合成直链烷基苯的锆磷铝固体酸催化剂 I.催化剂合成及其影响因素

合成了一系列用于苯与直链烯烃烷基化反应的含有杂原子的磷铝分子筛固体酸催化剂 (MeZrAPO 5 ) ,同晶取代磷铝分子筛骨架中磷和铝的杂原子包括锆和至少一种选自硅、硼、镓、锗、铁、镁、锡等的元素。考察了晶化温度、晶化时间、杂原子种类、铝源等因素对催化剂合成的影响 ,探索了合成样品中模板剂脱除的最佳条件。结果表明 ,晶化温度高于 15 0℃、n(TEA) /n(Al2 O3 )≥ 1 5以及加入Zr原子都有利于直接生成MeZrAPO 5晶相 ;用小晶粒和高结晶度的铝源合成时 ,分子筛的结晶度高。     

Polyurethane foams with 1,3‐pyrimidine ring

Attempts of obtaining of polyurethane foams using polyetherols with 1,3‐pyrimidine ring (obtained in reactions of 6‐aminouracil with oxiranes) are reported. Properties of the foams are investigated, especially their thermal stability. The foams show an improved thermal stability up to 200°C for a long time. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Multifunctional heteroatom zeolites: construction and applications

Multifunctional heteroatom zeolites have drawn broad attentions due to the possible synergistic effects in the catalytic reactions. Remarkable achievements have been made on the synthesis, characterization and catalytic applications of multifunctional heteroatom zeolite, while a review on this important topic is still missing. Herein, current research status of multifunctional heteroatom zeolites is briefly summarized, aiming to boost further researches. First, the synthesis strategies toward heteroatom zeolites are introduced, including the direct synthesis and postsynthesis routes; then, the spectroscopic techniques to identify the existing states of heteroatom sites and the corresponding physiochemical properties are shown and compared; finally, the catalytic applications of multifunctional heteroatom zeolites in various chemical reactions, especially in one-step tandem reactions, are discussed.     

CrAPO-5和CrAPSO-5的合成及对环己烷氧化的研究

以三乙胺为模板剂，在合成过程中直接加入了硝酸铬及硅溶胶，水热合成了CrAPO-5和CrAPSO-5杂原子磷铝分子筛。以丙酮为溶剂，过氧化氢为氧化剂，考察了环己烷氧化制取环己酮的反应。反应12h、n(H2O2)／n(C6H12)=1．0、催化剂通量0．01-0．05g，环己烷的转化率最高可达到11．0％，酮醇比可达到1．39。     

杂原子MCM-41分子筛的合成及对环己烷氧化的研究

用十六烷基三甲基溴化铵为模板剂,水玻璃为硅源,在合成过程分别加入Cr3+、Co2+、Fe3+杂原子,在150℃晶化48h,水热合成了Cr-MCM-41、Co-MCM-41、Fe-MCM-41等杂原子分子筛。考察了时间、温度、催化剂用量、过氧化氢用量及催化剂再生等因素对环己烷氧化反应的影响。最佳反应条件为:温度100℃;环己烷30mmol,Cr-MCM-41为催化剂,用量0 12g;n(H2O2)/n(C6H12)=1;反应时间16h,环己烷的转化率可达28 6%,产物的酮醇摩尔比为1 89。     

Synthesis and light‐emitting properties of new poly(p‐phenylenevinylene) derivatives containing oxadiazole moiety

Two new poly(p‐phenylenevinylene) (PPV) derivatives containing oxadiazole moiety (OXA‐PPV1 and OXA‐PPV2) were synthesized by the Wittig condensation polymerization reaction. Their thermal and light‐emitting properties were investigated. The single‐ and triple‐layer electroluminescent (EL) devices with configurations of ITO/polymer/Al and ITO/polymer/OXD‐7/Alq₃/Al were fabricated. They exhibited blue emission at 470 nm for OXA‐PPV1 and green emission at 560 nm for OXA‐PPV2. The turn‐on voltages of triple‐layer device were 11 V for OXA‐PPV1 and 8 V for OXA‐PPV2. The triple‐layer EL devices showed much better performance than did the single‐layer devices. The spectra indicated energy transfer occurred from segments of side chain to polymer backbone. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 422–428, 2002     

Influence of nitrogen hetero-substitution on the electrochemical performance of coal-based activated carbons measured in non-aqueous electrolyte

Nitrogen-containing carbons were prepared by modification of activated carbons. The modified carbons were used as electrode materials with improved electrochemical performance. Precursor anthracite was activated by KOH (KOH: anthracite= 1:1), modified by melamine or urea and then treated at 1173 K to obtain the modified carbons. The porous structure, the chemical composition and the electrochemical characteristics of the carbons were investigated by nitrogen sorption, XPS and electrochemical methods respectively. Electrochemical experiments were performed in an organic electrolytic solution of 1 M (C2H5)4NBF4/PC.The samples modified by the different methods showed differences in chemical composition that introduced varying degrees of electrochemical performance enhancement. The presence of nitrogen enhanced the electron donor properties and the surface wettability of the activated carbons: this ensured a sufficient utilization of the exposed surface for charge storage.     

Cobalt Phosphide Coupled with Heteroatom‐Doped Nanocarbon Hybrid Electroctalysts for Efficient,Long‐Life Rechargeable Zinc–Air Batteries

Metal phosphides and heteroatom‐doped carbons have been regarded as promising candidates as bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, both have suffered from stability issues during repeated ORR and OER operations in zinc–air batteries (ZABs). Herein, this study reports a versatile cobalt‐based hybrid catalyst with a 1D structure by integrating the metal‐organic framework‐derived conversion approach and an in situ crosslinking method. Among them, the 1D hybrid catalyst composed of ultrasmall cobalt phosphide nanoparticles supported by nitrogen‐, sulfur‐, phosphorus‐doped carbon matrix shows remarkable bifunctional activity close to that of the benchmark precious‐metal catalysts along with an excellent durability in the full potential range covering both the OER and ORR. The overall overpotential of the rechargeable ZABs can be greatly reduced with this bifunctional hybrid catalyst as an air‐electrode, and the cycling stability outperforms the commercial Pt/C catalyst. It is revealed that the cobalt phosphide nanoparticles are in situ converted to cobalt oxide under the accelerated conditions during OER (and/or ORR) of the ZABs and reduces the anodic current applied to the carbon. This contributes to the stability of the carbon material and in maintaining the high initial catalytic properties of the hybrid catalyst.     

杂原子掺杂生物质基炭材料的研究进展

生物质基炭材料具有低成本、来源广泛、导电性良好和电化学稳定性好等优点,通过杂原子掺杂,生物质基炭材料的性能得到进一步的提升。本文总结了杂原子引入生物质基炭材料的方法（原位掺杂和扩散掺杂）及其各自的优缺点,简述了杂原子掺杂的种类（氮掺杂、氧掺杂、磷掺杂、硫掺杂、卤素掺杂和多元素共掺杂）及杂原子掺杂对生物质基炭材料结构与性能的影响,综述了目前杂原子掺杂炭材料在能源存储、吸附分离、催化氧化等领域的应用状况,并对杂原子掺杂生物质基炭材料的发展方向进行了展望。