费-托合成铁-钼/活性炭催化剂还原和碳化的穆斯堡尔谱研究

以原位穆斯堡尔谱研究了活性炭担载的费-托合成铁-钼双金属催化剂的还原和碳化行为。在H_2中不同温度下还原催化剂,其中的Fe~(3+)还原为Fe~(2+),进而还原为Fe~0。但在400—450℃间发生了还原铁物类的再氧化现象,可归因于磷钼酸根Keggin结构的热分解。在500℃H_2中,铁和钼都还原为金属并形成合金,其穆斯堡尔谱为一单峰,同质异能移为-0.16mm/s。再在300℃合成气(2H_2/CO)中碳化,可生成Fe-Mo碳化物(Fe_(1-y)Mo_y)_xC,穆斯堡尔谱为δ～0.17mm/s,△～0.64mm/s的双峰。     

非担载铁—钼催化剂在氢还原过程中的物相研究

本文利用原位穆斯堡尔谱和XRD研究了10%Fe/MoO_3催化剂在氢还原过程中铁和钼的物相及其变化.结果表明.在铁和钼还原的同时,它们之间的相互作用增强,使得在350℃—500℃的温度范围内.升高还原温度,催化剂的还原度反而下降.在350℃铁可部分地还原为零价,这时钼仅还原为MoO_2在500℃,钼开始还原到零价.这时还原生成的Fe~0形成Fe-Mo合金,在550℃铁和钼全部还原为零价,铁以Fe-Mo合金存在,其穆斯堡尔谱显示精细结构.     

还原温度对Fe-Mo催化剂性质及F-T合成性能的影响

研究了还原温度对Fe-Mo催化剂性质及费托(F-T)合成性能的影响。采用N₂物理吸附、X射线衍射、穆斯堡尔谱和H₂程序升温脱附技术对催化剂进行了表征。结果表明,随还原温度升高,金属铁晶粒粒径增大,金属铁上的H₂吸附量先升后降;催化剂还原度提高,反应态催化剂碳化铁含量递增。催化剂F-T合成性能在280 ℃、1.5 MPa、2 000 h^-1、合成气H₂/CO比为2.0条件下在固定床反应器中测试。反应结果表明,随还原温度提高,催化剂接近稳态时的活性和重质烃选择性(C₅⁺)先升后降,而甲烷选择性则先降后升。350 ℃还原催化剂具有最佳F-T合成反应性能。     

Effect of reduction temperature on the properties and Fischer-Tropsch synthesis performance of Fe-Mo catalysts

研究了还原温度对Fe-Mo催化剂性质及费托(F-T)合成性能的影响.采用N2物理吸附、X射线衍射、穆斯堡尔谱和H2程序升温脱附技术对催化剂进行了表征.结果表明,随还原温度升高,金属铁晶粒粒径增大,金属铁上的H2吸附量先升后降;催化剂还原度提高,反应态催化剂碳化铁含量递增.催化剂F-T合成性能在280℃、1.5MPa、2000h-1、合成气H2/CO比为2.0条件下在固定床反应器中测试.反应结果表明,随还原温度提高,催化剂接近稳态时的活性和重质烃选择性(C5+)先升后降,而甲烷选择性则先降后升.350℃还原催化剂具有最佳F-T合成反应性能.     

Mn助剂加入方式对铁基催化剂F-T合成性能的影响

采用连续共沉淀与喷雾干燥成型技术相结合的方法制备了系列微球状Fe/Mn/K催化剂,结合H2 DTG、CO TPR、Mossbauer谱等表征手段,研究了Mn助剂的加入方式对铁基催化剂物相结构、还原和碳化行为以及F-T合成性能的影响。催化剂在浆态床反应器中以接近F-T合成实际工况条件 (250℃、1.5MPa、H2/CO=0.67和2.0L /(gcat·h)) 进行评价。结果表明,以共沉淀方式加入Mn助剂具有较强的Fe Mn相互作用,从而抑制了催化剂的还原和碳化,降低了催化剂的活性,提高了催化剂的稳定性。而以部分共沉淀和黏结剂方式加入Mn助剂促进了催化剂的还原和碳化,提高了反应活性加速了催化剂的失活。与共沉淀Mn相比,部分共沉淀和黏结剂Mn提高了重质烃和烯烃的选择性,同时抑制了有机含氧化合物的生成。     

氢还原下铁钼催化剂的表面性质

用XPS对H_2还原下的铁钼催化剂的表面性质进行了研究。实验表明:H_2还原使表面钼离子由Mo~(6+)还原为Mo~(5+)和Mo~(4+),并与Fe~(3+)作用氧化为Mo~(6+);Fe~(3+)则由于与Mo~(5+)和Mo~(4+)作用以及H_2还原而变为Fe~(2+),从而形成了一个没有O_2存在,仅有H_2作用下的Mars-Krevelen氧化还原循环过程。在催化剂表面上生成的FeMoO_4,其Mo~(6+)的3d3/2和3d5/2的结合能值比Fe_2(MoO_4)_3中的Mo~(6+)的3d能级结合能值低。Mo(或Mo和Fe)离子键合的O~(2-)与H_2作用生成的Mo(Fe)-OH,其Os结合能的测定值低于键合于Mo(Fe)离子中的O~(2-)的Os结合能值,并且该结合能峰由于-OH间的相互作用结合成的水的脱附而消失。此外.给出了还原过程中H_2与催化剂表面O~(2-)相互作用的反应图式。     

Effects of Zn promoter on the structure and Fischer-Tropsch performance of iron catalyst

采用低温N2吸附、XRD、MES、CO-TPR和H2-DTG研究了Zn(100 gFe/x gZn,x=7～100)助剂对Fischer-Tropsch(F-T)合成Fe基催化剂的织构性质、还原行为以及相变结构的影响；在H2/CO=2.0、260℃、1.5 MPa和4000 mL/(g·h)条件下在固定床反应器上考察了Zn助剂含量对Fe基催化剂F-T合成反应活性、烃产物选择性和运行稳定性的影响.研究结果表明,随着Zn含量的增加,氧化态催化剂的物相由α-Fe2O3和ZnFe2O4逐渐向ZnFe2O4和ZnO转变,ZnFe2O4在催化剂中优先生成,只有在超出其计量比1∶2之后才有ZnO出现.由于ZnFe2O4较为稳定,能够促进催化剂中Fe物相的分散,导致比表面积增加.在还原和反应态催化剂中,ZnFe2O4一方面抑制催化剂的过度还原和碳化；另一方面表现为稳定活性相铁碳化物.催化剂的F-T反应性能评价结果表明,纯铁催化剂由于铁碳化物氧化而迅速失活,而Zn助剂催化剂却由于ZnFe2O4的稳定作用,活性较为稳定.同时,由于催化剂在反应初相变的影响,导致Zn助剂催化剂的初始烯烃选择性随着Zn含量的增加而增加,在相态稳定之后选择性趋于一致.     

Zn对沉淀铁催化剂结构及其F-T合成性能的影响

采用低温N₂吸附、XRD、MES、CO-TPR和H₂-DTG研究了Zn(100 gFe/x gZn, x=7～100)助剂对 Fischer-Tropsch (F-T) 合成Fe基催化剂的织构性质、还原行为以及相变结构的影响;在H₂/CO=2.0、260 ℃、1.5 MPa和4000 mL/(g·h) 条件下在固定床反应器上考察了Zn助剂含量对Fe基催化剂F-T合成反应活性、烃产物选择性和运行稳定性的影响。研究结果表明,随着Zn含量的增加,氧化态催化剂的物相由α-Fe₂O₃和ZnFe₂O₄逐渐向ZnFe₂O₄和ZnO转变,ZnFe₂O₄在催化剂中优先生成,只有在超出其计量比1∶2之后才有ZnO出现。由于ZnFe₂O₄较为稳定,能够促进催化剂中Fe物相的分散,导致比表面积增加。在还原和反应态催化剂中,ZnFe₂O₄一方面抑制催化剂的过度还原和碳化;另一方面表现为稳定活性相铁碳化物。催化剂的F-T反应性能评价结果表明,纯铁催化剂由于铁碳化物氧化而迅速失活,而Zn助剂催化剂却由于ZnFe₂O₄的稳定作用,活性较为稳定。同时,由于催化剂在反应初相变的影响,导致Zn助剂催化剂的初始烯烃选择性随着Zn含量的增加而增加,在相态稳定之后选择性趋于一致。     

反应条件对固相合成负载羰基铑原子簇催化剂及其性能的影响

本文报告了由金属盐直接固相合成负载铑络合物或原子簇催化剂的新方法及IR谱表征。CO容易使表面吸附有水分子的RhCl_3/SiO_2还原并生成表面羰基物Rh~+-(CO)_2/SiO_2;CO、CO/H_2和CO/2H_2等不同还原气对表面络合物的生成没有影响。采用H_2还原只能得到金属Rh催化剂。水是重要影响因素,如果RhCl_3/SiO_2先抽空脱水,再用含水的CO还原,就会使Rh~+(CO)_2/SiO_2转化为Rh_6(CO)_(16)/SiO_2。此外,还考察了负载原子簇的CO加氢和热分解反应性能。采用CO还原RhCl_3/SiO_2制备的催化剂同负载原子簇催化剂的反应行为非常相近,而且比传统催化剂具有更高的反应活性。     

浸渍钠对铁基催化剂F-T合成浆态床反应性能的影响

以FeCuK/Si O2为母体催化剂,通过乙酸钠浸渍得到一组不同Na含量的费托合成铁基催化剂.采用原子发射光谱、低温N2吸附、程序升温还原和M ssbauer谱等技术对催化剂进行了表征.在H2/CO摩尔比为0.67,空速为2 000 h-1,压力为1.5 MPa和温度为250℃的条件下进行了浆态床F-T合成反应性能评价实验.结果表明,浸渍少量Na能提高催化剂的比表面积,促进铁物相的分散,而浸渍大量Na却大大降低了催化剂的比表面积,使催化剂中的铁物相聚集形成较大的颗粒;浸渍Na抑制了催化剂在H2中的第一步还原,但促进了催化剂在CO中的碳化;在原位合成气还原过程中,浸渍Na有利于催化剂的碳化.在500 h的运行实验中,浸渍Na的催化剂均表现出不同程度的失活现象.反应结果表明,浸渍Na对水煤气变换反应活性影响不大,对费托合成反应活性和烃产物选择性有较大的影响.在铁基催化剂上浸渍Na有利于C12 重质烃和低碳烯烃的生成.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.