Theoretical infrared spectrum of the ethanol hexamer

The hydrogen bond network of ethanol clusters is among the most complex hydrogen bond networks of molecular clusters. One of the reasons of its complexity arises from the number of possible ethanol monomers (there are three isoenergetic isomers of the ethanol monomer). This leads to difficulties in the exploration of potential energy surfaces (PESs) of ethanol clusters. In this work, we have explored the PES of the ethanol hexamer at the MP2/aug-cc-pVDZ level of theory. We have provided structures and their relative stability at 0 K and for temperatures ranging from 20 to 400 K in the gas phase. These structures are used to compute the theoretical infrared (IR) spectrum of the ethanol hexamer at the MP2/aug-cc-pVDZ level of theory. As a result, 98 different structures have been investigated, and six isomers are reported to be the most isoenergetically stable structures of the ethanol hexamer. These isomers are folded cyclic structures in which the stability is enhanced by the implication of CH⋯O interactions. Our investigations show that the PES of the ethanol hexamer is very flat, yielding several isoenergetic structures. Furthermore, we have noted that several isomers contribute to the population of the ethanol hexamer at high temperatures. As far as the IR spectroscopic study is concerned, we have found that the IR spectra of the most stable structures are in good agreement with the experiment. Considering this agreement, these structures are used to assign the experimental peaks in the CH-stretching region. We concluded that the stability of the structures of the ethanol hexamer is related both to OH⋯O hydrogen bonds and CH⋯O interactions. Overall, we have found that the IR spectrum of the ethanol hexamer, calculated from the contribution of all the possible stable structures weighted by their probability, excellently reproduce the experimental spectrum of the ethanol hexamer.     

Direct Catalytic Conversion of Ethanol to C5+ Ketones: Role of Pd–Zn Alloy on Catalytic Activity and Stability

Ethanol can be used as a platform molecule for synthesizing valuable chemicals and fuel precursors. Direct synthesis of C₅₊ ketones, building blocks for lubricants and hydrocarbon fuels, from ethanol was achieved over a stable Pd‐promoted ZnO‐ZrO₂ catalyst. The sequence of reaction steps involved in the C₅₊ ketone formation from ethanol was determined. The key reaction steps were found to be the in situ generation of the acetone intermediate and the cross‐aldol condensation between the reaction intermediates acetaldehyde and acetone. The formation of a Pd–Zn alloy in situ was identified to be the critical factor in maintaining high yield to the C₅₊ ketones and the stability of the catalyst. A yield of >70 % to C₅₊ ketones was achieved over a 0.1 % Pd‐ZnO‐ZrO₂ mixed oxide catalyst, and the catalyst was demonstrated to be stable beyond 2000 hours on stream without any catalyst deactivation.     

Β-d-Xylosidase from Selenomonas ruminantium: Catalyzed Reactions with Natural and Artificial Substrates

Catalytically efficient β-d-xylosidase from Selenomonas ruminantium (SXA) exhibits pK _as 5 and 7 (assigned to catalytic base, D14, and catalytic acid, E186) for k _cat/K _m with substrates 1,4-β-d-xylobiose (X2) and 1,4-β-d-xylotriose (X3). Catalytically inactive, dianionic SXA (D14⁻E186⁻) has threefold lower affinity than catalytically active, monoanionic SXA (D14⁻E186^H) for X2 and X3, whereas D14⁻E186⁻ has twofold higher affinity than D14⁻E186^H for 4-nitrophenyl-β-d-xylopyranoside (4NPX), and D14⁻E186⁻ has no affinity for 4-nitrophenyl-α-l-arabinofuranoside. Anomeric isomers, α-d-xylose and β-d-xylose, have similar affinity for SXA. 4-Nitrophenol competitively inhibits SXA-catalyzed hydrolysis of 4NPX. SXA steady-state kinetic parameters account for complete progress curves of SXA-catalyzed hydrolysis reactions. The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

乙醇在Ni-ZnO-ZrO_2-YSZ阳极SOFC上的发电性能

为考察乙醇用于固体氧化物燃料电池的可行性,用柠檬酸溶胶-凝胶制备阳极催化材料Ni-ZnO-ZrO2,利用机械混合法制备Ni-ZnO-ZrO2-YSZ(Y2O3稳定的ZrO2)阳极。用涂覆法,在YSZ电解质上,制备了Ni-ZnO-ZrO2-YSZ/YSZ/LSM(La0.85Sr0.15MnO3)与Ni-YSZ/YSZ/LSM的单体电池。在不同蒸发器操作温度、电池操作温度和乙醇蒸气流量下,以乙醇为燃料进行发电实验,对两种阳极的电池发电性能进行比较。实验结束后,用SEM检测了两种电池阳极的表面。结果表明,Ni-ZnO-ZrO2-YSZ阳极SOFC的电池输出性能明显高于Ni-YSZ阳极,且Ni-ZnO-ZrO2-YSZ阳极具有较好的抗积炭能力。     

桦甸页岩油柴油馏分加氢精制生产清洁燃料油的研究

柴油馏分(200℃~360℃)在桦甸页岩油中约占41%。其中,硫、氮及不饱和烃含量较高,含硫化合物以苯并噻吩类及二苯并噻吩类化合物为主,而氮化物中的碱性氮化物和非碱性氮化物的含量相当。实验中分别以硫化态的CoMo/Al2O3及NiW/Al2O3为催化剂,利用固定床小型加氢反应装置,考察了不同工艺条件对桦甸页岩油柴油馏分加氢脱硫及加氢脱氮效果的影响。结果表明,反应温度升高,增大反应压力,降低体积空速,对脱硫、脱氮都是有利的,特别是对加氢脱氮影响最为明显,而氢油体积比的影响相对较小。两种催化剂活性比较发现,对于该页岩馏分油而言,两种催化剂的加氢脱硫效果相差不大,而NiW/Al2O3的加氢脱氮效果却明显好于CoMo/Al2O3。在选择的工艺条件下,对桦甸页岩油柴油馏分进行加氢精制得到的产品油中杂原子和不饱和烃含量低,密度小,芳香烃含量少,可作为优质清洁柴油直接使用。     

Ni/Al2O3和Ni/La2O3催化剂上低温乙醇水蒸气重整制氢

 采用浸渍、热分解和氢还原等步骤制备了两种纳米晶载体催化剂Ni/Al2O3和Ni/La2O3,应用X射线衍射、X射线光电子能谱、N2吸附和扫描电镜对催化剂的体相和表面结构进行了测定,采用固定床反应器考察了催化剂对乙醇水蒸气重整制氢反应的催化性能. 实验结果表明, 15.3%Ni/La2O3催化剂对乙醇的低温水蒸气重整反应表现出较高的催化活性和稳定性. 250 ℃时乙醇的转化率已达到80.7%,氢气的选择性为49.5%; 330 ℃时乙醇的转化率达到100%,氢气的选择性可达54.3%. 16.1%Ni/Al2O3催化剂对低温乙醇水蒸气重整反应的催化活性较低.     

新型Pt-Sn/C阳极催化剂对乙醇的电催化氧化性能

 研究了用于直接乙醇燃料电池的自制Pt-Sn/C阳极催化剂对乙醇的电催化氧化性能. 采用直流伏安法和交流阻抗法分析了电池温度和极化电位对乙醇电催化氧化性能的影响,比较了不同温度下甲醇和乙醇通过Nafion 117膜的扩散系数. 结果表明,乙醇通过Nafion 117膜的扩散系数小于甲醇的扩散系数. 伏安法测试结果表明,Pt-Sn/C催化剂对乙醇的催化氧化活性高于商品化的Pt-Ru/C催化剂. 在实验温度范围内,乙醇在Pt-Sn/C催化剂上的初始氧化电位比在Pt-Ru/C催化剂上低约0.2 V; 同一电位下Pt-Sn/C催化剂比Pt-Ru/C催化剂的氧化电流密度高出20～60 mA/cm2,且电流密度的差值随温度的升高而增大. 交流阻抗法测试结果表明,Pt-Sn/C催化剂对乙醇具有更高的催化活性. 在90 ℃下,以1 mol/L的乙醇为燃料,氧气为氧化剂时,Pt-Sn/C催化剂显示出良好的电池性能,电池最高功率密度为44 mW/cm2,而Pt-Ru/C催化剂的电池最高功率密度仅为27 mW/cm2.     

加碱萃取精馏制取无水乙醇

乙醇-水体系存在共沸点,难以通过普通精馏方法制取高纯度乙醇,萃取精馏是分离共沸体系的有效途径。目前常用的萃取溶剂是乙二醇。在分离乙醇-水体系的过程中,将适当的盐类(醋酸钾)溶于乙二醇形成溶盐萃取剂,会有效提高溶剂的选择性。本文用萃取精馏方法并加入乙二醇分离效果更明显。     

Ethanol steam reforming over Ni-Cu/Al2O3-MyOz （M = Si, La, Mg, and Zn） catalysts

Ni-based catalysts doped with copper additives were studied on their role in ethanol steam reforming reaction.The effects of Ca content,support species involving Al2O3-SiO2,Al2O3-MgO,Al2O3-ZnO,and Al2O3-La2O3,on the catalytic performance were studied.Characterizations by TPR,XRD,NH3-TPD,XPS,and TGA indicated that catalysts 30Ni5Cu/Al2O3-MgO and 30NiSCu/Al2O3-ZnO have much higher H2 selectivity than 30NiSCu/Al2O3-SiO2,as well as good coke resistance.H2 selectivity for 30Ni5Cu/Al2O3-MgO catalyst was 73.3% at 450℃ and increased to 94.0% at 600 ℃,whereas for 30NiSCu/Al2O3-ZnO catalyst,the H2 selectivity was 63.6% at 450 ℃ and 95.2% at 600 ℃.These Al2O3-MgO and Al2O3-ZnO supported Ni-Cu bimetallic catalysts may have important applications in the production of hydrogen by ethanol steam reforming reactions.