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71.
Hydrogenation of acetophenone over nano‐Cu/SiO2 catalysts was investigated. The catalysts, prepared by a liquid precipitation method using various precipitating agents, were characterized using low‐temperature nitrogen adsorption, X‐ray diffraction, temperature‐programmed desorption of ammonia, hydrogen temperature‐programmed reduction, transmission electron microscopy and X‐ray photoelectron spectroscopy. It was found that the catalysts prepared by a homogeneous precipitation method had better activity and stability than those prepared by a co‐precipitation method. The catalyst prepared using urea as precipitating agent had well‐dispersed copper species, high surface area and abundant pore structure. The catalytic performance and mechanism of the Cu/SiO2 catalysts were further studied. It was found that the activity and stability of the catalysts could be improved by adjusting the proportion of Cu+/(Cu+ + Cu0). The sample prepared using urea as precipitating agent presented higher activity and selectivity. Also, the catalyst prepared using urea maintained a high catalytic performance while being continuously used for 150 h under the optimal reaction conditions. 相似文献
72.
Yeong‐Tarng Shieh Pei‐Yu Tai Chih‐Chia Cheng 《Journal of polymer science. Part A, Polymer chemistry》2019,57(21):2149-2156
Poly(methyl methacrylate) (PMMA) nanoparticles with a sensitive CO2‐responsive hydrophilic/hydrophobic surface that confers controlled dispersion and aggregation in water were prepared by emulsion polymerization at 50 °C under CO2 bubbling using amphiphilic diblock copolymers of 2‐dimethylaminoethyl methacrylate (DMAEMA) and N‐isopropyl acrylamide (NIPAAm) as an emulsifier. The amphiphilicity of the hydrophobic–hydrophilic diblock copolymer at 50 °C was triggered by CO2 bubbling in water and enabled the copolymer to serve as an emulsifier. The resulting PMMA nanoparticles were spherical, approximately 100 nm in diameter and exhibited sensitive CO2/N2‐responsive dispersion/aggregation in water. Using copolymers with a longer PNIPAAm block length as an emulsifier resulted in smaller particles. A higher concentration of copolymer emulsifier led to particles with a stickier surface. Given its simple preparation and reversible CO2‐triggered amphiphilic behavior, this newly developed block copolymer emulsifier offers a highly efficient route toward the fabrication of sensitive CO2‐stimuli responsive polymeric nanoparticle dispersions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2149–2156 相似文献
73.
Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair
Dr. María Carmona Dr. Joaquina Ferrer Dr. Ricardo Rodríguez Dr. Vincenzo Passarelli Prof. Dr. Fernando J. Lahoz Dr. Pilar García-Orduña Dr. Laura Cañadillas-Delgado Prof. Dr. Daniel Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13665-13670
[Cp*Rh(κ3N,N′,P- L )][SbF6] (Cp*=C5Me5), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H2 and H2O in a reversible manner. When D2O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp3)−H bond activation. 相似文献
74.
We investigate cosmological dark energy models where the accelerated expansion of the universe is driven by a field with an anisotropic universe. The constraints on the parameters are obtained by maximum likelihood analysis using observational of 194 Type Ia supernovae(SNIa) and the most recent joint light-curve analysis(JLA) sample. In particular we reconstruct the dark energy equation of state parameter w(z) and the deceleration parameter q(z). We find that the best fit dynamical w(z) obtained from the 194 SNIa dataset does not cross the phantom divide line w(z) =-1 and remains above and close to w(z)≈-0.92 line for the whole redshift range 0 ≤ z ≤ 1.75 showing no evidence for phantom behavior. By applying the anisotropy effect on the ΛCDM model, the joint analysis indicates that ?_(σ0)= 0.0163 ± 0.03,with 194 SNIa, ?_(σ0)=-0.0032 ± 0.032 with 238 the SiFTO sample of JLA and ?_(σ0)= 0.011 ± 0.0117 with 1048 the SALT2 sample of Pantheon at 1σ′confidence interval. The analysis shows that by considering the anisotropy, it leads to more best fit parameters in all models with JLA SNe datasets. Furthermore, we use two statistical tests such as the usual χ_(min)~2/dof and p-test to compare two dark energy models with ΛCDM model. Finally we show that the presence of anisotropy is confirmed in mentioned models via SNIa dataset. 相似文献
75.
Graphene oxide is a two-dimensional carbon nanomaterial that has risen to prominence over the last decade as graphenes water-dispersible counterpart. This key feature offers tremendous potential in the formation of waterborne hybrid materials, coatings, membranes and adsorbents that make use of its diverse surface chemistry and extraordinary surface area. However, the fundamental colloidal properties of graphene oxide remain incompletely understood, with conflicting reports on how the material's amphiphilic nature and adsorption at interfaces render it surfactant-like or particle-like in nature. In the present work, recent developments in understanding the bulk and interfacial colloidal properties of graphene oxide are explored in the context of its chemistry and system thermodynamics, giving insight into the fundamental question of whether its aqueous behaviour is most accurately described as particle-like, surfactant-like or indeed something entirely different. 相似文献
76.
Jacek Koput 《Journal of computational chemistry》2019,40(21):1911-1918
Accurate structure and potential energy surface of germylene, GeH2, in its ground electronic state 1A1 were determined from ab initio calculations using the coupled-cluster approach in conjunction with the correlation-consistent basis sets up to sextuple-zeta quality. The Born-Oppenheimer equilibrium structural parameters for the 1A1 state are estimated to be re(GeH) = 1.5793 Å and ∠e(HGeH) = 91.19∘. The term value Te for the lowest excited electronic state ã3B1 of GeH2 is predicted to be 9140 cm–1. The vibration-rotation energy levels for the 1A1 state of the 74GeH2, 74GeD2, 72GeH2, and 70GeH2 isotopologues were determined using a variational approach and compared with the experimental data. The role of the core-electron correlation, higher-order valence-electron correlation, scalar relativistic, spin-orbit, and adiabatic effects for prediction of the structure and vibration-rotation dynamics of the GeH2 molecule is discussed. © 2019 Wiley Periodicals, Inc. 相似文献
77.
Recent advances in photocatalysis focus on the development of materials with hierarchical structure and on the surface plasmon resonance (SPR) phenomenon exhibited by metal nanoparticles (NPs). In this work, both are combined in a material where size‐controllable Ag‐NPs are uniformly loaded onto the hierarchical microporous and mesoporous and nanocolumnar structures of ZnO, resulting in Ag‐NP/ZnO nanocomposites. The embedded Ag‐NPs slightly decrease the hydrophobicity of fibrous ZnO, improve its wettability, and increase the absorption of formaldehyde (H2CO) onto the photocatalyst, all of this resulting in excellent photodegradation of formaldehyde in aqueous solution. Besides, we found that Ag‐NPs with optimal size not only accelerate the charge transfer to the surface of ZnO, but also strengthen the SPR effect in the intercolumnar channels of fibrous ZnO particles combining with high concentration of photo‐generated radical species. The micro‐to‐mesoporous ZnO is like a nanoarray packed Ag‐NPs. With Ag‐NPs of diameter 2.5 < ? < 6.5 nm, ZnO exhibits the most superior photodegradation rate constant value of 0.0239 min?1 with total formaldehyde removal of 97%. This work presents a new feasible approach involving highly sophisticated Ag‐NP/ZnO architecture combining the SPR effect and hierarchically ordered structures, which results in high photocatalytic activity for formaldehyde photodegradation. 相似文献
78.
Dr. Xiaoyan Sun Prof. Dr. Shaodong Zhou Dr. Lei Yue Dr. Maria Schlangen Prof. Dr. Helmut Schwarz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(14):3550-3559
Thermal gas-phase reactions of the ruthenium-oxide clusters [RuOx]+ (x=1–3) with methane and dihydrogen have been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. For methane activation, as compared to the previously studied [RuO]+/CH4 couple, the higher oxidized Ru systems give rise to completely different product distributions. [RuO2]+ brings about the generations of [Ru,O,C,H2]+/H2O, [Ru,O,C]+/H2/H2O, and [Ru,O,H2]+/CH2O, whereas [RuO3]+ exhibits a higher selectivity and efficiency in producing formaldehyde and syngas (CO+H2). Regarding the reactions with H2, as compared to CH4, both [RuO]+ and [RuO2]+ react similarly inefficiently with oxygen-atom transfer being the main reaction channel; in contrast, [RuO3]+ is inert toward dihydrogen. Theoretical analysis reveals that the reduction of the metal center drives the overall oxidation of methane, whereas the back-bonding orbital interactions between the cluster ions and dihydrogen control the H−H bond activation. Furthermore, the reactivity patterns of [RuOx]+ (x=1–3) with CH4 and H2 have been compared with the previously reported results of Group 8 analogues [OsOx]+/CH4/H2 (x=1–3) and the [FeO]+/H2 system. The electronic origins for their distinctly different reaction behaviors have been addressed. 相似文献
79.
Novel palladium‐doped nanoparticles have been explored to serve as the first metal oxide‐derived heterogeneous catalyst for Ullmann reaction of chloroarenes under mild condition (34 °C). This heterogeneous catalyst exhibited high catalytic activity towards the Ullmann homocoupling of chloroarenes into a series of useful symmetrically biaryl products with good to excellent yields in the presence of ethanol and NaOH, thereby leading to green and economical Ullmann reaction. The produced nanoparticles were successfully characterized by various techniques including PXRD, XPS, HRTEM, SEM‐EDS, BET, TGA techniques, elemental mapping analysis and ICP‐OES. Interestingly, based on characterization and experimental data, a reasonable mechanism has been proposed. Also, the formation of aryl methyl ketone as a by‐product has been further confirmed by isotopic labelling experiments that the acetyl moiety is derived from ethanol. Moreover, the catalyst was stable and could be easily reused up to 5 times under atmospheric air without suffering significant loss in catalytic activity. 相似文献
80.
Santosh Kumar Sejy Lee Reju George Thomas Seung‐Jea Lee Hong‐Joon Lee In‐Kyu Park Yong Yeon Jeong Tae‐Ho Yoon Dong‐Chan Shin Jae‐Suk Lee 《Journal of polymer science. Part A, Polymer chemistry》2019,57(11):1165-1172
Self‐emulsion polymerization (SEP), a green route developed by us for the polymerization of amphiphilic monomers, does not require any emulsifier or an organic solvent except that the water‐soluble initiators such as 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane]dihydrochloride (VA‐044) and potassium persulfate (KPS) are only used. We report here the polymer nanoscaffolds from a number of amphiphilic monomers, which can be used for in situ encapsulation of a variety of nanoparticles. As a demonstration of the efficacy of these nanoscaffolds, the synthesis of a biocompatible hybrid nanoparticle (nanohybrid), prepared by encapsulating Fe3O4 magnetic nanoparticle (Fe3O4 MNPs) in poly(2‐hydroxyethyl methacrylate) in water, for MRI application is presented. The nanohybrid prepared following the SEP in the form of an emulsion does not involve the use of any stabilizing agent, crosslinker, polymeric emulsifier, or surfactant. This water‐soluble, spherical, and stable nanohybrid containing Fe3O4 MNPs of average size 10 ± 2 nm has a zeta potential value of ?41.89 mV under physiological conditions. Magnetic measurement confirmed that the nanohybrid shows typical magnetic behavior having a saturation magnetization (Ms) value of 32.3 emu/g and a transverse relaxivity (r2) value of 29.97 mM?1 s?1, which signifies that it can be used as a T2 contrast agent in MRI. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 相似文献