焙烧条件对浆态床CO甲烷化Ni-Al2O3催化剂性能的影响

结合行星式球磨机,采用机械化学法制备Ni-Al₂O₃催化剂,考察了焙烧温度和焙烧时间对Ni-Al₂O₃催化剂晶相结构、还原特征、孔道结构和浆态床CO甲烷化性能的影响。通过XRD、H₂-TPR、BET、XPS和TPH等方法对反应前后催化剂进行表征。结果表明,焙烧温度从350℃升高到700℃,活性前体NiO仍在载体表面高度分散,催化剂还原峰温向高温方向偏移。其中,450℃条件下焙烧所获得的cat-450试样比表面积最大,为350 m²/g。评价结果显示,焙烧温度从350℃升高到700℃,CO转化率、CH₄选择性和收率均呈先升高后降低的趋势,于450℃达到最大值,分别为97.8%、88.2%和86.2%。另外,焙烧时间对催化剂的还原性能影响较小,对载体Al₂O₃的晶相结构有一定影响。随焙烧时间延长,CO转化率稍有降低,而后增大;焙烧时间为4 h,CH₄选择性和收率均较大。     

Fe/Ti-PILC用于C_3H_6选择性催化还原NO的研究

采用二氧化钛对蒙脱土进行柱撑改性后,以离子交换法制备了铁负载二氧化钛柱撑蒙脱土催化剂Fe/Ti-PILC,考察了其在富氧条件下催化C_3H_6选择性还原NO(C_3H_6-SCR)的性能。并借助N_2等温吸附-脱附、XRD、UV-vis、H_2-TPR、Py-FTIR等表征方法研究了催化剂的结构与性能之间的关系。结果表明,所制备的19Fe/Ti-PILC催化剂在400℃时即可实现到NO的完全脱除,N2选择性能够达到90%以上。且具有较好的抗水蒸气和抗SO_2的能力。N_2吸附-脱附和XRD结果显示,蒙脱土的结构被撑开,交联柱撑有效,形成了较大的比表面积和孔体积。UV-vis结果表明,催化剂的脱硝活性与铁氧低聚物种FexOy的含量有关,Py-FTIR结果表明,催化剂表面同时存在Lewis酸和Brnsted酸,Fe~(3+)负载到柱撑黏土中能够显著增加Lewis酸的含量,Lewis酸是影响催化剂脱硝活性的影响因素之一。H_2-TPR表征表明,催化剂在400℃左右有较强的还原能力,催化剂的还原能力主要体现为Fe~(3+)→Fe~(2+)的还原。     

1H NMR study of the kinetics of substituted aniline polymerization. II. Copolymerization of 2‐methoxyaniline and 3‐aminobenzenesulfonic acid

We investigated the kinetics of the oxidative chemical copolymerization of 2‐methoxyaniline (OMA) and 3‐aminobenzenesulfonic acid (MA) by monitoring monomer depletion with ¹H NMR spectroscopy. We adapted a semiempirical kinetic model, previously used for OMA homopolymerization, for the consumption of both OMA and MA monomers with a large difference in their reactivities. The OMA polymerization rate and end conversion showed a similar dependence on the reaction conditions, as described in the first part of this series, for its homopolymerization. Generally, the MA comonomer had an inhibition effect on the OMA polymerization rate. However, an increase in the initial MA concentration resulted in an increased OMA initiation rate. Because of the higher reactivity of OMA compared with that of MA, the OMA conversion began before the MA conversion, and both the initiation and propagation rates were higher than those for MA. The molar ratios of the converted monomers (MA/OMA) were always significantly lower than the corresponding MA/OMA feed fractions. They depended on the reaction conditions used for the copolymerization. In particular, higher oxidant or MA concentrations, higher temperatures, and a 1 M DCl concentration favored MA conversion, that is, its insertion into the copolymer. The MA end conversion was much smaller than that of OMA, only up to 23%; for a low oxidant concentration (oxidant/monomer‐deficient molar ratio), it was only 6%. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2482–2493, 2001     

Release of Singlet Oxygen from Aromatic Endoperoxides by Chemical Triggers

The generation of reactive singlet oxygen under mild conditions is of current interest in chemistry, biology, and medicine. We were able to release oxygen from dipyridylanthracene endoperoxides (EPOs) by using a simple chemical trigger at low temperature. Protonation and methylation of such EPOs strongly accelerated these reactions. Furthermore, the methyl pyridinium derivatives are water soluble and therefore serve as oxygen carriers in aqueous media. Methylation of the EPO of the ortho isomer affords the parent form directly without increasing the temperature under very mild conditions. This exceptional behavior is ascribed to the close contact between the nitrogen atom and the peroxo group. Singlet oxygen is released upon this reaction, and can be used to oxygenate an acceptor such as tetramethylethylene in the dark with no heating. Thus, a new chemical source of singlet oxygen has been found, which is triggered by a simple stimulus.     

A THEORETICAL APPROACH TO P_(co_2) EVOLUTION IN THE ATMOSPHERE BASED ON ASSOCIATIONS OF SEDIMENTARY MINERALS

Based on the theory of pH evolution of sea water and the balance between the seawater and the atmosphere the authors discussed the problems about (i) the method ofcalculating P_(CO_2) in the ancient atmosphere with the associations of sedimentary miner-als; (ii) the evolution of P_(CO_2) values in the geologic history; (iii) the relations of thepH evolution of sea water with carbonate precipitations; and (iv) calculation of the pHlimit for some associations of sedimentary minerals and its corresponding P_(CO_2) valuesin the atmosphere. The authors pointed out that though carbonates had deposited little in the Archaean,the content of CO_2 gas in the Archaean atmosphere was very high and was gradually go-ing up to form a thick CO_2 atmosphere. Up to 2600 Ma ago, the P_(CO_2) had reached a gradeof 10- 50 atm. There was a general trend of evolution that from the early Proterozoicera to the present the depositional horizon of carbonate layers was gradually risingand finally surpassed the horizons of clay min     

Nickel-oxide-based electrochromic films with optimized optical properties

Reactive DC magnetron sputtering was used to grow thin films of Ni (93%)-V (7%) oxide and Ni (62%)-Al (38%) oxide. Both films showed electrochromism in KOH. The addition of Al diminished the luminous absorbance significantly, while the charge capacity was maintained. The Al-containing films are superior to the conventional Ni oxide electrodes as regards applications requiring high-bleached-state transmittance.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic     

YDHC-10催化剂用于不饱和植物油脂肪酸氢化工艺条件的研究

采用自制的催化剂YDHC-10对氢化工艺条件进行了研究。找出了植物油脂肪酸氢化时,氢化压力2MPa、氢化温度180-200℃、氢化时间60min以及催化剂浓度对植物油脂肪酸氢化的影响．     

Photocatalytic Organic Syntheses: Selective Cyclization of Amino Acids in Aqueous Suspensions

Photocatalytic reactions occurring at semiconductor particles/solution interfaces can be applied to organic syntheses. In this review article, examples of photocatalytic syntheses of cyclic amino acids by suspended semiconductor particles, e.g., titanium(IV) oxide or cadmium(II) sulfide are introduced and interpreted. Different from the photocatalytic decomposition of pollutants under aerobic conditions, selective conversion of organic compounds can be driven by the photocatalytic reactions under deaerated conditions.     

Seeded Polymerization of an Amide-Functionalized Diketopyrrolopyrrole Dye in Aqueous Media

The self-assembly of an amide-functionalized dithienyldiketopyrrolopyrrole (DPP) dye in aqueous media was achieved through seed-initiated supramolecular polymerization. Temperature- and time-dependent studies showed that the spontaneous polymerization of the DPP derivative was temporally delayed upon cooling the monomer solution in a methanol/water mixture. Theoretical calculations revealed that an amide-functionalized DPP derivative adopts an energetically favorable folded conformation in the presence of water molecules due to hydration. This conformational change is most likely responsible for the trapping of monomers in the initial stage of the cooperative supramolecular polymerization in aqueous media. However, the monomeric species can selectively interact with externally added fragmented aggregates as seeds through concerted π-stacking and hydrogen-bonding interactions. Consequently, the time course of the supramolecular polymerization and the morphology of the aggregated state can be controlled, and one-dimensional fibers that exhibit a J-aggregate-like bathochromically shifted absorption band can be obtained.     

以天然矿物为全部硅铝源低成本绿色合成ZSM-5分子筛的研究

ZSM-5分子筛被广泛地应用于催化、吸附分离、离子交换和绿色化工等领域,但目前其合成主要是以无机化学品为硅铝源,从源头来看是非绿色化的过程.我们以热活化的硅藻土和亚熔盐活化的累托土为全部硅铝源,通过调变两种矿物的加入比例调变合成体系的硅铝比,在水热合成体系中制备ZSM-5分子筛.系统地考察模板剂用量、碱度、投料硅铝比、晶化时间等合成条件对产物结构和性质的影响,并对在最优条件下合成的ZSM-5分子筛的物化性质进行了详细地表征,结果表明：以天然矿物为全部硅铝源可以合成出具有较高结晶度、晶粒尺寸约为4 μm的六面体挛晶形貌的ZSM-5分子筛,该分子筛比商业ZSM-5分子筛具有更高的水热稳定性和更优的加氢异构性能.