纳米固体超酸SO42-/TiO2的研究

The new nanosolid superacid catalyst SO₄^2-/TiO₂ is compounded with nanometer chemical technology. This catalyst SO₄^2-/TiO₂ has good catalytic effects on esterificational reactions of ethylic acid and ethyl alcohol. It has many other advantages such as strong water-proof quality, being able to be used repeatedly, being easy to be re-claimed, non-corroding, non-polluting. So it is a green industrial catalyst which is helpful to the environment and possesses wide prospect of applications. The crystallo-process, specific surface area and sulphur content of the SO₄^2-/TiO₂ system have been studied with the method of XRD, XPS and the chemical analysis, the result of which indicates that catalytic activity and acid strength of SO₄^2-/TiO₂ is affected by the H₂SO₄ saturant concentration, baking temperature, precipitating condition, specific surface area and sulphur content. The best preparation conditions of SO₄^2-/TiO₂ are: ageing temperature at 0℃, 0.5mol·L^-1 of H₂SO₄ concentration, baking temperature at 500℃and 3 hours of baking time.     

不同稀土改性SO42-/ZrO2催化剂的结构与性能表征

Solid superacid catalyst SO₄^2-/ZrO₂ was modified by different rare earth compounds and applied to the esterification of acetic acid and n-butanol. The effects of rare earth elements loading on the catalytic properties were studied and the correlation between the structure and properties was investigated by means of XRD, IR, UV, DTA and TG. The results show that the (NH₄)₂Ce(NO₃)₆ modification can enhance catalytic activity more and exhibit better stability than the other two compounds La(NO₃)₃ and Ce(NO₃)₃. Meanwhile,(NH₄)₂Ce(NO₃)₆ modification can restrain the loss of SO₄^2- efficiently. The optimum calcination temperature and molar ratio of Ce(NH)∶Zr for SO₄^2-/ZrO₂ catalyst modified by (NH₄)₂Ce(NO₃)₆ are 450 ℃ and 2, respectively.     

Dehydrocyclization of Diphenylamine to Carbazole over Platinum-Based Bimetallic Catalysts

 Gas phase dehydrocyclization of diphenylamine (DPA) to carbazole over monometallic and bimetallic 0.4 wt% Pt-based catalysts in a fixed bed reactor was studied in the presence of hydrogen at a temperature of 550 ^oC. Alumina and carbon supported Pt catalysts showed very high initial activity (> 95%). The selectivity for carbazole over carbon supported Pt catalysts was slightly lower. Doping of the catalyst with potassium led to an increase in the selectivity for carbazole by 15%. Bimetallic Pt-Sn catalysts prepared by co-impregnation were less selective than catalysts prepared by successive impregnation. The selectivity for carbazole over bimetallic Pt-Sn catalysts prepared by successive impregnation was 75%, but their activity decreased with increased Sn loading. Highly active and reasonably selective catalysts were Ir-doped bimetallic Pt-based catalysts. The conversion of diphenylamine over Pt-Ir catalysts was above 98% and the selectivity for carbazole was nearly 55%, while the lifetime was much longer.     

Hydroisomerization of n-heptane over bimetal-bearing H_3PW_(12)O_(40) catalysts supported on dealuminated USY zeolite

The bimetal-bearing (CePt or LaPt) 12-tungstophosphoric acid (H3PW12O40 (PW)) catalysts supported on dealuminated USY zeolite (DUSY) were prepared by impregnation and characterized by XRD, BET, IR, and H2-chemisorption. Their catalytic activities were tested in the hydroisomerization of n-heptane with a continuous atmospheric fixed-bed reactor. After the steam treatment combined with the acid leaching, as well as the supporting with PW and the bimetals, the DUSY support retains the Y zeolite porosity and the PW well keeps its Keggin structure in catalysts. The doping of Ce into the catalysts enhances the dispersion of Pt on the catalyst surface. The Pt-bearing PW catalysts doped with Ce or La, especially Ce, exhibit much higher catalytic activity and selectivity than the catalysts without dopants at lowered reaction temperatures. At the optimal reaction conditions, i.e., the reaction temperature of 250℃ and WHSV of 1.4 h1, the catalyst with a Pt loading of 0.4%, PW loading of 10% and a molar ratio of Ce to Pt of 15:1 shows a conversion of n-heptane of 70.3% with a high selectivity for isomerization products of 94.1%.     

石墨负载Pt催化剂的制备、表征及活性研究

Pt/graphite catalyst was prepared by incipient wetness impregnation using H₂PtCl₆·6H₂O as precursor. The catalyst was characterized by SEM, XRD, XPS and its degradation ability for oxalic acid was evaluated. The preparation parameters, including the reduction temperature, Pt loading and pyrolysis were studied. The optimal preparation conditions were 350 ℃ with Pt loading of 1.0%. Results show that the loading of Pt can significantly enhance catalytic activity of graphite and that Pt/graphite catalytic ozonation can effectively remove oxalic acid in aqueous solution. The BET surface area of graphite is much smaller than that of activated carbon, however, the catalytic activity of Pt/graphite towards oxalic acid degradation is higher than that of Pt/AC. The XPS results indicate that the active phase at catalyst surface is in the form of Pt⁰. Compared with that of reduction process in hydrogen, the activity of Pt/graphite catalyst decreases when it is prepared by pyrolysis in air due to the lower Pt dispersion on graphite surface.     

Phosphonated USY,a promising catalyst for the development of environmentally benign biodiesel(methyl acetate) process

The present study focuses on the evaluation of the potential applicability of Ultra Stable Y(USY) and phosphonated USY(1 wt%-4 wt%phosphorous loading) as heterogeneous catalysts for biodiesel(methyl acetate) production.The synthesized catalysts were characterized by powder X-ray diffraction(XRD),Brunaer-Emmett-Teller(BET) surface area,total acidity by temperature-programmed desorption of ammonia(TPD-NH3) and Fourier Transform Infrared(FTIR) spectra.The performances of catalysts were evaluated for the transesterification of butyl acetate with methanol(a model reaction in biodiesel production).In view to obtain a maximum yield of methyl acetate,the optimization of process parameters such as reactant molar ratio,catalyst loading,reaction temperature and reaction time was performed.All the phosphonated USY catalysts showed higher catalytic activity than the parent USY,which can be attributed to the increase of total acidity due to phosphonation.2 wt% P/USY(2% phosphorous loaded on USY) exhibited 92% methyl acetate yield with 100% selectivity,which was proved to be a potential catalyst for biodiesel production.The invented catalyst was found to be stable and reusable for five catalytic cycles,demonstrating that it might be a environmentally benign catalytic process.     

PdCl2/ O-MCM-41催化剂制备及其在苯酚氧化羰化反应中的应用

Hybrid mesoporous silica MCM-41 (O-MCM-41) was prepared using γ-aminopropyltriethoxysilane (APTES) as spacer, tetraethoxysilane as precursor and 2-acetylpyridine as organic moiety. The heterogeneous palladium catalyst (PdCl₂/ O-MCM-41) was then prepared by reaction of the hybrid MCM-41 with PdCl₂(PhCN)₂. The products were characterized by means of IR, XRD, XPS and N₂ adsorption-desorption isotherms. The catalytic properties of the supported catalyst in the oxidative carbonylation of phenol to diphenyl carbonate (DPC) were investigated. The yield of DPC and turnover number (TON) reached 5.8% and 29 mol DPC·mol Pd^-1, and Pd loss was only 2.7% at 110 ℃, 4.4 MPa for catalytic reaction of 5 h with 4.2wt% Pd loading, and molar ratio of phenol to Pd being 1000 in the presence of Cu₂O and terahydrofuran (THF).     

钒催化剂选择性氧化乳酸乙酯制丙酮酸乙酯

The structure and surface acidity of vanadium oxide supported on α-Al₂O₃、TiO₂、SiO₂ have been studied by XRD、IR、TPR and adsorption microcalorimetry. The catalytic performance of the catalysts for selective oxidation of ethyl lactate to ethyl pyruvate was determined in a continuous flow fix-bed reactor. The results showed that the dispersion of vanadium oxide on the supports weakened the V=O bond and actived the terminal oxygen, which increased the reaction activity. On the otherhand, The surface acidity is harmful to the selectivity of ethyl pyruvate. V/α-Al₂O₃ exhibited a lower conversion since its dispersion is low. The low selectivity on V/SiO₂ is due to its fairly strong surface acidity. Addition of K⁺ weakened the surface acidty and enhanced selectivity of V/SiO₂. V/TiO₂ exhibited the best activity and selectivity among the catalysts studied because of its weak surface activity. The conversion of ethyl lactate and selectivity to ethyl pyruvate are 97% and 81%, respectively, over the V/TiO₂ catalyst at 473K.     

Electrodeposited Pt and Pt-Sn nanoparticles on Ti as anodes for direct methanol fuel cells

Electro-oxidation of methanol was studied on titanium supported nanocrystallite Pt and Pt_x-Sn_y catalysts prepared by electrodeposition techniques. Their electro-catalytic activities were studied in 0.5mol/L H₂SO₄ and compared to those of a smooth Pt, Pt/Pt and Pt-Sn/Pt electrodes. Platinum was deposited on Ti by galvanostatic and potentiostatic techniques. X-ray diffractometer (XRD) and energy dispersive X-ray (EDX) techniques were applied in order to investigate the chemical composition and the phase structure of the modified electrodes. Scanning electron microscopy (SEM) was used to characterize the surface morphology and to correlate the results obtained from the two electrochemical deposition methods. Results show that modified Pt/Ti electrodes prepared by the two methods have comparable performance and enhanced catalytic activity towards methanol electro-oxidation compared to Pt/Pt and smooth Pt electrodes. Steady state Tafel plots experiments show a higher rate of methanol oxidation on a Pt/Ti catalyst than that on a smooth Pt.  Introduction of a small amount of Sn deposited with Pt improves the catalytic activity and the stability of prepared electrode with time as indicated from the cyclic votlammetry and the chronoamperometric experiments. The effect of variations in the composition for binary catalysts of the type Pt_x-Sn_y/Ti towards the methanol oxidation reaction is reported. Consequently, the Pt_x-Sn_y/Ti (x∶y (8∶1), molar ratio) catalyst is a very promising one for methanol oxidation.     

Selective catalytic methanation of CO in hydrogen-rich gases over Ni/ZrO2 catalyst

Ni/ZrO2 catalysts were prepared by the incipient-wetness impregnation method and were investigated in activity and selectivity for the selective catalytic methanation of CO in hydrogen-rich gases with more than 20 vol% CO2. The result showed that Ni loadings significantly influenced the performance of Ni/ZrO2 catalyst. The 1.6 wt% Ni loading catalyst exhibited the highest catalytic activity among all the catalysts in the selective methanation of CO in hydrogen-rich gas. The outlet concentration of CO was less than 20 ppm with the hydrogen consumption below 7%, at a gas-hourly-space velocity as high as 10000 h-1 and a temperature range of 260 °C to 280 °C. The X-ray diffraction （XRD） and temperature programmed reduction （TPR） measurements showed that NiO was dispersed thoroughly on the surface of ZrO2 support if Ni loading was under 1.6 wt%. When Ni loading was increased to 3 wt% or above, the free bulk NiO species began to assemble, which was not favorable to increase the selectivity of the catalyst.     

Physico-chemical properties of Chitosan films

Chitosan films obtained by dry phase inversion were prepared from an aqueous solution of chitosan in acetic acid. The films, of thickness less than 20 μm, were transparent, very flexible and had smooth surfaces. Increasing the film thickness induced an increase of the internal tensions and the consequent formation of a rough surface. Structural investigations by X-ray diffraction and Fourier transform IR analysis, showed that the chitosan films, as prepared, are amorphous. Further annealing to evaporate acetic acid and water traces, changed the amorphous phase into a more ordered phase, characterized by diffraction peaks at 2θ values of 9, 17, 20 and 23 degrees. Thermal investigations by TG, DTG, and DTA revealed that the decomposition of the chitosan films as prepared proceeds in two stages, starting from 180°C and 540°C.     

Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy

Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by¹³C and ¹⁵N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists.     

Aqueous p-nitrotoluene oxidation induced with direct glow discharge plasma

A plasma induced degradation process has been studied to treat 4-nitrotoluene (4-NT) present as an aqueous pollutant. The plasma was locally generated from a glow discharge around a tip of a platinum anode in an electrolytic solution. The influence of initial pH and Fe²⁺ on the degradation was examined. Major intermediates resulting from the degradation process were identified. Amongst the aromatic intermediates, p-hydroxybenzoic acid was the predominant degradation product. The formation of oxalic acid, malic acid was also observed. The final products of degradation were NH ₄ ⁺ , NO ₃ ⁻ and CO₂. Based on the analysis of intermediates and the kinetic considerations, the degradation was shown to follow a pseudo-first order reaction hence, a possible reaction pathway was proposed.     

Catalytic air oxidation of manganese in synthetic waters

An attempt was made to study the oxidation of manganese by air in synthetic waters. A series of batch experments were performed at differnet values of concentration, temperature and pH. Unoxidized manganese in the solution was determined by formaldoxime spectrometric method. Results of these studies indicated that the air oxidation of manganese soluble in water can be effectively performed in basic media and that oxidation yield increasedwith an increase in pH and concentration. The yield was very high in the presence of manganese dioxide, sepiolite or clinoptilolite in solution and, the oxidation was almost completed especially at high values of pH and concentration. The reaction was found to be first order with respect to Mn²⁺ with a very low activation energy. A yield of 62% was obtained for the air oxidation of wastewater taken from the treatment plant of Corum Municipality.     

Zur Kenntnis der Reaktionsfähigkeit des Thiomorpholins und alkylsubstituierter Thiomorpholine, 4. Mitt.

Thiomorpholine as well as alkyl substituted thiomorpholines and their Sdioxides, respectively, are transformed into the corresponding N-Aminothiomorpholines by nitrosation (1–5) followed by the reduction with zinc in acetic acid/acetic acid anhydride under simultaneous formation of the corresponding N-acetyl derivates, and hydrolysis by hydrochloric acid (6–9). Examples of this method are described. 4-Aminothiomorpholines and their Sdioxides react with aldehydes or ketones to give azomethines (10–31). Acylation with mono-and dicarbonic acid chlorides leads to the N-acyl derivatives32–44.Mannich condensation is also possible. By oxidation with yellow mercury oxide tetracenes are formed (46–47).

Teil der DissertationM. Schmitz, Techn. Hochschule Aachen, 1975.     

Präparation und röntgenographische Untersuchung eines neuen Kupfer-Oxoaluminats: Cu2Al4O7

Solid state reaction of CuO and Al₂O₃ with a flux of PbO about 930°C and reaction time of 8d gives the new compound Cu₂Al₄O₇. The red single crystals were examined by energydispersive microanalysis and X-ray diffraction methods. Cu₂Al₄O₇ has cubic symmetry, space group ,a=908.0 pm. The typical coordination of Cu⁺ (CN=6 and CN=12) and the interstitial arrangement of the AlO₄-tetrahedra are discussed with respect to related compounds.

     

Beiträge zur Chemie der Pyrrolpigmente, 39. Mitt.: Ein Kraftfeldmodell zur konformationsanalytischen Untersuchung von Gallenfarbstoffen

A force field model was designed with respect to the special needs of bile pigments. It is parametrized and tested using partial structures of bile pigments as well as an integral pigment; the solution structures of the molecules were previously deduced using independent experimental methods.

38. Mitt::Falk, H., Schlederer, T., Wolshann, P., Mh. Chem.112, 199 (1981).     

Hydrazyl,Nitronyl-, and imino-nitroxides: Synthesis,properties and reaction with nitric oxide and nitrogen dioxide

Ten novel and stable free radicals of nitronyl-, imino-nitroxide and hydrazyl type compounds were synthesized and their physico-chemical properties investigated. UV-Vis and ESR spectroscopic data, as well as the lipophilicities and specific hydrophobic areas of the compounds are compiled. The reaction of these radical compounds with nitric oxide and nitrogen dioxide was also investigated. The radicals synthesized, show selectivity in their reaction with these nitric oxides, depending on their structure (nitronyl-nitroxide radicals react with NO, while hydrazyl radicals react with NO₂). The processes are easily monitored by UV-Vis or ESR spectroscopy.     

Neue Synthesemethoden, 4. Mitt.: Milde einphasenoxidation von Sulfiden und Sulfoxiden zu Sulfonen

The mild oxidation of sulfides and sulfoxides to sulfones with benzyltriethylammoniumpermanganate in organic solvents is described.

1Scholz, D., in Vorbereitung.     

A kinetic method for <Emphasis Type="Italic">para</Emphasis>-nitrophenol determination based on its inhibitory effect on the catalatic reaction of catalase

The inhibitory effect of para-nitrophenol on the catalytic reaction of catalase was investigated. Michaelis-Menten kinetic parameters were determined from Lineweaver-Burk plots obtained in the absence or in the presence of the inhibitor. The inhibitor pattern, revealed by the Lineweaver-Burk plots, suggested a fully mixed inhibition mechanism. Spectrophotometric monitoring of the indicator reaction: in conjunction with initial rate measurements was employed for the kinetic determination of the inhibitor. Calibration plots of initial rate vs. para-nitrophenol concentration were linear in the concentration range 0.9·10⁻⁵–2.5·10⁻⁵ mol/L and the detection limit was 3·10⁻⁶ mol/L (417 μg/L) para-nitrophenol. Interferences from other phenolic compounds like orto-cresole, meta-and orto-nitrophenol were observed.