TiO2晶面依赖的Ir-TiOx相互作用对Ir/TiO2催化剂巴豆醛选择性加氢性能的影响

α,β-不饱和醇是一类重要的精细化学品,主要通过α,β-不饱和醛选择性加氢获得.由于α,β-不饱和醛分子中含有共轭的C=C键和C=O键,且后者键能更大,在热力学和动力学上均不利于C=O键的选择性加氢生成α,β-不饱和醇.因此,提高α,β-不饱和醛中C=O的加氢选择性是催化领域中一项挑战性的课题.巴豆醛属于典型的α,β-不饱和醛,研究其选择性加氢生成巴豆醇具有广泛的代表意义;Ir负载在具有还原性载体(如TiO2)上时,表现出很好的C=O加氢选择性,因此,成为近年来的研究热点.由于暴露不同晶面的TiO2具有不同的形貌和电子结构,因此研究Ir-TiO2相互作用的晶面依赖性及其对巴豆醛选择性加氢反应的影响具有重要意义.本文以分别暴露{101}、{100}和{001}晶面的锐钛矿TiO2纳米晶为载体,制备了负载型Ir/TiO2催化剂,系统研究了催化剂经过不同的预处理过程(在不同温度下H2还原和O2再氧化)后对巴豆醛的气相选择性加氢的性能.利用高分辨透射电镜、原位X射线光电子能谱和原位漫反射红外光谱及氨程序升温脱附等技术研究发现,预处理条件显著改变了Ir-TiOx的相互作用,包括Ir金属的几何、电子性质及催化剂表面酸性.这种相互作用与TiO2的暴露晶面密切相关,从而改变了不同Ir/TiO2催化剂上不同加氢反应行为.研究结果表明,经300℃预还原的Ir/TiO2-{101}催化剂催化性能最好,在80℃下初始反应速率为166.1 μmol g-Ir-1 s-1,巴豆醇的生成转化频率为0.022 s-1.与其他催化剂相比,Ir/TiO2-{101}催化剂表面Ir0浓度最高,表面酸度适中,因此表现出最佳的催化性能.同时Ir-TiOx界面在反应中的协同作用,对H2和巴豆醛分子中C=O键的吸附和活化起到了关键作用.然而当催化剂经过400℃的H2预还原后,由于产生了强的金属-载体相互作用使得TiOx对Ir粒子进行了包裹从而导致Ir-TiOx界面缺失,因而催化剂催化巴豆醛加氢性能降低.本文为理解金属-载体相互作用对巴豆醛选择性加氢反应的影响提供了新的见解,并为设计高性能α,β-不饱和醛选择性加氢催化剂提供了理论依据.     

CHARACTERIZATIONS AND RELATIONSHIPS BETWEEN OUTDOOR AND INDOOR BIOAEROSOLS IN AN OFFICE BUILDING

1.IntroductionBioaerosolsaremicroorganismsorparticles,gases,vapors,orfragmentsofbiologicalorigin(i.e.,aliveorreleasedfromalivingorganism)thatexistintheair.Bioaerosolsareeverywhereintheenvironment.Underfavorableconditions,bioaerosolsareabletogrowandpropagateonavarietyofbuildingmaterialsandindoorsurfaces,causingindoorairpollution.Therefore,owingtotheirubiquitouspresenceinnature,bioaerosolsasapollutionsourcearealmostinevitableinarangeofenclosedenvironmentsandincommunityair(Kodama&McGee,1986;Lig…     

THERMODYNAMIC AND PARTICLE-DYNAMIC STUDIES ON SYNTHESIS OF SILICA NANOPARTICLES USING MICROWAVE-INDUCED PLASMA CVD

1. Introduction1.1 Silica nanoparticles and synthesis methods Silica (SiO2) nanoparticles are widely used in industry asan active filler for polymer reinforcement, a rheologicaladditive in fluids, a free flow agent in powders, and anagent for chemical mechanical polishing during IC (inte-grated circuit) fabrication (Sniegowski & de Boer, 2000).Silica powder is also used for producing silicon carbide(Koc & Cattamanchi, 1998) or opaque silica aerosols (Leeet al., 1995). Many methods can …     

OFDMA中继系统中基于QoS保证的资源分配算法

研究了 OFDMA 中继下行链路通信系统中的动态资源分配问题,提出了一种可以保证用户最低 QoS 需求的资源分配算法.首先在简化资源优化问题的过程中,采用等功率分配方法以降低算法复杂度,然后通过拉格朗日松弛优化方法推导出了子载波分配和中继选择最优解,并在此基础上引入用户速率权衡因子,根据速率权衡因子越大的用户,越具有选择子载波和中继的优先权这一准则进行子载波分配和中继选择.仿真结果表明:新算法能够获得较高的系统容量,同时也能很好地保证不同用户的最低速率需求.     

Synthesis and gelation behaviors of five new dimeric cholesteryl derivatives

Five new diacid amides of di-cholesteryl L-glycinates were designed and prepared.The compounds with linkers containing 0,1, 2,3,or 4 methylene units are denoted as 1,2,3,4,and 5,respectively.Their gelation behaviors in 25 solvents were tested as novel low-molecular-mass organic gelators(LMOGs).It was shown that the length of the linker connecting the two-cholesteryl residues in a gelator plays a crucial role in the gelation behavior of the compound.1 gels 11 of the 25 solvents tested at a concentration lowe...     

NO在Ag/Pt(110)-(1×2)双金属表面的吸附：亚硝酸盐/硝酸盐表面物种的生成

以俄歇电子能谱、X射线光电子能谱和热脱附谱研究了室温下NO在Ag/Pt(110)-(1×2)双金属表面的吸附. 在该双金属表面上观察到了可能的亚硝酸盐/硝酸盐表面物种,其在更高温度下分解生成N₂. 然而,室温下NO在清洁Pt(110)表面和Ag-Pt合金表面上并不会生成这种亚硝酸盐/硝酸盐表面物种. 亚硝酸盐/硝酸盐表面物种的形成归因于高度配位不饱和Ag粒子的高活性及其与Pt基底之间的协同作用.     

Two New Diterpene Alkaloids from the Roots of Spiraea japonica var. Acuta

Spiraea japonica L. (Rosaceae) is widely distributed in Yunnan Provence, P. R. China. Previous chemical investigations on S. japonica and its varieties have led to the report of 7 new atisane-type diterpenoids and 38 new diterpene alkaloids of atisine- and hetisine-type1-11. This paper describes the isolation and structure elucidation of two new diterpene alkaloids named spiratines A and B (1-2). Their structures were elucidated on the basis of 1D and 2D NMR experiments (HMQC, HMBC, 1…