105-57-7Relevant articles and documents
Application of Microwave Heating Techniques for Dry Organic Reactions
Alloum, Abdelkrim Ben,Labiad, Bouchta,Villemin, Didier
, p. 386 - 387 (1989)
A commercially available microwave oven operating at 2450 MHz has been used for activation of organic compounds adsorbed on inorganic solids.
Photocatalytic Reaction of Ethanol over Titanium Diselenide
Iseda, Kozo,Osaki, Toshihiko,Taoda, Hiroshi,Yamakita, Hiromi
, p. 1038 - 1042 (1993)
A suspension of TiSe2 in ethanol was illuminated with ultraviolet light in an atmosphere of Ar, air, or O2 at 298 K.The main products were acetaldehyde, acetaldehyde diethyl acetal (acetal), acetic acid, water, hydrogen, ethylene, methane, and carbon dioxide.Each yield of the products under air or O2 was higher than under Ar, except for that of hydrogen and ethylene.Platinum under an O2 atmosphere exerted its effect for producing CH3COOH, acetal, CO2, CH3CHO, CH4, and H2O, while under Ar it contributed to generating CO2, CH4, and H2.No effect of Pt was observed for generating C2H4 under either an atmosphere of Ar or O2.
Visible-Light Direct Conversion of Ethanol to 1,1-Diethoxyethane and Hydrogen over a Non-Precious Metal Photocatalyst
Chao, Yuguang,Zhang, Wenqin,Wu, Xuemei,Gong, Nana,Bi, Zhihong,Li, Yunqin,Zheng, Jianfeng,Zhu, Zhenping,Tan, Yisheng
, p. 189 - 194 (2019)
Converting renewable biomass and their derivatives into chemicals and fuels has received much attention to reduce the dependence on fossil resources. Photocatalytic ethanol dehydrogenation–acetalization to prepare value-added 1,1-diethoxyethane and H2 was achieved over non-precious metal CdS/Ni-MoS2 catalyst under visible light. The system displays an excellent production rate and high selectivity of 1,1-diethoxyethane, 52.1 mmol g?1 h?1 and 99.2 %, respectively. In-situ electron spin resonance, photoluminescence spectroscopy and transient photocurrent responses were conducted to investigate the mechanism. This study provides a promising strategy for a green application of bioethanol.
Photocatalytic direct conversion of ethanol to 1,1- diethoxyethane over noble-metal-loaded TiO2 nanotubes and nanorods
Zhang, Hongxia,Wu, Yupeng,Li, Li,Zhu, Zhenping
, p. 1226 - 1231 (2015)
As one of the most important biomass platform molecules, ethanol needs to have its product chain chemically extended to meet future demands in renewable fuels and chemicals. Additionally, chemical conversion of ethanol under mild and green conditions is still a major challenge. In this work, ethanol is directly converted into 1,1-diethoxyethane (DEE) and H2 under mild photocatalytic conditions over platinum-loaded TiO2 nanotubes and nanorods. The reaction follows a tandem dehydrogenation-acetalization mechanism, in which ethanol is first dehydrogenated into acetaldehyde and H+ ion by photogenerated holes, and then acetalization between acetaldehyde and ethanol proceeds through promotion by H+ ions formed in real time. Excess H+ ions are simultaneously reduced into H2 by photogenerated electrons. This photocatalytic process has a very high reaction rate over nanosized tubular and rod-like TiO2 photocatalysts, reaching 157.7 mmol g-1 h-1 in relatively low photocatalyst feeding. More importantly, the reaction is highly selective, with a nearly stoichiometric conversion of reacted ethanol into DEE. This photocatalytic dehydrogenation C-O coupling of ethanol is a new green approach to the direct efficient conversion of ethanol into DEE and provides a promising channel for sustainable bioethanol applications.
One Nanometer PtIr Nanowires as High-Efficiency Bifunctional Catalysts for Electrosynthesis of Ethanol into High Value-Added Multicarbon Compound Coupled with Hydrogen Production
Chao, Yuguang,Gu, Lin,Guo, Shaojun,Li, Hongbo,Li, Menggang,Lu, Shiyu,Lv, Fan,Tao, Lu,Yin, Kun,Zhang, Qinghua,Zhang, Weiyu
, p. 10822 - 10827 (2021)
The electrosynthesis of high-value-added multicarbon compounds coupled with hydrogen production is an efficient way to achieve carbon neutrality; however, the lack of effective bifunctional catalysts in electrosynthesis largely hinders its development. Herein, we report the first example on the highly efficient electrosynthesis of high-value-added 1,1-diethoxyethane (DEE) at the anode and high-purity hydrogen at the cathode using 1 nm PtIr nanowires (NWs) as the bifunctional catalysts. We demonstrate that the cell using 1 nm PtIr nanowires as the bifunctional catalysts can achieve a reported lowest voltage of 0.61 V to reach the current density of 10 mA cm-2, much lower than those of the Pt NWs (0.85 V) and commercial Pt/C (0.86 V), and also can have the highest Faraday efficiencies of 85% for DEE production and 94.0% for hydrogen evolution in all the reported electrosynthesis catalysts. The in situ infrared spectroscopy study reveals that PtIr NWs can facilitate the activation of O-H and C-H bonds in ethanol, which is important for the formation of acetaldehyde intermediate, and finally DEE. In addition, the cell using PtIr NWs as bifunctional catalysts exhibits excellent stability by showing almost no obvious decrease in the Faraday efficiency of the DEE production.
A Strategy for the Simultaneous Synthesis of Methallyl Alcohol and Diethyl Acetal with Sn-Β
Hu, Wenda,Wan, Yan,Zhu, Lili,Cheng, Xiaojie,Wan, Shaolong,Lin, Jingdong,Wang, Yong
, p. 4715 - 4724 (2017)
A new strategy was developed to simultaneously produce two important chemicals, namely, methallyl alcohol (Mol) and diethyl acetal (Dal) from methacrolein in ethanol solvent at low temperature with the use of Beta zeolites modified by tin (Sn-β catalysts). All the Sn-β catalysts were prepared by the solid-state ion-exchange method, wherein the calcination step was conducted under different gas atmospheres. The catalyst precalcined in Ar (Sn-β-Ar) had a reduced number of extra-framework Sn species and enabled more Sn species to be exchanged into the framework as isolated tetrahedral SnIV, enhancing the catalytic activity of the Meerwein–Ponndorf–Verley (MPV) reaction. The sodium-exchanged Sn-β-Ar, with a reduced number of weak Br?nsted acid sites, led to an even better selectivity for Mol, owing to the restriction of the side reactions such as acetalization, addition, and etherification. Under optimized catalyst and reaction conditions, the yield of Mol and Dal reached approximately 90 % and 96 %, respectively. The possible reaction pathways, along with a complex network of side products, was proposed after a detailed investigation through the use of different substrates as reactants. The fine-tuning of Sn-β catalysts through different treatments discussed in this work is of great significance toward the understanding and manipulation of complex reactions between α,β-unsaturated aldehydes and primary alcohols.
The role of oxide location in HMF etherification with ethanol over sulfated ZrO2 supported on SBA-15
Barbera,Lanzafame,Pistone,Millesi,Malandrino,Gulino,Perathoner,Centi
, p. 19 - 32 (2015)
The etherification of 5-hydroxymethyl-2-furfural (HMF) over ZrO2 and sulfated ZrO2-SBA-15 was chosen as a case study to analyze (i) the quantitative relationship between the concentration of Lewis and Bronsted acid sites and the catalytic behavior in the above reaction, which is also of industrial relevance for the production of biodiesel additives, and (ii) how the location of zirconia nanoparticles inside or outside the mesoporous channels of SBA-15 could significantly influence the specific reactivity in this reaction, both before and after sulfation. Depending on the loading of zirconia (about 10 or 35 wt%), the characterization data by different techniques (TEM, XRD, BET, Dr-UV-vis, and XPS) agree in indicating that zirconia is located predominantly outside the mesoporous channels as small zirconia nanoparticles for the lower loading, and predominantly inside the mesoporous channels for the higher loading. The concentration of medium-strong Lewis and Bronsted acid sites were determined by pyridine chemisorption monitored by IR spectroscopy. While the concentration of Bronsted acid sites (formed after sulfation) is linearly dependent on the amount of zirconia in SBA-15, a marked deviation is observed for Lewis acid sites. The same conclusion was derived from analysis of the dependence of the catalytic activity in Lewis- or Bronsted-acid-site-promoted reactions. The analysis of these results indicated that the characteristics of the zirconia nanoparticles deposited outside or inside the mesoporous silica channels differ in terms of acid features and in turn of catalytic reactivity.
Meadows,Darwent
, p. 1015 (1952)
(V)/Hydrotalcite, (V)/Al2O3, (V)/TiO2 and (V)/SBA-15 catalysts for the partial oxidation of ethanol to acetaldehyde
Hidalgo,Ti?ler,Kubi?ka,Raabova,Bulanek
, p. 178 - 189 (2016)
Vanadium-based catalysts have been investigated in the partial oxidation of ethanol to acetaldehyde with the aim of understanding relationship between vanadium structure and acetaldehyde productivity. Hydrotalcite, Al2O3, TiO2 and SBA-15 with and without a 5% of vanadium content were prepared to study the oxidative dehydrogenation of ethanol. They were characterized by XRF, TPR (H2), NH3-TPD, CO2-TPD, RAMAN, UV-vis, Nitrogen physisorption, XRD and SEM. The most easily reducible catalysts (as determined by TPR) were the most active ones. In the low temperature region (150 °C), the most active catalyst was the V/TiO2 which presented stable activity in the production of acetaldehyde up to TOS = 200 h. On the contrary, in the high temperature region (250 °C), the most active catalyst was the V/Al2O3catalyst. The most promising result was obtained over V/TiO2 catalyst that afforded a total ethanol conversion of 60.4%wt. and a selectivity to acetaldehyde of 76.2%wt. at TOS = 164 h and T = 150 °C. Also, hydrotalcite was tested for the first time for this type of reaction providing a conversion lower than 7%wt. with a selectivity of 100%wt. to acetaldehyde at T = 150-225 °C.
P-Benzoquinone adsorption-separation, sensing and its photoinduced transformation within a robust Cd(II)-MOF in a SC-SC fashion
Yang, Fan,Liu, Qi-Kui,Wu, Dan,Li, An-Yan,Dong, Yu-Bin
, p. 7443 - 7446 (2015)
p-Benzoquinone (Q) adsorption-separation, sensing and its photoinduced transformation within a robust Cd(ii)-MOF (1) is reported. All the adsorption, sensing and photochemical reactions are directly performed on the single-crystals of 1. This journal is
Efficient synthesis of 1,1-diethoxyethane via sequential ethanol reactions on silica-supported copper and H-Y zeolite catalysts
He, Xiaohui,Liu, Haichao
, p. 133 - 139 (2014)
1,1-Diethoxyethane (DEE) is an important chemical with versatile applications. Here, we report the efficient synthesis of DEE via two-sequential reactions of ethanol including the selective dehydrogenation of ethanol to acetaldehyde and the subsequent acetalization of acetaldehyde with ethanol to DEE. The ethanol dehydrogenation was examined on Cu catalysts supported on SiO2, Al2O3, ZrO2 and TiO 2 supports with similar Cu dispersions, and Cu/SiO2 was more selective to acetaldehyde with 99.0% selectivity at 493 K, due to the inert surface of SiO2, compared to the other three oxide supports with stronger acidity and basicity facilitating the side reactions of acetaldehyde. For the equilibrium-limited acetalization reaction, comparison of representative solid acids (e.g. SO42-/ZrO2, Amberlyst 15, H-Y zeolite and AlCl3/SiO2) showed that while they offered nearly 100% DEE selectivities, the Br?nsted acid sites were more active than the Lewis acid sites. This was confirmed by the higher activities (normalized per acid site) for the H-Y zeolites with higher factions of the Br?nsted acid sites obtained by calcination at lower temperatures in the range 773-1073 K. Combination of the ethanol dehydrogenation on Cu/SiO 2 at 493 K and the acetalization reaction on H-Y (calcined at 773 K) at 293 K in the two-sequential flow microreactors led to the steady conversion of ethanol to DEE in a yield of as high as 35.0%. This yield could be further improved, for example, to 70.5%, the highest yield from ethanol reported to date, after removal of water in the acetalization reactor by 3A zeolite. Such two-sequential reactor configuration also applied to the efficient synthesis of other important acetals, and as an example, dimethoxymethane was synthesized directly from methanol in a yield of 84.1% on iron molybdate and H-ZSM-5 catalysts.
Chemical interconversions in the system Tp Zn/CO2/alcohol [Tp = substituted tris(pyrazolyl)borate]
Ruf, Michael,Schell, Friedrich Alexander,Walz, Rainer,Vahrenkamp, Heinrich
, p. 101 - 104 (1997)
The zinc hydroxide complexes Tp*Zn-OH with TpCum,Me = tris(3-cumenyl-5-methylpyrazolyl)borate and TptBu,Me = tris(3-tert-butyl-5-methylpyrazolyl)borate can be converted to the alkyl carbonate complexes Tp*Zn-OCOOR by reaction with dialkyl dicarbonates or with alcohol and CO2. An alternative formation reaction is the treatment of the pyrazolyl borate with zinc perchlorate and potassium carbonate in alcohol. The interconversion between TpCum,MeZn-OH and TpCum.MeZn_OCOoMe in methanol-containing solution can be repeatedly performed in both directions by bubbling either CO2 or N2 through the solution. The alkyl carbonate complexes show a variable sensitivity towards hydrolytic destruction with reformation of the hydroxide complexes. The complexes TptBu,MeZn-OCOOR (R = Me, Et) release CO2 under high vacuum to form the alkoxide complexes TptBU,Me-Zn-OR, which could not be obtained pure due to their extreme water sensitivity. Indirect evidence for their existence is also obtained by the reaction between TpCum,MeZnOCOOMe and methyl iodide, forming TpCum,MeZn-I and dimethyl ether. The zinc hydroxide complexes catalyse the formation of diethyl carbonate from ethanol and CO2. VCEI Verlagsgcsellschaft mbH.
Making H2 from light and biomass-derived alcohols: The outstanding activity of newly designed hierarchical MWCNT/Pd@TiO2 hybrid catalysts
Beltram,Melchionna,Montini,Nasi,Fornasiero,Prato
, p. 2379 - 2389 (2017)
Hydrogen evolution is among the most investigated catalytic processes given the importance of H2 from an industrial and an energy perspective. Achieving H2 production through green routes, such as water splitting or more realistically photoreforming of alcohols, is particularly desirable. In this work, we achieve a remarkable H2 productivity through photoreforming of either ethanol or glycerol as a sacrificial electron donor by employing a hybrid nanocatalyst where the properties of multi-walled carbon nanotubes (MWCNTs), Pd nanoparticles and crystalline TiO2 are optimally merged through appropriate engineering of the three components and an optimised synthetic protocol. Catalysts were very active both under UV (highest activity 25 mmol g-1 h-1) and simulated solar light (1.5 mmol h-1 g-1), as well as very stable. Critical to such high performance is the intimate contact of the three phases, each fulfilling a specific task synergistically with the other components.
REACTIONS OF ALIPHATIC ALDEHYDES AND ALCOHOLS CATALYZED BY A GIANT PALLADIUM CLUSTER
Zagorodnikov, V. P.,Vargaftik, M. N.
, p. 2457 (1985)
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Selective Formation of Acetal by Photooxidation of Ethanol over Silica-supported Niobium Oxide Catalysts
Tanaka, Tsunehiro,Takenaka, Sakae,Funabiki, Takuzo,Yoshida, Satohiro
, p. 809 - 812 (1994)
UV-irradiation of silica-supported niobium oxide suspended in liquid ethanol under atmospheric oxygen led to the selective production of 1,1-diethoxyethane.The absence of oxygen or UV-irradiation with wavelengths of λ > 320 nm remarkably suppressed the reaction.The activity normalized to the number of niobium ions suggests that the active site is highly dispersed niobate species.Ethanal is the primary product of the photooxidation and 1,1-diethoxyethane is formed by acid catalysis.
Reaction of 1-alkoxy-1-haloalkanes with orthoformic esters [3]
Gazizov,Pudovik,Gazizov,Karimova,Khairullin,Romakhin,Nikitin
, p. 1488 - 1489 (2002)
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Improving the selectivity to C4 products in the aldol condensation of acetaldehyde in ethanol over faujasite zeolites
Zhang, Lu,Pham, Tu N.,Faria, Jimmy,Resasco, Daniel E.
, p. 119 - 129 (2015)
The selective conversion of acetaldehyde to C4 products, minimizing the production of secondary (C6, C8) condensation products, could be a potential path in the production of butadiene from ethanol, a process of commercial interest. Therefore, we have investigated the selective aldol condensation of acetaldehyde in liquid phase over faujasite zeolites, NaX and NaY. Specifically, we have examined the influence of the number and location of the exchangeable cations, type of cations, and post-synthesis treatments on product selectivity. At 230 °C, NaY results in higher C4/(C6 + C8) product ratio than NaX, which can be explained in terms of the strength, density, and accessibility of basic sites, which are less favorable in NaX than NaY. In fact, the CO2 TPD measurements indicate the presence of three types of basic sites of varying strength, of which those with weak and medium strength are most important for the selective condensation. A confinement effect is observed when adding K to the NaY zeolite. The observed selectivity changes suggest that when larger cations partially occupy the supercages, the production of C8 products decreases, while C6 products increase. Also, post-synthesis washing treatments show significant variations in selectivity, which demonstrate the effects of partial occupation of the zeolite pores in the reaction. It is also shown that at a given conversion, the C4/(C6 + C8) ratio can be adjusted by modifying the micro/mesoporosity balance in the zeolite.
Photocatalytic ethanol to H2 and 1,1-diethoxyethane by Co(II) diphenylphosphinate/TiO2 composite
Li, Aihong,Li, Dongyang,Mao, Jianwei,Ge, Zhimeng,Guo, Jianping,Liu, Bo
, (2021)
Through a facile solvothermal method, the novel composites of cobalt(II) diphenylphosphinate/TiO2 have been synthesized and used for photocatalytic hydrogen production in ethanol solution. The chemical composition and surface morphology were an
Reactions of palladium(i) carbonylacetate cluster with alcohols
Chernysheva,Stromnova,Vargafiik,Moiseev
, p. 2327 - 2330 (1996)
Reactions of a telranuclear palladium cluster (Pd(CO)(OAc)l4 with C,-Cj alcohols have been found to proceed simultaneously via several routes to form CO? and dialkyl carbonates, the products of oxidation of coordinated CO ligands, along with carbonyl compounds which form due to oxidation of the corresponding alcohols. Alkoxy, alkoxycarbonyl, and acyl palladium derivatives are shown to be the intermediates of the reactions studied.
Effect of SSIE structure of Cu-exchanged β and Y on the selectivity for synthesis of diethyl carbonate by oxidative carbonylation of ethanol: A comparative investigation
Zhang, Pingbo,Huang, Shouying,Yang, Yang,Meng, Qingsen,Wang, Shengping,Ma, Xinbin
, p. 202 - 206 (2010)
Cu-exchanged β and Y catalysts were investigated by oxidative carbonylation of ethanol in the gas-phase reaction. Cuβ catalyst has shown better catalytic selectivity for oxidative carbonylation of ethanol to diethyl carbonate (DEC), without the principal by-product 1,1-diethoxyethane (DEE) for CuY catalysts. In order to investigate the effect of zeolite structure on the selectivity for products, computational analysis of molecular dimensions and diffusion parameters of DEC and DEE within Cuβ and CuY catalysts zeolite framework has been performed using molecular mechanics and quantum mechanics methods. The computational analysis results are in good agreement with the experimental results to some extent. DEC having a kinetic diameter of 3.663 A? and the lowest energy barrier was formed preferentially over both zeolites. However, the DEE molecule was not detected among the products over Cuβ because of its greater kinetic diameter 6.059 A? and higher energy barrier. The special architecture of β zeolite did not allow the diffusion of DEE molecules through its pores. The formation of the higher sterically hindered DEE over CuY catalyst could be explained by involvement of the outer surface.
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von Sonntag et al.
, p. 4333,4334-4339 (1972)
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Oxygen-implanted MoS2 nanosheets promoting quinoline synthesis from nitroarenes and aliphatic alcohols via an integrated oxidation transfer hydrogenation-cyclization mechanism
Gao, Zhuyan,Huang, Zhipeng,Lu, Jianmin,Mu, Junju,Ren, Puning,Su, Kaiyi,Wang, Feng,Zhang, Chaofeng,Zhang, Shichao
supporting information, p. 1704 - 1713 (2022/03/08)
We herein report that MoS2 with oxygen-implanting modification (O-MoS2) can work as a multifunctional catalyst to achieve the one-pot quinoline synthesis from basic nitroarenes and aliphatic alcohols. Different from common knowledge that the application of MoS2-based catalysts and above quinoline synthesis need anaerobic conditions, we conduct the heterogeneous catalysis under an unusual air atmosphere. Catalyst characterization and experimental results indicate that the MoOx clusters implanted in the MoS2 skeleton, not the coordinatively unsaturated Mo sites (CUS Mo), dominate the generation of quinolines. By overturning the catalysis perception that O2 adsorption on MoSx can deactivate the MoS2-based catalysts using an efficient method for in situ healing of the MoOx structure in O-MoS2 and protecting the O-MoS2 catalyst by inhibiting unwanted MoOx elimination with extra H*, we innovatively introduce O2 into the quinoline synthesis. The robust O-MoS2 can be consecutively used ten times without regeneration and it offers 69-75% yields of 2-methylquinoline from nitrobenzene and ethanol. Furthermore, different from the traditional transfer hydrogenation-condensation mechanism, an integrated oxidation-transfer hydrogenation-cyclization mechanism is proposed over the O-MoS2 catalyst.