HYDROLYTIC CLEAVAGE OF ACMET-GLY PROMOTED BY CIS-[Pd(MET)(D_2O)_2](NO_3)_2

ＨＹＤＲＯＬＹＴＩＣＣＬＥＡＶＡＧＥＯＦＡＣＭＥＴ－ＧＬＹＰＲＯＭＯＴＥＤＢＹＣＩＳ－［Ｐｄ（ＭＥＴ）（Ｄ２Ｏ）２］（ＮＯ３）２￥ＸｉａｏＨｕａＣＨＥＮ；ＬｏｎｇＧｅｎＺＨＵ；Ｎ．Ｍ．Ｋｏｓｔｉｃ（ＣｏｏｒｄｉｎａｔｉｏｎＣｈｅｍｉｓｔｒｙＩｎｓｔｉ...     

SYNTHESIS OF CHIRAL TETRAHEDRAL TRANSITION METAL CARBONYL CLUSTERS SFeCoM（CO）_8（RCOCp）（M＝Mo，W；R＝H，CH_3，C_2H_5O）AND THE CRYSTAL STRUCTURE OF SFeCoW（CO）_8（C_2H_5O_2CCp）

ＳＹＮＴＨＥＳＩＳＯＦＣＨＩＲＡＬＴＥＴＲＡＨＥＤＲＡＬＴＲＡＮＳＩＴＩＯＮＭＥＴＡＬＣＡＲＢＯＮＹＬＣＬＵＳＴＥＲＳＳＦｅＣｏＭ（ＣＯ_８（ＲＣＯＣｐ）（Ｍ＝Ｍｏ，Ｗ；Ｒ＝Ｈ，ＣＨ_３，Ｃ_２Ｈ_５Ｏ）ＡＮＤ　ＴＨＥ　ＣＲＹＳＴＡＬ　ＳＴＲＵＣＴＵＲＥ...     

MOLECULAR AND CRYSTAL STRUCTURE OF Co_3（μ－PSCH_2CH_2O）_3（CO）_6 CONTAINING NEW BRIDGING HETEROCYCLIC PHOSPHIDO LIGANDS

ＭＯＬＥＣＵＬＡＲＡＮＤＣＲＹＳＴＡＬＳＴＲＵＣＴＵＲＥＯＦＣｏ_３（μ－ＰＳＣＨ_２ＣＨ_２Ｏ）_３（ＣＯ）_６ＣＯＮＴＡＩＮＩＮＧＮＥＷＢＲＩＤＧＩＮＧＨＥＴＥＲＯＣＹＣＬＩＣＰＨＯＳＰＨＩＤＯＬＩＧＡＮＤＳ￥ＱｉＷａｎｇＬＩＵ；ＸｉａｎｇＨＵ；Ｓｈ?..     

SYNTHESIS AND CHARACTERIZATION OF Pt－M（M＝Cr，Mo，W） HETEROBINUCLEAR METAL HYDRIDO CARBONY COMPOUNDS

ＳＹＮＴＨＥＳＩＳＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＰｔ－Ｍ（Ｍ＝Ｃｒ，Ｍｏ，Ｗ）ＨＥＴＥＲＯＢＩＮＵＣＬＥＡＲＭＥＴＡＬＨＹＤＲＩＤＯＣＡＲＢＯＮＹＣＯＭＰＯＵＮＤＳ￥ＣｈａｎｇＰｉｎｇＳＨＡＯ；ＪｉｅＹｕＷＡＮＧａｎｄＨｅＦｕＧＵＯ（Ｄａ...     

MOLECULAR MECHANICAL AND QUANTUM CHEMICAL CALCULATION ON ACYLATION REACTIVITY FOR 1－（NITRO SUBSTITUTED ANILINO）－4－SUBSTITUTED－2，6－PIPERAZINEDIONES

ＭＯＬＥＣＵＬＡＲＭＥＣＨＡＮＩＣＡＬＡＮＤＱＵＡＮＴＵＭＣＨＥＭＩＣＡＬＣＡＬＣＵＬＡＴＩＯＮＯＮＡＣＹＬＡＴＩＯＮＲＥＡＣＴＩＶＩＴＹＦＯＲ１－（ＮＩＴＲＯＳＵＢＳＴＩＴＵＴＥＤＡＮＩＬＩＮＯ）－４－ＳＵＢＳＴＩＴＵＴＥＤ－２，６－ＰＩＰＥＲＡＺ...     

ELECTROCHEMICAL BEHAVIOR OF MOLYBDOTUNGSATE HETEROPOLY COMPLEX WITH NEODYMIUMK_（10）H_3［Nd（SiMO_7W_4O_（39）_2）］xH_20 IN AQUEOUS SOLUTION

ＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬＢＥＨＡＶＩＯＲＯＦＭＯＬＹＢＤＯＴＵＮＧＳＡＴＥＨＥＴＥＲＯＰＯＬＹＣＯＭＰＬＥＸＷＩＴＨＮＥＯＤＹＭＩＵＭＫ_（１０）Ｈ_３［Ｎｄ（ＳｉＭＯ_７Ｗ_４Ｏ_（３９）_２）］ｘＨ_２０ＩＮＡＱＵＥＯＵＳＳＯＬＵＴＩＯＮＸｉｕＭ?..     

IN－SITU FTIR AND UV－VISIBLE－NEAR－IR SPECTROELECTROOHEMICAL STUDIES OF MIXED－VALENCE ISOPOLYANION Mo＿6O＿（19）￣（3－） IN APROTIC MEDIA

ＩＮ－ＳＩＴＵ　ＦＴＩＲ　ＡＮＤ　ＵＶ－ＶＩＳＩＢＬＥ－ＮＥＡＲ－ＩＲ　ＳＰＥＣＴＲＯＥＬＥＣＴＲＯＯＨＥＭＩＣＡＬ　ＳＴＵＤＩＥＳ　ＯＦ　ＭＩＸＥＤ－ＶＡＬＥＮＣＥ　ＩＳＯＰＯＬＹＡＮＩＯＮ　Ｍｏ＿６Ｏ＿（１９）￣（３－）　ＩＮ　ＡＰＲＯＴＩＣ　Ｍ...     

PARAMAGNETIC AND DIAMAGNETIC DICOPPER（Ⅱ） COMPLEXES WITH DI－SCHIFF BASE DERIVED FROM 2－HYDROXY－1－NAPHTHALDEHYDE AND1，3－DIANINO－2－PROPANOL

ＰＡＲＡＭＡＧＮＥＴＩＣＡＮＤＤＩＡＭＡＧＮＥＴＩＣＤＩＣＯＰＰＥＲ（Ⅱ）ＣＯＭＰＬＥＸＥＳＷＩＴＨＤＩ－ＳＣＨＩＦＦＢＡＳＥＤＥＲＩＶＥＤＦＲＯＭ２－ＨＹＤＲＯＸＹ－１－ＮＡＰＨＴＨＡＬＤＥＨＹＤＥＡＮＤ１，３－ＤＩＡＮＩＮＯ－２－ＰＲＯＰＡＮＯＬ...     

SIMULATION CALCULATION FOR CHEMICAL SPECIATION OF LEAD BY FEEDBACK NEURAL NETWORK

ＳＩＭＵＬＡＴＩＯＮＣＡＬＣＵＬＡＴＩＯＮＦＯＲＣＨＥＭＩＣＡＬＳＰＥＣＩＡＴＩＯＮＯＦＬＥＡＤＢＹＦＥＥＤＢＡＣＫＮＥＵＲＡＬＮＥＴＷＯＲＫ￥ＨｕａＭＯ；ＢｏＤＥＮＧ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＴｓｉｎｇｈｕａＵｎｉｖｅｒｓｉｔｙ...     

SYNTHESIS AND CRYSTAL STRUCTURE OF THE CLUSTER COMPOUND MoS_4Cu_2Ag（Ph_3P）_3Br．H_2O

ＳＹＮＴＨＥＳＩＳ ＡＮＤ ＣＲＹＳＴＡＬ ＳＴＲＵＣＴＵＲＥ ＯＦ ＴＨＥ ＣＬＵＳＴＥＲ ＣＯＭＰＯＵＮＤ ＭｏＳ_４Ｃｕ_２Ａｇ（Ｐｈ_３Ｐ）_３Ｂｒ．Ｈ_２Ｏ￥ＤｅＬｉａｎｇＬＯＮＧ；ＸｉｎＱｕａｎＸＩＮ（ＳｔａｌｅＫｅｙＬａｂｏｒａｔｏｒｙｏｆ?..     

Sonochemical preparation of supported hydrodesulfurization catalysts

Sonochemical preparation of Co and Ni promoted MoS(2) supported on alumina was achieved by high-intensity ultrasonic irradiation of isodurene solutions containing molybdenum carbonyl, dicobalt octacarbonyl, elemental sulfur, and Al(2)O(3) or Ni-Al(2)O(3) under Ar flow. The sonochemically prepared catalysts were characterized by elemental analysis, XPS, SEM, TEM, and XEDS, and hydrodesulfurization (HDS) activity evaluated for thiophene and dibenzothiophene substrates. The TEM studies on the sonochemically prepared catalysts indicate the formation of layered hexagonal MoS(2) (lattice fringes approximately 6.2 A) on the alumina support. The sonochemically prepared Co-Mo-S/Al(2)O(3), Ni-Mo-S/Al(2)O(3), and Co-Ni-Mo-S/Al(2)O(3) are extremely active catalysts for the HDS of thiophene and dibenzothiophene, with activities severalfold those of comparable commercial catalysts under identical conditions. The layered structure of MoS(2) remained intact after 120 h of HDS, and the catalyst is reusable.     

磷对预硫化型NiMo/Al2O3催化剂加氢脱硫脱氮性能的影响

利用等体积浸渍法制备了不同磷含量的预硫化型NiMo/Al2O3催化剂,并利用XRD、BET、TPR和HRTEM等分析方法对其进行了表征,研究了磷对其加氢脱硫脱氮性能的影响.结果表明,由于预硫化型NiMo加氢催化剂上活性组分和载体的相互作用较弱,MoS2或Ni-Mo-S相主要以TypeⅡ形式存在,磷通过增加MoS2的堆积...     

二硫化钼中空微球的制备、表征以及光催化性能

以四丁基溴化铵为添加剂,采用水热法制备出直径为2～5μm的二硫化钼(MoS2)空心微球,研究了反应温度、添加剂量和时间对MoS2物相和形貌的影响。XRD、SEM、EDS、TEM、XPS表征结果表明,当反应温度为240℃时可得到结晶良好的六方相2H-MoS2,MoS2的形貌主要受四丁基溴化铵用量的影响,随着用量的增多MoS2历经了球状-花球状-不规则堆积状的递变。对MoS2中空微球的形成机制进行了探讨,认为在反应中四丁基溴化铵起到了模板的作用。通过制备样品对罗丹明B的降解评估了二硫化钼中空微球的光催化性能,其对罗丹明的降解效率达到90%。     

Cluster-support interactions and morphology of MoS2 nanoclusters in a graphite-supported hydrotreating model catalyst

Supported MoS(2) nanoparticles constitute the active component of the important hydrotreating catalysts used for industrial upgrading and purification of the oil feedstock for the production of fossil fuels with a low environmental load. We have synthesized and studied a model system of the hydrotreating catalyst consisting of MoS(2) nanoclusters supported on a graphite surface in order to resolve a number of very fundamental questions related to the atomic-scale structure and morphology of the active clusters and in particular the effect of a substrate used in some types of hydrotreating catalysts. Scanning tunneling microscopy (STM) is used to image the atomic-scale structure of graphite-supported MoS(2) nanoclusters in real space. It is found that the pristine graphite (0001) surface does not support a high dispersion of MoS(2), but by introducing a small density of defects in the surface, highly dispersed MoS(2) nanoclusters could be synthesized on the graphite. From high-resolution STM images it is found that MoS(2) nanoclusters synthesized at low temperature in a sulfiding atmosphere preferentially grow as single-layer clusters, whereas clusters synthesized at 1200 K grow as multilayer slabs oriented with the MoS(2)(0001) basal plane parallel to the graphite surface. The morphology of both single-layer and multilayer MoS(2) nanoclusters is found to be preferentially hexagonal, and atom-resolved images of the top facet of the clusters provide new atomic-scale information on the MoS(2)-HOPG bonding. The structure of the two types of catalytically interesting edges terminating the hexagonal MoS(2) nanoclusters is also resolved in atomic detail in STM images, and from these images it is possible to reveal the atomic structure of both edges and the location and coverage of sulfur and hydrogen adsorbates.     

W-Ni/Al2O3-USY催化剂中USY的作用

采用ＥＳＣＡ，ＴＰＲ及高压连续流动反应色谱等技术研究了在Ｗ－Ｎｉ／Ａｌ２Ｏ３中引入超稳Ｙ型分子筛对载体表面性质及催化剂加氢脱氮活性的影响。结果表明：ＵＳＹ可明显改善Ｗ和Ｎｉ的分散状态，提高催化剂的总酸，并可调变Ｂ酸和Ｌ酸的分布；加入ＵＳＹ可提高催化剂的比表面积，但不利于发挥Ｎｉ的助剂作用；加入适宜量的ＵＳＹ，可明显提高催化剂的加氢脱氮活性。     

碳化钼催化剂加氢脱氮性能研究

MoO3在CH4/H2气氛中程序升温还原碳化反应制备了Mo2C催化剂,用XRD、BET、SEM、XPS进行了表征。以吡啶/环己烷溶液为模型化合物,在高压微反装置上评价了碳化钼催化剂的吡啶加氢脱氮性能。结果表明,MoO3在CH4/H2气氛中程序升温至675℃可制得高纯度的β-Mo2C,SEM表征其形貌为板块状颗粒,平均粒径约3.9μm,比表面积达到了10.7m2/g,高于其前驱体MoO3 的2.7倍。在反应压力3.0MPa,空速为8h－1,H2/原料液体积比为500∶1,体积分数为5%的吡啶/环己烷溶液中,碳化钼催化剂在340℃下的吡啶加氢脱氮转化率达到了86.30%,高于相应MoS2约8%。随还原碳化温度的升高,碳化钼催化剂的比表面积降低,表面积炭增多,导致其吡啶加氢脱氮活性下降。确定的碳化钼催化剂的合成条件以还原碳化温度675℃、还原碳化气体空速1.8×104h－1左右较为适宜。     

载体对Ni_2P催化剂加氢脱氮反应性能的影响

使用TiO2、Al2O3以及TiO2-Al2O3复合载体考察了载体对磷化镍催化剂活性相和加氢脱氮性能的影响。不同钛铝原子比的TiO2-Al2O3复合载体采用原位-溶胶凝胶法制备,负载的磷化镍催化剂采用等体积浸渍法和H2原位还原法制备。以喹啉为模型化合物在固定床反应器上对催化剂的加氢脱氮性能进行评价,采用XRD、N2吸附、TEM和H2-TPR等技术对催化剂和载体进行了表征。结果表明,制成的复合载体基本保留了最初引入的γ-Al2O3的孔特征,分散在γ-Al2O3表面的TiO2以锐钛矿晶型存在。不同载体对催化剂的H2还原行为有显著影响,所形成的活性物种也不相同。Al2O3中引入TiO2可以减弱P物种和Al2O3之间的相互作用,有利于Ni2P活性相的生成和催化活性的提高。当Ti/Al的原子比为1∶8时,Ni2P/TiO2-Al2O3催化剂比Ni2P/TiO2、Ni2P/Al2O3催化剂具有更高的加氢脱氮活性。     

不同晶型纳米CdS的合成及其光催化活性

以醋酸镉为镉源,硫脲为硫源,采用配合物热分解法,通过改变硫脲/醋酸镉的摩尔配比,合成了具有不同晶型的纳米CdS．当n（S）／n（Cd）=0．5—3时,合成的CdS相分别为立方相（n（S）／n（Cd）=0．5）,立方相和六方相的混相（n（S）／n（Cd）=1．0～1．5）,六方相（n（S）／n（Cd）≥2）．通过XRD,TEM,UV—Vis光谱,IR光谱等对CdS的相组成,形貌,粒径,吸光性能,表面结构等进行了表征．光催化降解罗丹明B的活性结果表明,不同CdS相组成的活性顺序为立方相〉六方相〉混相（立方＋六方）,其中立方CdS相由于有较强的吸附作用、光吸收性能和较小的粒径（10～13nm）,对罗丹明B具有最好的光催化降解活性．     

Synthesis of Ni2P promoted trimetallic NiMoW/γ-Al2O3 catalysts for diesel oil hydrotreatment

The Ni2P promoted and γ-Al2O3 supported NiMoW sulfide catalyst consisting of 4 wt% Mo, 22 wt% W, 2 wt% Ni and 2.5 wt% Ni2P was synthesized by a co-impregnation method. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, NH3 temperature-programmed desorption (NH3-TPD) and transmission electron microscopy (TEM). The results showed that Ni2P, Ni, Mo and W species were highly dispersed over γ-Al2O3. The hydrodesulfurization (HDS) of dibenzothiophene (DBT) showed that the presence of Ni2P brought a strong promotional effect on the HDS activity, which was further confirmed by the HDS and hydrodenitrogenation (HDN) of diesel oil under industrial conditions. The enhancement in HDN activity and stability by Ni2P addition could be attributed more to the effect of new active sites of Ni2P than that of acidity modification. The as-prepared Ni2P-NiMoW/γ-Al2O3 catalyst showed better hydrotreating performance than NiMoW/γ-Al2O3 and commercial catalysts.     

XPS study of molybdenum sulfide catalyst exposed to CO and H2

Amorphous MoS(3) (air-dried precipitate), crystalline MoS(2) (made in the laboratory under nitrogenous atmosphere), and commercial molybdenum disulfide catalysts have been investigated by X-ray photoelectron spectroscopy (XPS). The chemical species present on the surface and the S/Mo atomic ratios of laboratory catalysts were compared to those present on a commercial molybdenum disulfide catalyst before and after treatment with CO and H(2). Pretreatment of MoS(2) with CO followed by H(2) showed that CO was adsorbed on the surface with no change in the chemical oxidation state of Mo and S. However, the results indicated that CO was not adsorbed when the sequence of gas exposures was reversed.