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1.
《Mendeleev Communications》2022,32(5):597-600
Calorimetric monitoring of the autoclave reaction N2O4 + C2H4 at –85 to +10 °C under argon pressure 10–30 bar revealed that the exothermic chemical reaction started at temperatures above –52 °C at 10 bar, whereas an intensive exothermic reaction started at –85 °C and pressure of 30 bar. IR study showed that oligo/polynitroethylene was formed at 30 bar, while carbonyl and hydroxy compound as well as nitrate R–ONO2 formation occurred upon processing at 10 bar. 相似文献
2.
Shilin Jiang Dr. Yalan Liu Dr. Lin Wang Prof. Zhifang Chai Prof. Wei-Qun Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201145
The coordination chemistry of f-block elements (lanthanide and actinide) in molten salts has become a resounding topic in view of its great importance to the research and development (R&D) of molten salt reactors and pyroprocessing. In this Review article, a general overview of the coordination chemistry of f-block elements in molten salts is provided including past achievements and recent advances. Particular emphases are placed on the oxidation state, speciation, and solution structure of f-block metal ions in molten salts, as well as their relationships with the salt composition. Furthermore, this review briefly discusses the spectroscopic and theoretical methods that complement each other in revealing the coordination properties. 相似文献
3.
Dr. Zaifa Shi Dr. Yihuang Jiang Dr. Jingxiong Yu Prof. Shanjun Chen Prof. Jun Chen Prof. Zichao Tang Prof. Lansun Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202103546
At present, the reactivity of cyclic alkanes is estimated by comparison with acyclic hydrocarbons. Due to the difference in the structure of cycloalkanes and acycloalkanes, the thermodynamic data obtained by analogy are not applicable. In this study, a molecular beam sampling vacuum ultraviolet photoionization time-of-flight mass spectrometer (MB-VUV-PI-TOFMS) was applied to study the low-temperature oxidation of cyclopentane (CPT) at a total pressure range from 1–3 atm and low-temperature range between 500 and 800 K. Low-temperature reaction products including cyclic olefins, cyclic ethers, and highly oxygenated intermediates (e. g., ketohydroperoxide KHP, keto-dihydroperoxide KDHP, olefinic hydroperoxides OHP and ketone structure products) were observed. Further investigation of the oxidation of CPT – electronic structure calculations – were carried out at the UCCSD(T)-F12a/aug-cc-pVDZ//B3LYP/6-31+ G(d,p) level to explore the reactivity of O2 molecules adding sequentially to cyclopentyl radicals. Experimental and theoretical observations showed that the dominant product channel in the reaction of CPT radicals with O2 is HO2 elimination yielding cyclopentene. The pathways of second and third O2 addition – the dissociation of hydroperoxide – were further confirmed. The results of this study will develop the low-temperature oxidation mechanism of CPT, which can be used for future research on accurately simulating the combustion process of CPT. 相似文献
4.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
5.
Dr. Ruijuan Yao Prof. Di Liu Dr. Huihui Wan Dr. Yongqiang Mei Jiahui Wang Dr. Rui Cai Dr. Huimin Zhang Dr. Yuzhen Zhao Dr. Zemin He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(71):e202202269
By linking the carbazole unit to the nitrogen atom of acridone through phenyl or pyridyl, two compounds, named 10-(4-(9H-carbazol-9-yl)phenyl)acridin-9(10H)-one (AC-Ph-Cz) and 10-(5-(9H-carbazol-9-yl)pyridin-2-yl)acridin-9(10H)-one (AC-Py-Cz) were designed and synthesized. These two materials, characterized with highly twisted and rigid structure, good thermal stability, and balanced carrier-transporting properties, were employed as host materials for green phosphorescent and thermally activated delayed fluorescent organic light-emitting diodes (OLEDs). The carbazole group, despite its small contribution to the highest occupied molecular orbitals (HOMOs) of these two materials, plays an essential role as an intramolecular host in energy delivering and improving the hole transporting ability of these two hosts. The incorporation of the electron-deficient pyridyl group as a linking group slightly improves the electron transporting capability of AC-Py-Cz. The green phosphorescent OLED (PhOLED) based on AC-Py-Cz exhibited excellent device performance with a turn-on voltage of 2.5 V, a maximum power efficiency and an external quantum efficiency (ηext) of 89.8 lm W−1 and 25.2 %, respectively, benefitting from the better charge-balancing ability of AC-Py-Cz host due to the presence of the pyridyl bridge. More importantly, all the devices based on these two hosts showed low efficiency roll-off at high brightness due to the suppressed non-radiative transition in the emitting layer. In particular, the AC-Py-Cz-hosted green PhOLED exhibited an efficiency roll-off of 1.6 % from the maximum next at a high brightness of 1000 cd m−2 and a roll-off of 15.9 % at an extremely high brightness of 10000 cd m−2. This study manifests that acridone-based host materials have great potential in fabricating OLEDs with low efficiency roll-off. 相似文献
6.
Ajit Kumar Singh Seulgi Ji Baghendra Singh Chittaranjan Das Heechae Choi Prashanth W. Menezes Arindam Indra 《Materials Today Chemistry》2022
Herein, we report a Mott-Schottky catalyst by entrapping cobalt nanoparticles inside the N-doped graphene shell (Co@NC). The Co@NC delivered excellent oxygen evolution activity with an overpotential of merely 248 mV at a current density of 10 mA cm–2 with promising long-term stability. The importance of Co encapsulated in NC has further been demonstrated by synthesizing Co nanoparticles without NC shell. The synergy between the hexagonal close-packed (hcp) and face-centered cubic (fcc) Co plays a major role to improve the OER activity, whereas the NC shell optimizes the electronic structure, improves the electron conductivity, and offers a large number of active sites in Co@NC. The density functional theory calculations have revealed that the hcp Co has a dominant role in the surface reaction of electrocatalytic oxygen evolution, whereas the fcc phase induces the built-in electric field at the interfaces with N-doped graphene to accelerate the H+ ion transport. 相似文献
7.
Haruki Inoue Dr. Shin-ichi Naya Atsunobu Akita Dr. Hisashi Sugime Prof. Dr. Hiroaki Tada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(46):e202201653
Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (dAu) at 5.3 nm≤dAu≤8.2 nm. Light irradiation (λex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs. 相似文献
8.
A liquid dewetting method for the determination of the viscoelastic properties of ultrathin polymer films has been extended to study thickness effects on the properties of ultrathin polycarbonate (PC) films. PC films with film thicknesses ranging from 4 to 299 nm were placed on glycerol at temperatures from below the macroscopic glass transition temperature (Tg) to above it with the dewetting responses being monitored. It is found that the isothermal creep results for films of the same thickness, but dewetted at different temperatures can be superposed into one master curve, which is consistent with the fact of PC being a thermorheologically simple material. Furthermore, the results show that the Tg of PC thin films is thickness dependent, but the dependence is weaker than the results for freely standing films and similar to literature data for PC films supported on rigid substrates. It was also found that the rubbery plateau region for the PC films stiffens dramatically, but still less than what has been observed for freely standing polycarbonate films. The rubbery stiffening is discussed in terms of a recently reported model that relates macroscopic segmental dynamics with the stiffening. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1559–1566 相似文献
9.
Two highly ordered isonicotinamide (INA)‐functionalized mesoporous MCM‐41 materials supporting indium and thallium (MCM‐41‐INA‐In and MCM‐41‐INA‐Tl) have been developed using a covalent grafting method. A surface functionalization method has been applied to prepare Cl‐modified mesoporous MCM‐41 material. Condensation of this Cl‐functionalized MCM‐41 with INA leads to the formation of MCM‐41‐INA. The reaction of MCM‐41‐INA with In(NO3)3 or Tl(NO3)3 leads to the formation of MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts. The resulting materials were characterized using various techniques. These MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts show excellent catalytic performance in the selective oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides. Finally, it is found that the anchored indium and thallium do not leach out from the surface of the mesoporous catalysts during reaction and the catalysts can be reused for seven repeat reaction runs without considerable loss of catalytic performance. 相似文献
10.
Zinc polyoxometalate on activated carbon: an efficient catalyst for selective oxidation of alcohols with hydrogen peroxide 下载免费PDF全文
[PW11ZnO39]5? was immobilized on activated carbon and characterized using Fourier transform infrared, X‐ray diffraction, Brunauer–Emmett–Teller and elemental analysis techniques. Effective oxidation of various alcohols with hydrogen peroxide was performed in the presence of this catalyst. Easy separation of the catalyst from the reaction mixture, cheapness, high activity and selectivity, stability as well as retained activity in subsequent catalytic cycles make this supported catalyst suitable for small‐scale synthesis. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献