Effects of some nucleating agents on the supercooling of erythritol to be applied as phase change material

Nine nucleating agents, calcium pimelate (CaPi), bicyclic [1, 2, 2]heptane di-carboxylate (HPN-68), a commercially obtained aryl amide nucleating agent (TMB-5), calcium salt of hexahydrophthalic acid (HPN-20E), 1,3:2,4-di-p-methylbenzylidene sorbitol (MDBS) and sodium, potassium, magnesium and calcium salt of benzene-1, 3, 5-tricarboxylic acid (Na₃BTC, K₃BTC, Mg₃BTC₂ and Ca₃BTC₂, respectively), were applied to reduce the supercooling of erythritol, and their effects were investigated by cyclic differential scanning calorimetry (DSC). The results revealed that Na₃BTC and K₃BTC could not induce erythritol to crystallize under the experiment condition. MDBS could only make erythritol to crystallize at a temperature slightly higher than that of pure erythritol, and the effect was unstable. Mg₃BTC₂, Ca₃BTC₂ and HPN-68 could induce erythritol to crystallize at relatively high temperature, but the peak temperature of crystallizing (T _{p, cr}) and the phase change enthalpy of crystallizing (Δ_cr H) decreased greatly as the melting–crystallizing cycles increased. HPN-20E-doped erythritol crystallized at a high temperature with the T _{p, cr} of 69.3 °C at the first cycle, but the T _{p, cr} and Δ_cr H varied greatly during the melting–crystallizing cycles. CaPi and TMB-5 could induce erythritol to crystallize at a stable temperature with the T _{p, cr} of about 69 °C and 64 °C, respectively, and with a stable Δ_cr H of about 204 and 185 J g^?1, respectively, in all melting–crystallizing cycles. Hence, CaPi- and TMB-5-doped erythritol could be used as PCMs and applied in thermal energy storage in which the energy was absorbed at a high temperature and released at a lower but stable temperature.     

Comparison of Gasoline-Ranged <Emphasis Type="Italic">n</Emphasis>-Alkanes Conversions Using Dielectric Barrier Discharge: A Kinetic Study

Here, we compared the conversion of gasoline-ranged n-alkanes (C₆–C₉) using dielectric barrier discharge. For an energy density of ~68 J/L and an initial n-alkane concentration of ~230 ppm, when carbon number increased from 6 to 9, the energy efficiency of n-alkane conversion increased from 117 to 240 mmol/kWh, CO _x selectivity decreased from 46 to 20%, and ozone concentration increased from 216 to 240 ppm. The effect of energy density and initial n-alkane concentration were also investigated. The understanding of initial step of conversion was greatly aided by a proposed kinetic model. The pathways of consecutive reactions from the initiation to products were also discussed.     

Research on the Solid State Fermentation of Jerusalem Artichoke Pomace for Producing <Emphasis Type="Italic">R</Emphasis>,<Emphasis Type="Italic">R</Emphasis>-2,3-Butanediol by <Emphasis Type="Italic">Paenibacillus polymyxa</Emphasis> ZJ-9

R,R-2,3-butanediol (R,R-2,3-BD) was produced by Paenibacillus polymyxa ZJ-9, which was capable of utilizing inulin without previous hydrolysis. The Jerusalem artichoke pomace (JAP) derived from the conversion of Jerusalem artichoke powder into inulin extract, which was usually used for biorefinery by submerged fermentation (SMF), was utilized in solid state fermentation (SSF) to produce R,R-2,3-BD. In this study, the fermentation parameters of SSF were optimized and determined in flasks. A novel bioreactor was designed and assembled for the laboratory scale-up of SSF, with a maximum yield of R,R-2,3-BD (67.90 g/kg (JAP)). This result is a 36.3% improvement compared with the flasks. Based on the same bath of Jerusalem artichoke powder, the total output of R,R-2,3-BD increased by 38.8% for the SSF of JAP combined with the SMF of inulin extraction. Overall, the utilization of JAP for R,R-2,3-BD production was beneficial to the comprehensive utilization of Jerusalem artichoke tuber.     

Phase Diagram of the Quaternary System KCl–MgCl<Subscript>2</Subscript>–NH<Subscript>4</Subscript>Cl–H<Subscript>2</Subscript>O at <Emphasis Type="Italic">t</Emphasis> = 60.00 °C and Their Application

Based on the requirement for the comprehensive exploitation and utilization of the salt lake resources magnesium chloride and potassium chloride, a new technology to produce KCl and ammonium carnallite (NH₄Cl·MgCl₂·6H₂O) by using NH₄Cl as salting-out agent to separate carnallite is proposed. The solubilities of quaternary system KCl–MgCl₂–NH₄Cl–H₂O were measured by the isothermal method at t = 60.00 °C and the corresponding phase diagram was plotted and analyzed. The analysis of this phase diagram shows that there are seven saturation points and eight regions of crystallization. These eight regions of crystallization represent salts corresponding to KCl, NH₄Cl, MgCl₂·6H₂O, (K_1?n (NH₄) _n )Cl, ((NH₄) _n K_1?n )Cl, (K_1?n (NH₄) _n )Cl·MgCl₂·6H₂O, KCl·MgCl₂·6H₂O and NH₄Cl·MgCl₂·6H₂O. According to the phase diagram analysis and calculations, ammonium carnallite (NH₄Cl·MgCl₂·6H₂O) and KCl can be obtained using carnallite as raw materials and ammonium chloride as salting-out agent at t = 60.00 °C. The new technology shows the advantages of being easy to operate and having low energy consumption. The research on this quaternary phase diagram is the foundation for reasonable development of carnallite resources and comprehensive utilization of the salt lake brines.     

A “Mitsubishi emblem” tetrauclear aluminum complex containing two unsymmetric N2O2‐ligands and a symmetric NO3‐ligand as initiator for polymerization of rac‐lactide

A novel hydroxy‐, methoxy‐, and phenoxy‐bridge “Mitsubishi emblem” tetranuclear aluminum complex ( 1 ) is synthesized from an unsymmetric amine‐pyridine‐bis(phenol) N₂O₂‐ligand (H₂L¹) and a symmetric amine‐tris(phenol) NO₃‐ligand (H₂L²). Two same configuration chiral nitrogen atoms are formed in the tetranuclear Al complex upon coordination of the unsymmetric tertiary amine ligand to central Al. Complex 1 initiates controlled ring‐opening polymerization (ROP) of rac‐lactide and afford polylactide (PLA) with narrow molecular weight distributions (M_w/M_n = 1.05–1.19). The analysis of ¹H NMR spectra of the oligomer indicates that the methoxy group is the initiating group and the ring‐opening polymerization of lactide follows a coordination‐insertion mechanism. The Homonuclear decoupled ¹H NMR spectroscopy suggests the isotactic‐rich chains is preferentially formed in PLA. The study on kinetics of the ROP of lactide reveals the homopropagation rate is higher than the cross‐propagation rate, which is in agreement with the observed isotactic selectivity in the ROP of rac‐lactide. The stereochemistry of the polymerization was also supported by activation parameters. The introduction of unsymmetric ligand H₂L¹ has an effect on stereoslectivity of polymerization. This result may be of interest for the design of multinuclear metal complex catalysts containing functionalized ligands. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2084–2091     

N-heterocyclic carbene-mediated formal [3+3] annulation of isatin-derived α, β-unsaturated acids: Access to functionalized 3,4′-spirooxindole δ-lactones

An in situ activation of isatin-derived α,β-unsaturated acids 2 for the generation of isatin-derived α,β-unsaturated acyl azoliums II was described. The acyl azoliums II were successfully applied to undergo a formal [3 + 3] annulation with 1,3-dicarbonyl compounds to access functionalized 3,4′-spirooxindole δ-lactones 4. A scale-up synthesis and an enantioselective variant of this protocol were also investigated. The stable and easily prepared acids 2 may be further utilized as promising versatile electrophilic 1,3-synthons for divergent synthesis of spirooxindoles.     

An efficient method for the synthesis of gem-difluoroolefins

A series of gem-difluoroolefin derivatives were synthesized in moderate to good yields by the reaction of α,α-difluoro-β-carbonyl benzothiazol-2-yl sulfones (DFBTs) with various carbon nucleophiles. Using dl-proline as organocatalyst, the reaction of DFBT with acetone gave a tertiary alcohol, which could be further converted to the corresponding difluoroolefin by LDA.     

蒸汽辅助结晶法合成多级孔整体型ZSM-5分子筛

多级孔分子筛由于其高的比表面积、良好的传质性能和可调控的孔径等特性,引起了广大科研工作者的研究兴趣.近年来,通过选择性脱除骨架硅或铝,成功合成了多级孔沸石分子筛材料.但是由于骨架原子的脱除使分子筛的结晶度降低,进而使其催化效率降低.通过硬模板法(如炭黑、介孔硅球、气凝胶等),也用于合成多级孔沸石分子筛.然而,这种方法制备过程较为复杂,且成本较高.因此,亟需发展新的多级孔分子筛的制备方法.此外,在工业应用中,沸石分子筛催化剂通常需要做成整体柱状或片形以消除固定床反应器的床层压降.合成整体型沸石分子筛的传统方法是在沸石分子筛成型过程中添加SiO2和Al2O3等无机粘结剂.虽然该方法简单易行,但沸石分子筛的孔道结构容易被破坏,而且无机粘结剂的存在使分子筛活性中心的密度减少.为了解决这些问题,合成整体型多级孔沸石分子筛,不仅具有较强的机械稳定性,适应于工业,而且其多级孔道有利于分子的扩散,从而具有较高的催化活性.针对上述问题,我们以海绵作为模板,通过蒸汽辅助结晶(steam-assisted crystallization,SAC)方法,制备具有多级孔道的整体型ZSM-5分子筛.通过X射线衍射(XRD)、氮吸附脱附、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、固态核磁共振和氨气的程序升温脱附(NH3-TPD)等手段对分子筛进行了结构与性质表征.XRD和固态核磁共振的结果表明,成功合成了不同Si/Al的ZSM-5分子筛.SEM和TEM结果进一步确定了合成的整体型多级孔ZSM-5分子筛(记作M-ZSM-n,n代表Si/Al的摩尔比),由于分子筛颗粒的堆积形成的介孔,海绵模板提供的固体骨架形成的大孔,分子筛本身的微孔,共同构成了微孔-介孔-大孔的整体型ZSM-5分子筛.透射电子显微镜上配备的X射线能谱仪(EDS)结果表明,分子筛中的Si和Al元素能够均匀的分布.氮吸附脱附证明所得整体型分子筛具有明显的介孔结构.NH3-TPD结果表明,不同Si/Al的整体型多级孔ZSM-5分子筛具有不同强度的酸性,其酸性强度:ZSM-5(60)相似文献   

A Shifted Double-Diamond Titania Scaffold

Photonic crystals are expected to be metamaterials because of their potential to control the propagation of light in the linear and nonlinear regimes. Biological single-network, triply periodic constant mean curvature surface structures are considered excellent candidates owing to their large complete band gap. However, the chemical construction of these relevant structures is rare and developing new structures from thermodynamically stable double-network self-organizing systems is challenging. Herein, we reveal that the shifted double-diamond titania scaffold can achieve a complete band gap. The largest (7.71 %) band gap is theoretically obtained by shifting 0.332 c with the dielectric contrast of titania (6.25). A titania scaffold with similar shifted double-diamond structure was fabricated using a reverse core–shell microphase-templating system with an amphiphilic diblock copolymer and a titania source in a mixture of tetrahydrofuran and water, which could result in a 2.05–3.78 % gap.     

Zn-Co bimetallic supported ZSM-5 catalyst for phosgene-free synthesis of hexamethylene–1,6–diisocyanate by thermal decomposition of hexamethylene–1,6–dicarbamate

A set of mono-and bimetallic(Zn-Co) supported ZSM-5 catalysts was first prepared by PEG-additive method. The physicochemical properties of the catalysts were investigated by FTIR, XPS, XRD, N_2adsorption-desorption measurements, SEM, EDS and NH3-TPD techniques. The physicochemical properties showed that the Zn Co_2O_4 spinel oxide was formed on the ZSM-5 support and provided effectual synergetic effect between Zn and Co species for the bimetallic catalyst. Furthermore, bimetallic supported ZSM-5 catalyst exhibited weak, moderate and strong acidic sites, while the monometallic supported ZSM-5 catalyst showed only weak and moderate or strong acidic sites. Their catalytic performances for thermal decomposition of hexamethylene–1,6–dicarbamate(HDC) to hexamethylene–1,6–diisocyanate(HDI) were then studied. It was found that the bimetallic supported ZSM-5 catalysts,especially Zn-2Co/ZSM-5 catalyst showed excellent catalytic performance due to the good synergetic effect between Co and Zn species, which provided a suitable contribution of acidic sites. HDC conversion of 100% with HDI selectivity of 91.2% and by-products selectivity of 1.3% could be achieved within short reaction time of 2.5 h over Zn-2Co/ZSM-5 catalyst.