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1.
Racha Arundhathi Panyala Linga Reddy Chanchal Samanta Bharat L. Newalkar 《RSC advances》2020,10(67):41120
Development of a chromium (Cr)-free hydrogenation catalyst is very important to replace the existing hazardous Cr based catalyst used in the furfural hydrogenation to furfuryl alcohol. Herein, we report synthesis of well-dispersed copper nanoparticles supported on hydrothermally stable magnesium doped alumina (Cu@Mg/γ-Al2O3) for selective hydrogenation of furfural to furfuryl alcohol. The prepared catalyst was characterized by X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Powder X-ray Diffraction (PXRD), Surface Area Analysis (SAA), High Resolution-Transmission Electron Microscopy (HR-TEM), Temperature Programmed Reduction/Desorption (TPR/TPD) and Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) to understand textural properties of the catalyst. The prepared catalyst was found to be highly active and selective with 99% conversion of furfural and 94% selectivity for furfuryl alcohol under solvent free conditions at 443.15 K and 2 MPa of hydrogen pressure. It was also observed that the Cu@Mg/γ-Al2O3 catalyst is reusable (up to six runs) while maintaining its high activity and selectivity (≥94%) in the hydrogenation of furfural to furfuryl alcohol.A catalyst for selective hydrogenation of furfural to furfural alcohol in a solvent free environment. 相似文献
2.
Reduced graphene oxide (rGO) integrated with iron oxide nanoparticles (α-Fe2O3/rGO) composites with different morphologies were successfully obtained through the in situ synthesis and mechanical agitation methods. It was found that the α-Fe2O3 was densely and freely dispersed on the rGO layer. By comparing electrochemical properties, the sheet-like α-Fe2O3/rGO composites demonstrate excellent electrochemical performance: the highest specific capacitance, and excellent cycling stability and rate capacity. The specific capacitance is 970 F g−1 at a current density of 1 A g−1 and the capacitance retention is 75% after 2000 cycles with the current density reaching 5 A g−1. It is mainly due to the synergistic effect between the α-Fe2O3 and rGO, and the high conductivity of the rGO offers a fast channel for the movement of electrons.Preparation of α-Fe2O3/rGO composites for supercapacitor application using in situ synthesis and a mechanical agitation method. 相似文献
3.
In order to effectively clean oily seawater with anionic polyacrylamide (APAM), UiO-66 coated γ-Al2O3 (UA) composites were firstly synthesized using γ-Al2O3 as a template to induce the growth of high hydrophilic UiO-66 on its surface to form a uniform UA self-assembled membrane. The UA composites and self-assembled membrane were characterized and analyzed. Also, the membrane performance was investigated. The results show that the hydrophilicity of particles is enhanced with the water contact angle decreasing from 39.8° (γ-Al2O3 particles) to 26.2° (UA composites) by introducing the UiO-66 coating. Moreover, the UA self-assembled membrane performs attractive water yield and separation performance. The oil concentration in the permeate treated by the first class of UA self-assembled membrane declines apparently from 91.22 to 18.90 mg L−1, while the water yield is as high as 657.89 L m−2 h−1. The reclaimed separation experiments show that the membrane materials could be recycled by calcination at 200 °C and hydraulic cleaning, which gives the material potential application in cleaning oily seawater.The self-assembled membrane manufactured by UA composites exhibits excellent separation performance and water yield in the treatment of oily seawater. 相似文献
4.
Dry reforming of methane (DRM) enables an efficient utilization of two abundant greenhouse gases by converting them into syngas, a versatile feedstock for chemical synthesis. Aiming for high catalyst performance and enhanced coke resistance, different preparation techniques of La-promoted Ni/γ-Al2O3 catalysts for DRM were compared facilitating structure–performance correlations. The studied synthesis techniques comprehend incipient wetness impregnation and co-precipitation as well as alternative techniques such as spray drying. All catalysts were fully characterized before and after reaction by N2-physisorption, XRD, H2-TPR and STEM-EDX elemental mapping. Additionally, a thorough investigation of carbon deposits has been carried out by TGA/DSC and STEM-EDX, respectively. The different preparation techniques led generally to very different physical properties, structure, chemical species and anti-coking properties of the catalyst. However, some catalysts with similar physicochemical characteristics differed in catalytic performance and coking resistance. Superior catalytic performance could be reached for catalysts prepared by spray drying and related to excellent Ni dispersion, strong metal–support interaction and very low coke formation of only 2.7% of the catalyst weight. After 6 h time on stream only minor sintering occurred, with few Ni nanoparticles up to 10 nm.Clear structure-performance correlation for the dry reforming of methane – spray drying for excellent sintering and cocking resistivity. 相似文献
5.
Laurence Ardouin Jamila Ismaili Bernard Malissen Marie Malissen 《The Journal of experimental medicine》1998,187(1):105-116
The pre–T cell receptor (TCR) associates with CD3-transducing subunits and triggers the selective expansion and maturation of T cell precursors expressing a TCR-β chain. Recent experiments in pre-Tα chain-deficient mice have suggested that the pre-TCR may not be required for signaling allelic exclusion at the TCR-β locus. Using CD3-ε– and CD3-ζ/η–deficient mice harboring a productively rearranged TCR-β transgene, we showed that the CD3-γδε and CD3-ζ/η modules, and by inference the pre-TCR/CD3 complex, are each essential for the establishment of allelic exclusion at the endogenous TCR-β locus. Furthermore, using mutant mice lacking both the CD3-ε and CD3-ζ/η genes, we established that the CD3 gene products are dispensable for the onset of V to (D)J recombination (V, variable; D, diversity; J, joining) at the TCR-β, TCR-γ, and TCR-δ loci. Thus, the CD3 components are differentially involved in the sequential events that make the TCR-β locus first accessible to, and later insulated from, the action of the V(D)J recombinase. 相似文献
6.
With calculations based on density-functional theory (DFT) we investigated the adsorption of a single Au atom and a dimer on thin θ-Al2O3(001) films supported on NiAl(100). The interaction of the Au adsorbates with the surface was shown to depend on the thickness of the film. The adsorption energy for an Au atom on θ-Al2O3(001)/NiAl(100) of film thickness ≤four atomic layers was significantly enhanced—over three times that on a bulk θ-Al2O3(001) surface, and accompanied with a shortened Au-oxide bond and an uplifted Au-binding Al. The strong Au-surface interaction involved a decreased work function of θ-Al2O3(001)/NiAl(100) and consequently drove charge to transfer from the substrate to the adsorbed Au atom; the charge was transferred from NiAl, through alumina, on monolayer θ-Al2O3(001)/NiAl(100), but directly from alumina on thicker layers. For an Au dimer, both upright (end-on) and flat-lying (side-on) geometries existed. The flat-lying dimer was preferred on mono- and tri-layer alumina films, having a greater adsorption energy but a weakened Au–Au bond, whereas the upright geometry prevailed for films of other thickness, having a weaker adsorption energy and being less charged, similar to that on a bulk θ-Al2O3(001) surface. The results imply an opportunity to control the properties and morphologies of metal clusters supported on an oxide film by tuning its thickness.The adsorption behavior of a single Au atom and a dimer on thin-film θ-Al2O3(001)/NiAl(100) varies with the thickness of the film. 相似文献
7.
In an attempt to realize the efficient treatment of NOx, a mixed catalyst of Ti3+ self-doped TiO2−x and γ-Al2O3 was constructed by reducing commercial TiO2. The degradation effect on NOx was evaluated by introducing the mixed catalyst into a coaxial dual-dielectric barrier reactor. It was found that the synthesized TiO2−x could achieve considerable degradation effects (84.84%, SIE = 401.27 J L−1) in a plasma catalytic system under oxygen-rich conditions, which were better than those of TiO2 (73.99%) or a single plasma degradation process (26.00%). The presence of Ti3+ and oxygen vacancies in TiO2−x resulted in a relatively narrow band gap, which contributed to catalyzing deeply the oxidation of NOx to NO2− and NO3− during the plasma-induced “pseudo-photocatalysis” process. Meanwhile, the TiO2−x showed an improved discharge current and promoted discharge efficiency, explaining its significant activation effect in the reaction. Reduced TiO2−x could achieve an impressive degradation effect in a long-time plasma-catalysis process, and still maintained its intrinsic crystal structure and morphology. This work provides a facile synthesis procedure for preparing Ti3+ self-doped TiO2−x with practical and scalable production potential; moreover, the novel combination with plasma also provides new insights into the low-temperature degradation of NOx.TiO2−x has a smaller forbidden band width, more abundant Ti3+ and oxygen vacancies, so as to obtain a better and more stable degradation effect of NOx in plasma-catalysis process. 相似文献
8.
Xuan Ge Hang Sun Kun Dong Yanqi Tao Qi Wang Yazhong Chen Genlei Zhang Peng Cui Ye Wang Qinghong Zhang 《RSC advances》2019,9(26):14592
Mechanically mixed γ-Al2O3 and HZSM-5 (Si/Al = 50) with different mass ratio were utilized as support for Cu–Co higher alcohol synthesis catalysts prepared through incipient wetness impregnation. The textural and structural properties were studied using Ar low temperature adsorption and desorption, H2-temperature programmed reduction (H2-TPR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM) and catalytic performance measurements. The results indicated that the mechanically mixed HZSM-5 and γ-Al2O3 supported copper–cobalt catalysts were superior to either γ-Al2O3 or HZSM-5 supported ones with the same metal loading. The results revealed that using HZSM-5 and γ-Al2O3 mechanically mixed benefited the dispersion of metallic phases and stronger synergetic functions between smaller nanoparticles containing copper and/or cobalt, which is essential for HAS from CO hydrogenation. Under working conditions of P = 5.0 MPa, T = 300 °C, V(H2) : V(CO) : V(N2) = 4 : 2 : 1 and GHSV = 7200 mL g−1 h−1, mechanically mixed HZSM-5 and γ-Al2O3 supported catalysts showed higher catalytic activity than those over single support. For CuCo catalysts upon support containing 50.0 wt% HZSM-5 and 50.0 wt% γ-Al2O3, the CO conversion was 21.3% and the C2+ alcohol selectivity was 41.8%.CuCo bimetallic catalysts over the mixed supports showed smaller average particle size, better dispersion of cobalt and copper species, and good activity for higher alcohols synthesis. 相似文献
9.
Many materials used in energy devices or applications suffer from the problem of electron–hole pair recombination. One promising way to overcome this problem is the use of heterostructures in place of a single material. If an electric dipole forms at the interface, such a structure can lead to a more efficient electron–hole pair separation and thus prevent recombination. Here we model and study a heterostructure comprised of two polymorphs of Fe2O3. Each one of the two polymorphs, α-Fe2O3 and ε-Fe2O3, individually shows promise for applications in photoelectrochemical cells. The heterostructure of these two materials is modeled by means of density functional theory. We consider both ferromagnetic as well as anti-ferromagnetic couplings at the interface between the two systems. Both individual oxides are insulating in nature and have an anti-ferromagnetic spin arrangement in their ground state. The same properties are found also in their heterostructure. The highest occupied electronic orbitals of the combined system are localized at the interface between the two iron-oxides. The localization of charges at the interface is characterized by electrons residing close to the oxygen atoms of ε-Fe2O3 and electron–holes localized on the iron atoms of α-Fe2O3, just around the interface. The band alignment at the interface of the two oxides shows a type-III broken band-gap heterostructure. The band edges of α-Fe2O3 are higher in energy than those of ε-Fe2O3. This band alignment favours a spontaneous transfer of excited photo-electrons from the conduction band of α- to the conduction band of ε-Fe2O3. Similarly, photo-generated holes are transferred from the valence band of ε- to the valence band of α-Fe2O3. Thus, the interface favours a spontaneous separation of electrons and holes in space. The conduction band of ε-Fe2O3, lying close to the valence band of α-Fe2O3, can result in band-to-band tunneling of electrons which is a characteristic property of such type-III broken band-gap heterostructures and has potential applications in tunnel field-effect transistors.Electron–hole pair recombination is reduced in heterostructures if used in devices in place of single material. 相似文献
10.
Laura Fisher 《RSC advances》2022,12(10):5937
Expression of concern for ‘Self-assembled membrane manufactured by metal–organic framework (UiO-66) coated γ-Al2O3 for cleaning oily seawater’ by Cunlong Li et al., RSC Adv., 2019, 9, 10702–10714, DOI: 10.1039/C9RA00521H.The following article ‘Self-assembled membrane manufactured by metal–organic framework (UiO-66) coated γ-Al2O3 for cleaning oily seawater’ has been published in RSC Advances.The XRD data shown in Fig. 6b is the same for the UA composites (shown in green) and UiO-66 particles (shown in red), with the exception of two peaks that are not present in the UiO-66 pattern.In Fig. 7a, the panel for 0.03 MPa is a rotated and processed duplicate of the panel for 0.02 MPa.The authors were contacted for comment and asked to provide raw data but have not responded to these concerns. RSC Advances is publishing this Expression of Concern to alert readers to the concerns raised. An Expression of Concern will continue to be associated with the article until we receive conclusive evidence regarding the reliability of the reported data.Laura Fisher11th February 2022Executive Editor, RSC Advances 相似文献
11.
12.
In this work, we are interested in the synthesis of monophosphate α-NaCoPO4, β-NaCoPO4 and γ-NaCoPO4 compounds by mechanochemical method and their characterization by X-ray powder diffraction patterns. These compounds are crystallized in the orthorhombic, hexagonal and monoclinic system, in Pnma, P65 and P21/n space groups, respectively. The optical properties were measured by means of the UV-vis absorption spectrometry in order to deduce the absorption coefficient α and optical band gap Eg. The calculated values of the indirect band gaps (Egi) for three samples were estimated at 4.71 eV, 4.63 eV and 3.8 for compounds α, β and γ, respectively. The Tauc model was used to determine the optical gap energy of the synthesized compounds. Then, the results of the dielectric proprieties measured by varying the frequency are described.In this work, we are interested in the synthesis of monophosphate α-NaCoPO4, β-NaCoPO4 and γ-NaCoPO4 compounds by mechanochemical method and their characterization by X-ray powder diffraction patterns. 相似文献
13.
Xue-Yan Yang Ruizhe Wang Lu Wang Jianjun Li Shuai Mao San-Qi Zhang Nanzheng Chen 《RSC advances》2020,10(48):28902
A novel K2S2O8-promoted C–Se bond formation from cross-coupling under neutral conditions has been developed. A variety of aldehydes and ketones react well using K2S2O8 as the oxidant in the absence of catalyst and afford desired products in moderate to excellent yields. This protocol provides a very simple route for the synthesis of α-phenylseleno carbonyl compounds and α,β-unsaturated carbonyl compounds.K2S2O8-promoted C–Se bond formation from the cross-coupling of C(sp3)–H bond adjacent to carbonyl group with diphenyl diselenide under metal-free conditions.Selenium (Se) is an essential trace mineral nutrient that exerts multiple and complex effects on human health.1 Selenium has been widely applied in a variety of fields such as the organic synthesis, catalysis, agriculture chemistry, materials science and even the environment protection.2 Se-containing compounds have attracted vast interest because of their extensive bioactive functions and important roles in chemical reactions.3 As metabolites of Se in humans, phenylseleno (–SePh) groups are extremely important.4 It has been reported that SePh-containing compounds can act as redox agents suitable for targeting cancer cells or play a role in steroid chemistry. Several reported SePh-containing compounds that imitate glutathione peroxidase, like ebselen,5 that act as redox agents suitable for targeting cancer cells (naphthoquinone derivatives)6 or are important in steroid chemistry (estrogen derivatives)7 are shown in Fig. 1. Furthermore, α-phenylseleno carbonyl compounds have a special place since these substances also serve as versatile intermediates in organic synthesis.8 They can be converted into the corresponding synthetically useful α,β-unsaturated aldehydes or ketones through oxidation by H2O2 or NaIO4 followed by selenoxide elimination9 and Sahani''s group has used α-phenylselanyl ketones as substrates to obtain α-arylated ketones through organic photoredox catalysis.10Open in a separate windowFig. 1Examples of Se-containing biologically active compounds.Oxidative functionalization of carbonyl compounds has been known since 1935 (ref. 11) and was studied further by Saegusa, Mislow, Baran and others.12 While there generally exist various means, either direct or indirect, of accessing particular target molecules, in order to continue to advance this field, we must constantly study more efficient and green methods. Currently, several procedures have been developed for the preparation of α-phenylseleno aldehydes and ketones. One typical method to synthesize such compounds is by using an enolate coupling reaction.13 This approach suffers from the use of a stoichiometric amount of a strong base and metal oxidant to produce the enolate followed by an oxidative coupling reaction (see Scheme 1). In 2015, Yan''s group demonstrated that with the participation of a suitable oxidant, ketones can undergo direct oxidation functionalization.14 Despite the improvement of not using strong base, it still needed multiple times the amount of metal-free oxidants. In addition, K2S2O8 was found to be a useful oxidant in oxidative reactions because of its characteristics of easy availability, good stability, and low toxicity. Thus, studies focusing on the development of K2S2O8-mediated oxidative reactions meet the requirement of sustainable chemistry.15 Based on our research on the functionalization of the C(sp3)–H bond, and in connection to our continued interest in developing efficient metal-free functionalization strategies,16 herein we report an efficient K2S2O8-mediated C–Se bond formation for the synthesis of α-phenylseleno carbonyl compounds.Open in a separate windowScheme 1Synthesis of α-phenylseleno carbonyl compounds (M = metal).Initially, we utilized acetone (1a) as a standard substrate to evaluate the coupling of C(sp3)–H bonds adjacent to a carbonyl group with diphenyl diselenide (2). Treatment of 1a with 1.0 equiv. of (NH4)2S2O8 in DMSO at 80 °C under air for 3 h afforded the desired product 3a in 29% yield (17 Then various reaction parameters were screened, including the oxidant, solvent, and temperature. A range of oxidants such as PhI(OAc)2, IBX, Ag2O, Na2S2O8, K2S2O8, and oxone were tested, and K2S2O8 showed the highest efficiency (entries 2–7). The solvent also played a key role in this transformation. The product yield decreased when DMSO was replaced by DMF, DMA, CH3CN or EtOH (entries 8–11). Taking the place of air with argon, the reaction gave the desired product 3a in a similar yield (87%) (entry 12). Notably, a similar yield of 3a was obtained by lowering the amount of K2S2O8 to 0.5 equiv. (entry 13). However, a further decrease of the oxidant amount resulted in a lower yield of 3a (entry 14). The reaction temperature had little influence on the reaction efficiency, and 80 °C was still the best choice (entries 15 and 16). A control experiment revealed that K2S2O8 was necessary for the success of this reaction (entry 17).Optimization of the reaction conditionsa,b
Open in a separate windowaReaction conditions: 1a (0.5 mmol), 2 (0.25 mmol), oxidant, solvent (2 mL), under air atmosphere.bIsolated yield based on 1.cn.r. = no reaction.dUnder argon (1 atm) atmosphere.eYield on a 5 mmol scale is given in parentheses.fRoom temperature.With optimized reaction conditions in hands, we evaluated the scope of the reactions with a variety of ketones. A wide range of acyclic (
Entry | Oxidant (equiv.) | Solvent | Temp (°C)/time (h) | Yieldb (%) |
---|---|---|---|---|
1 | (NH4)2S2O8 (1) | DMSO | 80/3 | 29 |
2 | PhI(OAc)2 (1) | DMSO | 80/6 | <5 |
3 | IBX (1) | DMSO | 80/6 | <5 |
4 | Ag2O (1) | DMSO | 80/6 | n.r.c |
5 | Na2S2O8 (1) | DMSO | 80/3 | 70 |
6 | K2S2O8 (1) | DMSO | 80/3 | 93 |
7 | Oxone | DMSO | 80/6 | n.r. |
8 | K2S2O8 (1) | DMF | 80/3 | 52 |
9 | K2S2O8 (1) | DMA | 80/3 | 67 |
10 | K2S2O8 (1) | MeCN | 80/3 | <5 |
11 | K2S2O8 (1) | EtOH | 80/6 | <5 |
12d | K2S2O8 (1) | DMSO | 80/3 | 87 |
13 | K 2 S 2 O 8 (0.5) | DMSO | 80/3 | 90 (92) e |
14 | K2S2O8 (0.3) | DMSO | 80/12 | 50 |
15 | K2S2O8 (0.5) | DMSO | 40/8 | 85 |
16 | K2S2O8 (0.5) | DMSO | r.t./12f | 88 |
17 | — | DMSO | 80/6 | n.r. |