X射线荧光光谱(XRF)法测定喀斯特地区土壤样品中Al2O3、CaO、Fe2O3、K2O、MgO、SiO2含量

为揭示喀斯特地区不同自然环境下土壤的相似性和差异性,为后续喀斯特石漠化治理和植被恢复提供科学依据,本文利用微晶纤维素作为粘结剂黏结剂,采用粉末样品压片制样,使用波长色散X射线荧光光谱仪建立了同时测定喀斯特地区碳酸盐、硅酸盐土壤样品中关键元素Al₂O₃、CaO、Fe₂O₃、K₂O、MgO、SiO₂含量的方法。从黏结剂对压片效果的影响、探讨了黏结剂添加比例对元素含量检测结果的影响、Al₂O₃、CaO、Fe₂O₃、K₂O、MgO、SiO₂的测量条件参数,确定了分析线、分析晶体、基体效应和谱线重叠干扰等方面进行了方法参数确认。根据优化的参数,使用49个土壤标准物质绘制校准曲线建立了检测方法。结果表明,利用新建方法进行Al₂O₃、CaO、Fe₂O₃、K₂O、MgO、SiO₂元素检测,检出限多在61.0 mg/kg 以下,相对标准偏差(RSD,n=6)为0.00 %~3.74 %,同时,利用新建方法对采自喀斯特地区不同类型的土壤样品进行检测,Al₂O₃、CaO、Fe₂O₃、K₂O、MgO、SiO₂均可被检出。此方法具有操作简便、快速、准确的优点,可同时检测喀斯特地区碳酸盐、硅酸盐土壤样品中Al₂O₃、CaO、Fe₂O₃、K₂O、MgO、SiO₂元素含量。     

熔融制样X射线荧光光谱法测定碳酸盐岩样品中的主次成分

采用复合熔剂玻璃熔片法制备样片，X射线荧光光谱法测定碳酸盐岩样品中SiO₂、Fe₂O₃、Al₂O₃、TiO₂、CaO、MgO、K₂O、Na₂O、MnO和P₂O₅等主次成分.使用理论α系数校正基体效应，国家一级标准物质验证，方法简单快速.测量结果各元素相对标准偏差（RSD，n=12）低于10%（除含量在检出限附近的元素外），检出限低，能够符合地矿行业的要求.     

硅源量和晶化时间对SAPO-34分子筛结构和性能的影响

以吗啡啉为模板剂合成了SAPO-34分子筛，研究了晶化液SiO₂/Al₂O₃比(硅源量)的影响。当SiO₂/Al₂O₃ ≥ 0.6时，能合成出纯净的SAPO-34分子筛;SiO₂/Al₂O₃=1.0时，分子筛骨架中出现“硅岛”结构，此时合成的分子筛样品具有最高的(乙烯+丙烯)选择性。继续增大硅铝比对(乙烯+丙烯     

镍基催化剂上稻草水蒸气重整制富氢合成气

采用浸渍法制备了SiO₂, γ-Al₂O₃, CaO和TiO₂负载的Ni催化剂, 以及不同MgO含量的MgO-7.5%Ni/γ-Al₂O₃催化剂,利用X射线衍射和N₂吸附-脱附技术表征了催化剂的结构,在固定床反应器上评价了它们在稻草水蒸气催化重整制合成气反应中的催化性能,考察了反应条件对催化剂性能的影响.结果表明, 以γ-Al₂O₃为载体时Ni催化剂活性最高,其中7.5%Ni/γ-Al₂O₃催化剂的H₂收率可达1071.3ml/g,H₂:CO的体积比为1.4:1;同时,MgO的添加进一步提高了该催化剂的性能,当MgO含量为1.0%时,H₂收率可达1194.6ml/g,H₂:CO体积比可达3.9:1.可见MgO的加入促进了Ni基催化剂上稻草水蒸气催化重整制合成气反应的进行,同时使得合成气中CO发生水-汽转换反应,从而大大提高了合成气中H₂含量.     

间歇式水热合成制备丝光沸石膜及其异丙醇脱水应用

采用市售廉价大孔α-Al₂O₃管作为基质材料，通过热浸渍法在管外表面涂敷晶种，随后在无模板剂体系下，利用新型的间歇式水热合成法制备丝光沸石膜。对比了传统加热和间歇式加热对丝光沸石膜形貌、结构及渗透蒸发异丙醇脱水分离性能的差异。考察了合成液中Na₂O/SiO₂、SiO₂/Al₂O₃和NaF/SiO₂物质的量之比在间歇式水热合成下对丝光沸石膜的影响。研究结果表明，当合成液中Na₂O/SiO₂、SiO₂/Al₂O₃和NaF/SiO₂物质的量之比分别为0.24、16.7和0.25时，制备的丝光沸石膜渗透蒸发异丙醇脱水分离性能最佳，在75℃下，对异丙醇/水(9∶1，w/w)的渗透通量达5.60 kg·m^-2·h^-1，水对异丙醇的分离因数大于10 000。     

氧化钇掺杂块状SiO2气凝胶的制备与表征

以正硅酸四乙酯（TEOS）为前驱体,YCl₃·6H₂O为掺杂剂,采用溶胶-凝胶法并结合CO₂超临界干燥工艺得到了块状Y₂O₃-SiO₂气凝胶,其中Y₂O₃掺杂含量控制在5wt%~30wt%范围内。利用扫描电镜（SEM）、透射电镜（TEM）、X射线衍射（XRD）、比表面积测定（BET）、X射线荧光分析（XRF）等测试手段对样品进行表征。结果表明：经过氧化钇掺杂后得到的Y₂O₃-SiO₂气凝胶,不仅维持了SiO₂气凝胶原有的空间网络结构,而且具有更高的热稳定性,经过900℃热处理2h后,10wt%Y₂O₃（0.447g的YCl₃·6H₂O）掺杂的Y₂O₃-SiO₂气凝胶仍然处于无定形态,平均孔径约为21.3nm,比表面积高达643.8m₂·g^-1。     

Al2O3-CeO2复合电解质的制备及其半导体离子燃料电池性能

通过共沉淀法制备了Al₂O₃-CeO₂复合材料,并将其作为电解质应用于半导体离子燃料电池(SIFC)。探究了Al₂O₃、CeO₂物质的量之比不同的Al₂O₃-CeO₂复合电解质对SIFC电化学性能的影响。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对材料进行了表征。其中,Al₂O₃、CeO₂物质的量之比为1∶0.5的Al₂O₃-CeO₂ (1∶0.5)电池获得了最佳性能,在550 ℃下,开路电压为1.099 V时最大功率密度为1 142 mW·cm^-2。得益于复合电解质在测试气氛下两相间的界面效应,Al₂O₃-CeO₂ (1∶0.5)电池在较低测试温度下取得了优异的混合离子传导和功率输出性能。     

Al2O3-CeO2复合电解质的制备及其半导体离子燃料电池性能

通过共沉淀法制备了Al₂O₃-CeO₂复合材料,并将其作为电解质应用于半导体离子燃料电池（SIFC）。探究了Al₂O₃、CeO₂物质的量之比不同的Al₂O₃-CeO₂复合电解质对SIFC电化学性能的影响。采用X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）对材料进行了表征。其中,Al₂O₃、CeO₂物质的量之比为1：0.5的Al₂O₃-CeO₂（1：0.5）电池获得了最佳性能,在550℃下,开路电压为1.099 V时最大功率密度为1 142 mW·cm^-2。得益于复合电解质在测试气氛下两相间的界面效应,Al₂O₃-CeO₂（1：0.5）电池在较低测试温度下取得了优异的混合离子传导和功率输出性能。     

ZrO4/SiO2-Al2O3催化肉桂醛MPV转移加氢性能

以九水合硝酸铝（Al（NO₃）₃·9H₂O）与正硅酸乙酯（TEOS）为前驱盐,采用溶胶-凝胶法制备一系列不同Al₂O₃含量的SiO₂-Al₂O₃复合氧化物,并通过浸渍硝酸氧锆引入ZrO₂,制备ZrO₂/SiO₂-Al₂O₃复合氧化物催化剂,考察催化剂在肉桂醛（CAL）MPV转移加氢中的催化性能,并结合N₂物理吸附、X射线粉末衍射（XRD）、傅里叶变换红外光谱（FTIR）、NH₃-程度升温脱附（NH₃-TPD）、Py-原位红外（Py-IR）等技术,研究催化剂结构、织构以及表面性质与其催化性能间的构效关系.研究表明,所制备的催化剂均以L酸为主,并含有少量B酸中心,这使得加氢产物以肉桂醇（COL）为主,并含有少量1-苯丙烯-2-丙基醚（CPE）.Al₂O₃含量不仅影响催化剂表面的酸中心数量,而且对催化剂的织构参数有较大影响.随Al₂O₃含量的增加,催化剂表面L酸与B酸中心均有所增加,而孔径则持续变小,这使得催化反应呈现CAL转化率先增加后减少、目标产物COL选择性先稍有减小后有所增加的趋势.在Si/Al比为2时,催化剂具有最优的催化性能,优化反应条件下,CAL转化率达96%,目标产物COL选择性达90%.     

T型分子筛膜的合成、表征与渗透汽化性能

采用二次生长法,在不锈钢、α-Al₂O₃和莫来石多孔管状支撑体上分别合成了高渗透汽化性能的T型分子筛膜。考察了合成条件如合成时间、n(SiO₂)/n(Al₂O₃)、n(H₂O)/n(Al₂O₃)和硅源等对T型分子筛膜形成和分离性能的影响。通过XRD和SEM表征了膜的晶相和形貌。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.