Gas-Phase Oxidation of Aqueous Ethanol by Nanoparticle Vanadia/Anatase Catalysts

The gas-phase oxidation of aqueous ethanol with dioxygen has been examined with a new nanoparticle V₂O₅/TiO₂ catalyst. Product selectivity could to a large extent be controlled by small alterations of reaction parameters, allowing production of acetaldehyde at a selectivity higher than 90%, near quantitative conversion at 175–200 °C. Furthermore, a selectivity above 80% for acetic acid could be achieved at low gas hourly space velocity at temperatures as low as 165 °C.     

Selective Oxidation of Benzyl-Alcohol over Biomass-Supported Au/Pd Bioinorganic Catalysts

We report a novel biochemical method based on the sacrificial hydrogen strategy to synthesise bimetallic Au/Pd nanoparticles supported on bacterial cells. The synergistic effect of Au/Pd over monometallic preparations was demonstrated in the oxidation of benzyl alcohol. The bioinorganic catalysts outperformed a commercial Pd catalyst (5% Pd/C) showing no deactivation and high selectivity towards benzaldehyde.     

Low temperature CO oxidation over Au/TiO2 and Au/SiO2 catalysts

After a high-temperature reduction (HTR) at 773 K, TiO₂-supported Au became very active for CO oxidation at 313 K and was an order of magnitude more active than SiO₂-supported Au, whereas a low-temperature reduction (LTR) at 473 K produced a Au/TiO₂ catalyst with very low activity. A HTR step followed by calcination at 673 K and a LTR step gave the most active Au/TiO₂ catalyst of all, which was 100-fold more active at 313 K than a typical 2% Pd/Al₂O₃ catalyst and was stable above 400 K whereas a sharp decrease in activity occurred with the other Au/TiO₂ (HTR) sample. With a feed of 5% CO, 5% O₂ in He, almost 40% of the CO was converted at 313 K and essentially all the CO was oxidized at 413 K over the best Au/TiO₂ catalyst at a space velocity of 333 h^–1 based on CO + O₂. Half the chloride in the Au precursor was retained in the Au/TiO₂ (LTR) sample whereas only 16% was retained in the other three catalysts; this may be one reason for the low activity of the Au/TiO₂ (LTR) sample. The reaction order on O₂ was approximately 0.4 between 310 and 360 K, while that on CO varied from 0.2 to 0.6. The chemistry associated with this high activity is not yet known but is presently attributed to a synergistic interaction between gold and titania.     

Influence of Reactor Configuration on the Selective Oxidation of Glycerol over Au/TiO2

The oxidation of glycerol by molecular oxygen in the aqueous phase over Au/TiO₂ was investigated in both a batch reactor and a continuous upflow fixed bed reactor. The effects of catalyst particle size, gas flow rate, liquid flow rate, reaction temperature, dioxygen pressure, and solution pH were examined in the fixed bed system. The unique hydrodynamics of the fixed bed system allowed for secondary oxidation products such as tartronic acid and oxalic acid to form in substantial amounts, which contrasts the product distribution observed in a batch system. These results suggest that reactor configuration can play an important role in the observed product selectivity from oxidation reactions over highly active gold catalysts.     

A Highly Efficient Catalyst Au/MCM-41 for Selective Oxidation Cyclohexane Using Oxygen

The liquid-phase highly efficient selective oxidation cyclohexane to cyclohexanol and cyclohexanone over Au/MCM-41 catalyst was carried out in a solvent-free system, which oxygen as the only oxidant and the reaction conditions are very moderate. The Au/MCM-41 was characterized by XRD, N₂adsorption/desorption, UV-Vis, XPS, and ICP-AES.     

Ethylene adsorption on Pt/Au/SiO2 catalysts

Ethylene adsorption on a Pt/Au/SiO₂ catalyst (2 wt% Pt; Au/Pt atomic ratio of 10) was studied using adsorption microcalorimetry and FTIR spectroscopy. Ethylene adsorption at 300 K on Pt/Au/SiO₂ produced π‐bonded, di‐σ‐bonded, and ethylidyne species with an initial heat of 140 kJ/mol, compared to a heat of 157 kJ/mol for Pt/SiO₂ on which only ethylidyne species formed. At 203 and 263 K, ethylene adsorbed on Pt as well as on Au surface atoms for the Pt/Au/SiO₂ catalyst. Quantum chemical, DFT calculations indicate that Au exerts a significantly smaller electronic effect on Pt than does addition of Sn to Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

Advanced Oxidation of Tannic Acid in Aqueous Solution

Decomposition of tannic acid in aqueous solution in advanced oxidation processes has been studied. Different oxidizing agents: ozone, hydrogen peroxide and UV radiation have been used both as single and mutually combined components of the system. The course of reaction was examined by the changes of chemical oxygen demand (COD) and total organic carbon (TOC) in aqueous solutions. Particular attention has been paid to determine optimal concentration of hydrogen peroxide, when it is used alone, together with O₃ and in H₂O₂+O₃+UV combination. The most effective optimal concentration of H₂O₂ was found. The entire mineralization of tannic acid into final products CO₂ and H₂O can be accomplished in all combinations of advanced oxidation with ozone. Bacteriological test ToxAlert® with luminescence bacteria Vibro fisheri proved that toxicity of solutions decreased considerably during advanced oxidation of tannic acid solution.     

Effect of Pretreatment on Carbon-Supported Au/TiO2 Catalysts for Preferential Oxidation of CO

The impact of thermal treatment at various preparation stages of carbon supported Au/TiO₂ catalysts prior to oxidation of CO in the presence and absence of hydrogen was studied. An increase in catalytic activity for thermally treated samples due to a more ordered structure of TiO₂ was observed. A reversible deactivation of the catalysts occurred in the absence of hydrogen. However, the activity was restored at preferential CO oxidation conditions in presence of hydrogen.     

Ru/SiO2 Catalyst for Highly Selective Hydrogenation of Dimethyl Malate to 1,2,4-Butanetriol at Low Temperatures in Aqueous Solvent

Catalysis Letters - Catalytic selective hydrogenation of esterified malic acid to produce 1,2,4-butanetriol (1,2,4-BT) using H2 as the reducing reagent suffers from the low 1,2,4-BT selectivity....     

Mesoporous Au/TiO2 Catalysts for Low Temperature CO Oxidation

The activity and stability of structurally well defined mesoporous Au/TiO₂ catalysts with different support morphologies and pore sizes for low temperature CO oxidation was investigated by kinetic measurements and in-situ IR spectroscopy. The resulting catalysts with Au particle sizes of ∼3 nm exhibit a high activity for CO oxidation, similar to or exceeding that of highly active standard Au/TiO₂ catalysts with similar size Au nanoparticles and loading, and a significantly lower tendency for deactivation. Possible reasons for the improved performance of these catalysts are discussed.     

胜利褐煤在NaOCl水溶液中的氧化

在温和条件下用NaOCl水溶液氧化胜利褐煤,结果NaoCl水溶液能将胜利煤中大部分有机质转化为小分子水溶性化合物.氧化所得混和物依次用乙醚和乙酸乙酯萃取,经重氮甲烷酯化后用GC/MS进行分析,结果表明所得化合物主要为一元酸、二元酸和苯甲酸类化合物.其中苯甲酸类化合物含量最高,其次是一元酸.氯代短链烷酸的含量在一元酸中占...     

水中除草剂阿特拉津降解的高级氧化技术

近年来水体除草剂污染问题越来越严重,阿特拉津是目前应用广泛的化学除草剂之一,阿特拉津施用后在水中的残留对人类健康产生了极大威胁。综述了电化学Fenton法、γ-辐照法、超声化学法、催化臭氧氧化法、光催化法等各种高级氧化技术降解阿特拉津的效果、影响因素,同时阐述了可能的降解产物和降解机理,提出了今后水中阿特拉津处理方面应该进一步研究的问题。     

聚乙烯醇在乙醇水溶液中缩醛化的研究

聚乙烯醇（ＰＶＡ）在乙醇水溶液中在酸性条件下与醛类缩醛化制成ＰＶＡ缩醛的乙醇水溶液。缩醛化度可由乙醇的浓度来控制。ＰＶＡ缩醛的乙醇水溶液经氧化降解后可直接用作配制胶粘剂和涂料的胶料。     

Role of Preparation Techniques in the Activity of Au/TiO2 Nanostructures Stabilised on SiO2: CO and Preferential CO Oxidation

Au colloid and titania in different sequence or Au-oxide nano ensembles preformed in hydrosol were deposited on inert amorphous silica or mesoporous SBA-15. It was compared with gold colloid adsorbed on TiO₂ or silica support. The formation of the Au/TiO₂ interface is discussed in terms of surface charges. Preferential CO oxidation in the presence of hydrogen (PROX) has been correlated with the CO oxidation activity and structural properties, perimeter and the influence of the TiO₂ morphology on the catalytic activity has been demonstrated.     

Oxidation of Cyanuric Acid in Aqueous Solution by Catalytic Ozonation

The aim of this work was studying the activity of a Ru/CeO₂ powder catalyst in the ozonation of aqueous solution of cyanuric acid (CYA). Ozonation in the presence of the catalyst significantly enhances CYA degradation. Within this work, investigation of the influence of pH and initial concentration on the catalytic ozonation of CYA has been done in a semicontinuous reactor. The removing degree of CYA at pH 5.9 show better response in comparison to pH 2.5 and pH 8.2. The mineralization of CYA by catalytic ozonation formed nitrate ions (0.7 mol of NO₃^?/mol of CYA removed for 50% initial CYA abatement) and nitrite and ammonium ions in small amounts. Three transformation products formed during catalytic ozonation were identified from LC/MS and MS/MS analyses. The impact of oxidation on the toxicity was measured from the inhibition of Vibrio fisheri, which was found to increase continuously.     

The Promoting Effect of Europium on PtSn/C Catalyst for Ethanol Oxidation

Well‐dispersed PtSnEu/C and PtSn/C catalysts were prepared by the impregnation–reduction method using formic acid as a reductant and characterised by X‐ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersion X‐ray spectroscopy (EDX) and X‐ray photoelectron spectroscopy (XPS). The synthesised catalysts with different atomic ratios of Pt/Sn/Eu have the Pt face centered cubic (fcc) structure and their particle sizes are 3–4 nm. The PtSnEu/C catalyst is composed of many Pt (0), SnO₂, Eu(OH)₃, a small amount of Pt(II) and partly alloyed PtSn, but no metallic Eu. The electrochemical measurements indicate that in comparison with Pt₃Sn₁/C catalyst, the Pt₃Sn₁Eu₁/C catalyst for ethanol oxidation has more negative onset potential, smaller apparent activation energy and lower electrochemical impedance so that it exhibits very high catalytic activity. Its peak current density increases by 135% and 40%, compared with Pt₃Sn₁/C and Pt₁Ru₁/C (JM) catalysts, respectively. This is because the Eu(OH)₃ formed by adding Eu to PtSn/C catalyst can provide the OH group which is in favour of the removal of adsorbed intermediates and ethanol oxidation.     

N-异丙基丙烯酰胺凝胶在乙醇水溶液中的溶胀平衡

N-isopropylacrylamide (NIPAAm) was used to synthesize NIPAAm homopolymer (nonionized) and NIPAAm-sodium methacrylate copolymer (ionized). The swelling equilibria for both gels were obtained in aqueous solution of ethanol with concentration ranging from 0 to 100%(by mass) at 25℃. The swollen gel in water shrank first with the addition of a small amount of ethanol and then reswelled with further addition of ethanol showing not only a discontinuous volume phase transition but also a typical reentrant phenomenon. A thermodynamic model based on the UNIQUAC with the “free-volume“ contribution was applied to correlate and predict the swelling behavior of the poly(NIPAAM)-gels in ethanol-water mixture.