were O-alkylated product (ethyl phenyl ether), C-alkylated products (2-ethylphenol and 4-ethylphenol), and C-/O-alkylated products (ethyl ethylphenyl ether). The phenol conversion increased significantly with reaction temperature over all the catalysts. The activity of the catalysts followed the order CoAl-MCM-41 (20) > CoAl-MCM-41 (50) > CoAl-MCM-41 (80). Selectivity between the C-alkylation and the O-alkylation depended on the factors such as acidity of the catalyst and the reaction temperature. CoAl-MCM-41 (20) catalyst displayed a phenol conversion of 40% and a selectivity of more than 80% for 2-ethylphenol under the optimized reaction condition. The ethanol to phenol ratios and the reactant flow rate are also influential for both activity and selectivity of CoAl-MCM-41 catalysts.     

Determination of butyltin compounds in sediments using an improved aqueous ethylation method

We have determined tributyltin and dibutyltin species in various environmental sediment samples (marine, harbour and river sediment) using the in situ aqueous ethylation-gas chromatography-atomic absorption spectrometry method subsequent to extraction by methanol containing O.5M HCl. The present technique provides a significantly lower detection limit than previous methods, so that tributyltin can for the first time be measured in some of the samples. Thus, the method described is well suited for the determination of tributyltin and dibutyltin compounds in sediments with low levels of butyltin species (e.g., Main River, 1.7 ng of tributyltin as Sn/g dry sediment).     

Side-chain alkylation of toluene with methanol over zeolite catalysts

Catalytic properties of NaX-type zeolites modified by alkali metal cations under hydrothermal conditions have been studied. The highest process efficiency is obtained for CsNaX catalysts. The effect of operation conditions on the process results was examined.     

Selective Ortho alkylation of phenol with alcohols over catalysts derived from hydrotalcite-like anionic clays

The vapour phase alkylation of phenol with a series of alcohols containing different number of carbons ranging from C₁ to C₈ were investigated over catalysts derived from magnesium-aluminium hydrotalcite with Mg/Al atomic ratio 3 (MgAl 3.0-HT). The results indicated that at 623 K the catalytic activity for phenol conversion increased with increasing chain length of linear long chain alcohols to give 2-alkylated linear alkyl phenols, without any isomerisation of the alkyl moiety. Isomorphous substitution of Mg²⁺ by Cu²⁺ or Ni²⁺ in the MgAl 3.0-HT resulted in an increase in selectivity of 2-alkyl and 2,6-dialkylphenols (≈60%) in the alkylation of phenol with 1-hexanol or 1-octanol.     

Study on the “induction period” of toluene ethylation performed on HZSM-5 zeolite catalysts

Formation and consumption of activated toluene species results in an “induction period” in the toluene ethylation on HZSM-5 zeolite, and toluene pretreatment can enhance the activity of HZSM-5 in the reaction by producing activated toluene species.     

Intrinsic surface reaction equilibrium constants of structurally charged amphoteric hydrotalcite-like compounds

The relative equations among intrinsic surface reaction equilibrium constants (K in 1-pK model, K(a1)(int) and K(a2)(int) in 2-pK model, and *K(Na)(int) and *K(Cl)(int) in inert electrolyte chemical binding model), points of zero charge (PZC), and structural charge density (sigma(st)) for amphoteric solids with structural charge were established to investigate the effects of sigma(st) on intrinsic equilibrium constants and PZC. The intrinsic equilibrium constants of HTlc with general formulas [(Zn,Mg)(1-x)Al(x)(OH)(2)](Cl,OH)(x) and [Mg(1-x)(Fe,Al)(x)(OH)(2)](Cl,OH)(x) were evaluated. The following main conclusions were obtained. For amphoteric solids with structural charge, a point of zero net charge (PZNC) independent of electrolyte concentration (c) exists. A common intersection point (CIP) should appear among the acid-base titration curves at different c, and the pH at the CIP is pH(PZNC). The pK, pK(a1)(int), and pK(a2)(int) may be expressed as a function of pH(PZNC) and sigma(st), and these intrinsic equilibrium constants can be directly calculated from pH(PZNC) and sigma(st). The inert electrolyte chemical binding does not exist for amphoteric surfaces with structural charge. PZNC is not equal to the point of zero net proton charge (PZNPC) when sigma(st) not equal 0. pH(PZNC) > pH(PZNPC) when sigma(st)>0; pH(PZNC) < pH(PZNPC) when sigma(st)<0; and pH(PZNC) = pH(PZNPC) only when sigma(st)=0. With increasing c, the difference between pH(PZNC) and pH(PZNPC) decreases; i.e., pH(PZNPC) moves forward to pH(PZNC) with increasing c. For the HTlc samples studied, with increasing x, the pH(PZNC) and the pK(a1)(int) and pK(a2)(int) decrease, and the pK increases. These results can be explained on the basis of the affinity of metal cations for H(+) or OH(-) and the electrostatic interaction between the charging surface and H(+) or OH(-).