常压低温等离子体有效去除催化CO氧化的金原子团簇的保护剂（英文）

采用介质阻挡放电等离子体技术可以在低温、常压下实现对纳米金催化剂中保护基团的有效去除.本文通过对不同保护基团(聚乙烯吡咯烷酮和半胱氨酸)保护的金催化剂进行等离子体预处理,发现采用该技术能有效去除载体中的层间阴离子,还可能将金原子与保护基团之间的化学键打断.通过X射线粉末衍射对等离子体处理后的样品和未经处理的样品进行表征,发现经等离子体处理后的样品,载体从水滑石结构变为复合氧化物结构,这说明等离子体处理可将载体中的羟基和羰基除去,从而引起载体结构变化.热重分析结果显示,经等离子体处理后的样品失重量(19%-23%)与未处理样品的失重量(31%)相比差10%左右,这说明采用该方法可以在一定程度上去除纳米金表面保护基团和载体的层间阴离子.用紫外-可见光谱和高角环形暗场像-扫描透射电子显微镜对催化剂中金颗粒的尺寸分布和平均粒径进行分析,发现金颗粒在等离子体处理过后其粒径没有发生严重聚集,平均粒径由未处理时的1.4-1.7 nm轻微长大至2.4-3.7 nm.以含硫醇化合物(半胱氨酸)保护的金原子团簇催化剂为例考察了等离子体不同处理时间的影响,发现随着处理时间从25 min延长至150 min,样品的颜色从浅紫色变为暗紫色.结合XRD和TGA等结果可知,随着处理时间的延长,催化剂中保护基团的去除度逐渐提高.CO氧化反应活性评价结果显示,与未经处理的样品相比,经等离子体处理后的样品催化CO氧化反应活性有明显提高,且随预处理时间延长,活性有提高的趋势.动力学测试结果表明,经等离子体处理后的样品催化CO氧化的表观活化能低至1.2-2.9 k J/mol,接近于文献中报道的Au/TiO_2催化剂.这说明作为一种催化剂处理方法,介质阻挡放电等离子体技术可以有效去除催化剂中的保护剂,且因其处理条件相对温和,可在一定程度上保持金颗粒尺寸的稳定,这对于控制合成负载型小尺寸的金催化剂具有重要意义.     

Au促进Pt/WO3催化甘油氢解制1,3-丙二醇

近年来, 以生物质为基础的生物柴油得到了迅速发展, 导致了粗甘油过剩. 通过甘油选择性氢解制1,3-丙二醇, 进而被用于合成高价值的聚对苯二甲酸丙二醇酯被认为是最具工业应用潜力的反应之一, 对于提高生物柴油的利用效率有着极其重要的意义. 但由于反应空间位阻和热力学上的限制给甘油氢解制1,3-丙二醇带来了很大的挑战, 因此需要设计高活性的金属-酸双功能催化剂以降低甘油第二个C-O键断裂的活化能和减少其他副反应的发生. 目前Pt-W和Ir-Re双功能催化剂可高选择性制得1,3-丙二醇, 但仍需较严苛的反应条件实现对氢气的活化和解离. 本课题组曾将准单原子/单原子Pt高度分散于具有大量氧空位和酸位点的WOx载体上, 十分有利于甘油选择性氢解制1,3-丙二醇反应; 在Au-Pt/WOx催化剂中添加Au可促进B酸产生, 进而提高了甘油转化率和1,3-丙二醇的选择性.为了进一步研究Au对Pt/WOx催化剂结构和催化性能的影响, 本文利用CTAB辅助吸附法制备了Au/WO3, 再浸渍Pt制得Pt/Au/WO3双金属催化剂. 在甘油选择性氢解制1,3-丙二醇反应中, 所制催化剂表现出比Au-Pt/WOx更好的催化活性, 1,3-丙二醇时空收率为0.078 g1,3-PDO/(gcat·h), 是后者的1.95倍. 值得一提的是, Au-Pt/WOx催化剂在低压时活性较高, 而Pt/Au/WO3催化剂活性则在压力的升高而提高; 另外反应温度的升高导致副产物正丙醇的选择性上升, 1,3-丙二醇的选择性降低. 因此, 适宜的反应条件为155℃和5 MPa. 与Pt/WO3和Pt/WOx相比, Pt/Au/WO3表现出了更优异的催化性能, 其1,3-丙二醇的时空收率是Pt/WO3的2.36倍和Pt/WOx的4倍.为了探究Au的掺入对Pt/WOx催化剂性能的影响, 通过XRD, TEM, H2-TPR和XPS等技术对催化剂进行了深入表征. 结果表明, 与Pt/WO3相比, Pt/Au/WO3-600催化剂的XRD衍射峰向小角度偏移, 其原因是Au3+离子半径(0.85 ?)比W6+的(0.60 ?)大, Au3+以取代晶格W6+形式进入WO3晶格中; 对H2-TPR前300 ℃耗氢量的计算可知:Pt/WO3可被还原至Pt/WO2.96, 而Pt/Au/WO3可被还原至Pt/Au/WO2.91. 因此与Pt/WO3相比, Pt/Au/WO3表面氧空位更加丰富. TEM和XPS表征可知, 添加0.1 wt%Au后, 促进了更低价态的Pt均匀分散在WO3载体上, 其平均粒径为2.36 nm.综上所述, Au的掺杂改变了Pt/Au/WO3双金属催化剂的结构, 不仅降低了Pt和W的还原温度, 削弱了Pt和W之间的相互作用, 也促进了更低价态的Pt均匀分散于WO3载体上, 使得Pt/Au/WO3双金属催化剂在甘油氢解制1,3-丙二醇反应中具有更为优异的活性和产物选择性. 该催化剂有望被广泛运用于其他生物质平台化合物加氢脱氧的反应中.     

An efficient process for the synthesis of gem-dinitro compounds under high steric hindrance by nitrosation and oxidation of secondary nitroalkanes

A new nitrosation and oxidation process to synthesize gem-dinitro compounds was accomplished by using nitryl chloride as nitrosation reagent and ozone as oxidizing agent. The main features of the present protocol include the compatibility to substances with high steric hindrance, high yields and mild reaction conditions. A plausible mechanism involving the formation of an intermediate of gem-nitrosonitro compound by means of single electron transfer was also proposed.     

A colorimetric squaraine-based probe and test paper for rapid naked eyes detection of copper ion (II)

A colorimetric probe N,N’-bis(2-methoxy-ethyl)-2,3,3-trimethyl-3H-squaraine (MOESQ) with H₂O solubility was synthesized to detect Cu²⁺. MOESQ exhibits good selectivity, high sensitivity and fast UV-Vis response toward Cu²⁺ over other competing ions in CH₃CN. The detection limit of MOESQ for Cu²⁺ in CH₃CN can reach 1.88?×?10^?7?molL^?1. By adsorbing MOESQ on the chromatography paper, a colorimetric test paper for Cu²⁺ was prepared, which could detect Cu²⁺ with the color change from blue to faint yellow even in the limit of detection concentration of 10^?6?molL^?1.     

A novel fluorescent probe for formaldehyde based-on monomer-excimer conversion and its imaging in live cells

A novel fluorescent probe was developed for formaldehyde, which can be synthesized by one-step Buchwald–Hartwig reaction. When hydrazino-group of probe reacted with formaldehyde, hydrophobic reaction product aggregates into nanoparticles and results in the blue fluorescence due to the monomer-excimer effect. With enough sensitivity, high selectivity, good stability in physiological pH range and excellent biocompatibility, this probe can image formaldehyde in living cells.     

Sensitive and selective fluorescence detection of aqueous uranyl ions using water-soluble CdTe quantum dots

Herein we report a fluorescent method for sensitive and selective detection of uranyl ions using CdTe quantum dots functionalized with mercaptopropionic acid, which the fluorescence of the quantum dots could be quantitatively quenched through electron transfer mechanism. The detection limit of the method was estimated to be 4 nM, less than the maximum allowed content of 130 nM for uranyl in drinking water defined by the U.S. Environmental Protection Agency. Furthermore, the probe was successfully applied in detection of uranyl ions in real samples, demonstrating its potential practical applications for monitoring of uranyl ions in environment.     

A novel and convenient preparation of antibacterial polyacrylonitrile nanofibers via post-modification using nitrile click chemistry and electrospinning

An efficient, novel and convenient method for the synthesis of modified polyacrylonitrile (PAN) with antibacterial property is reported. The modification of PAN was prepared by a nitrile click chemistry reaction with sodium azide (NaN₃) and silver nitrate (AgNO₃) as catalyst to yield antibacterial polymeric materials with 5-vinyltetrazole units. The results showed that 5-vinyltetrazole units had coordinated with silver ion (Ag⁺). Through the electrostatic spinning technology, the post-modification PAN nanofibers (PAN–Ag⁺ nanofibers) were prepared and the fibers were tested for their antimicrobial properties by the bacterial infection experiment. Afterwards, the antibacterial and stable performance of different proportions of silver ions in PAN nanofibers has been compared. The PAN–Ag⁺ nanofibers are characterized for mechanical and thermomechanical properties, structural analysis, appearance characteristics, as well as the antibacterial properties. And the nanofibers exhibit marvelous chemical stability according to the thermogravimetric analysis. When at 800 °C, the PAN decomposed about 60%, while the decomposition of the PAN–Ag⁺s was 40%. Based on the bacterial infection experiment, PAN–Ag⁺ nanofibers’ antibacterial properties were stronger with the increase of silver ions, such as the number of bacteria clone was smaller and the bacteriostatic ring was larger. Hence, with combination of silver ions, the final polymers show strong antimicrobial properties.     

一种新的肉桂酸类化合物的脱羧/甲基化反应

近年来,脱羧反应得到了广泛而深入的研究.肉桂酸类化合物的脱羧串联反应也得到了较多的关注.这类反应一般包括两个过程,自由基加成和羧基的脱去,从而在苯环的侧链引入各种各样的官能团.我们在研究过程中发现,在碳酸钾作为碱,过氧叔丁醇作为氧化剂,以二甲基亚砜（DMSO）/水作为混合溶剂条件下（体积比为1：1）,肉桂酸类衍生物能够转化成苯丙酮类化合物.通过对反应机理的研究,产物中的甲基来自于过氧叔丁醇,反应经过自由基加成和进一步脱羧得到产物.该反应特点是没有用过渡金属盐作为催化剂,并且是在水相中反应,因此符合绿色化学的发展要求.     

5-二乙胺基-2-(吡啶-2’-亚氨甲基)苯酚的合成及其对Zn2+的识别

本文利用2-氨基吡啶与4-二乙胺基水杨醛反应合成了5-二乙胺基-2-(吡啶-2’-亚氨甲基)苯酚(探针L),对其结构进行了表征。在DMSO/Tris(6:4, v/v, pH =7.4)溶液中,探针L高选择性荧光“关-开”识别Zn₂₊,在365 nm紫外灯照射下,由无荧光变成蓝色荧光。实验表明,探针L与Zn₂₊的结合比为1:1,结合常数为2.6×10₃ L. mol_-1,检测限为 9.39×10_-7mol/L,pH适用范围为7-11,并可检测水样中的Zn₂₊。