F:Flammable;
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.
Electrochemically Generated cis-Carboxylato-Coordinated Iron(IV) Oxo Acid-Base Congeners as Promiscuous Oxidants of Water Pollutants
De Sousa, David P.,Miller, Christopher J.,Chang, Yingyue,Waite, T. David,McKenzie, Christine J.
, p. 14936 - 14947 (2017)
The nonheme iron(IV) oxo complex [FeIV(O)(tpenaH)]2+ and its conjugate base [FeIV(O)(tpena)]+ [tpena- = N,N,N′-tris(2-pyridylmethyl)ethylenediamine-N′-acetate] have been prepared electrochemically in water by bulk electrolysis of solutions prepared from [FeIII2(μ-O)(tpenaH)2](ClO4)4 at potentials over 1.3 V (vs NHE) using inexpensive and commercially available carbon-based electrodes. Once generated, these iron(IV) oxo complexes persist at room temperature for minutes to half an hour over a wide range of pH values. They are capable of rapidly decomposing aliphatic and aromatic alcohols, alkanes, formic acid, phenols, and the xanthene dye rhodamine B. The oxidation of formic acid to carbon dioxide demonstrates the capacity for total mineralization of organic compounds. A radical hydrogen-atom-abstraction mechanism is proposed with a reactivity profile for the series that is reminiscent of oxidations by the hydroxyl radical. Facile regeneration of [FeIV(O)(tpenaH)]2+/ [FeIV(O)(tpena)]+ and catalytic turnover in the oxidation of cyclohexanol under continuous electrolysis demonstrates the potential of the application of [FeIII(tpena)]2+ as an electrocatalyst. The promiscuity of the electrochemically generated iron(IV) oxo complexes, in terms of the broad range of substrates examined, represents an important step toward the goal of cost-effective electrocatalytic water purification.
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.
A site-holding effect of TiO2 surface hydroxyl in the photocatalytic direct synthesis of 1,1-diethoxyethane from ethanol
Zhang, Hongxia,Zhang, Wenqin,Zhao, Min,Yang, Pengju,Zhu, Zhenping
, p. 1518 - 1521 (2017)
To understand the mechanism of the photocatalytic direct synthesis of 1,1-diethoxyethane (DEE) from ethanol is vital for enhancing the reaction efficiency. Based on photocatalytic data of different phase TiO2 and F-TiO2 catalysts, radical trapping data, and GC-MS data, we proposed a photocatalytic mechanism for the preparation of both DEE in neat ethanol and 2,3-butanediol (2,3-BD) in ethanol-H2O using photocatalytic methods. In neat ethanol, hydroxyl isn’t involved in the catalytic cyclic process but hydroxyl has an indirect site-holding effect, thus leading to more hydroxyl groups with higher activity. In ethanol-H2O, although the strong oxidant ?OH radical is involved, fewer OH groups lead to higher selectivity of 2,3-BD. The interaction of the reactant/solvent with the surface group of the catalyst is important in the activity and selectivity of photocatalytic reactions. This finding gives fundamental insight into the role of TiO2 surface hydroxyl in the photocatalytic dehydrogenation process of alcohols and opens a promising path to obtaining both high selectivity and high conversion in TiO2-based photocatalytic activity.
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.
TiO2-photocatalytic acceptorless dehydrogenation coupling of primary alkyl alcohols into acetals
Zhang, Hongxia,Zhu, Zhenping,Wu, Yupeng,Zhao, Tianjian,Li, Li
, p. 4076 - 4080 (2014)
Primary alkyl alcohols can be directly converted into acetals and H 2via TiO2-photocatalytic dehydrogenation coupling at room temperature, with no need for any hydrogen acceptors. The reaction follows a tandem process integrating photocatalytic alcohol dehydrogenation and H +-catalytic acetalation, in which the H+ ion catalysts are provided by the alcohol dehydrogenation in real time. This approach exhibits a very high reaction rate and product selectivity, and represents a novel green process for the conversion of primary alkyl alcohols, especially for bio-renewable ethanol and 1-butanol. the Partner Organisations 2014.
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.
Upgrading of Ethanol to 1,1-Diethoxyethane by Proton-Exchange Membrane Electrolysis
Kawaguchi, Daisuke,Ogihara, Hitoshi,Kurokawa, Hideki
, p. 4431 - 4438 (2021)
The direct acetalization of ethanol is a significant challenge for upgrading bioethanol to value-added chemicals. In this study, 1,1-diethoxyethane (DEE) is selectively synthesized by the electrolysis of ethanol using a proton-exchange membrane (PEM) reactor. In the PEM reactor, a Pt/C catalyst promoted the electro-oxidation of ethanol to acetaldehyde. The Nafion membrane used as the PEM served as a solid acid catalyst for the acetalization of ethanol and electrochemically formed acetaldehyde. DEE was obtained at high faradaic efficiency (78 %) through sequential electrochemical and nonelectrochemical reactions. The DEE formation rate through PEM electrolysis was higher than that of reported systems. At the cathode, protons extracted from ethanol were reduced to H2. The electrochemical approach can be utilized as a sustainable process for upgrading bioethanol to chemicals because it can use renewable electricity and does not require chemical reagents (e. g., oxidants and electrolytes).
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.
