溶胶-凝胶法制备铈钴复合氧化物催化剂的研究

用溶胶－凝胶法制备了钴、铈及其复合氧化物催化剂，在以对甲酚氧化制取对羟基苯甲醛的反应中，其催化性能较好。用ＤＴＡ－ＴＧ、ＦＴ－ＩＲ、ＴＥＭ、ＸＲＤ等手段考察了复合氧化物前驱体的热分解行为以及焙烧温度对粒子晶态的影响。结果表明，在２５０℃下恒温焙烧２ｈ，可得到非晶态和高比表面的钴铈复合氧化物超细微粒（ｒ≤３０ｎｍ），且具有良好的保持非晶态结构的热稳定性。

硝基苯气相加氢催化剂Cu/SiO_2的改性研究

采用溶胶-凝胶法制备了不同配比的Cu-Cr/SiO2催化剂,采用程序升温(TPR)结合X射线衍射(XRD)手段考察了Cu-Cr/SiO2催化剂中CuO的还原行为,并对其催化活性进行了评价。结果表明,助剂Cr2O3的加入使催化剂在还原时提高了Cu微晶的分散度,阻止了新生铜微晶的迁移及烧结,使催化剂的活性及稳定性增大。当Cu/Cr质量比为6:4时,硝基苯加氢转化率及选择性最高。

Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalyst and Optimal Synthesis Conditions of the Support Prepared by Sol-gel Method

The support of catalyst for the direct synthesis of diphenyl carbonate （DPC） by heterogeneous catalytic reaction was prepared by the sol-gel method. Compared with activated charcoal, molecular sieve, porous ceramics, hopcalite, the support prepared by the sol-gel method has higher activity. The characterization of the support by X-ray diffraction （XRD） and transmission electron microscope （TEM） show that the mare crystal phase is Co2MnO4 and the average particle diameter is about 40 nm. The optimum conditions for synthesis of the support were determined by orthogonal experiments, which indicate that the proportion of Cu, Mn, and Co is the first important factor influencing the yield and selectivity of DPC. Temperature of calcination is the second one. The optimum conditions are： molar proportion of Cu, Mn, and Co being 1 ： 1 ： 1, temperature of calcination 700℃, drying at 100~C, temperature of water bath 85~C. The yield and selectivity of DPC in the process can reach 38% and 99% in the batch operation, respectively. The copper cobalt manganese mixed oxides chosen as the support contribute more to the high catalytic activity than the sol-gel method.

Effects of Ni doping contents on photocatalytic activity of B-BiVO_4 synthesized through sol-gel and impregnation two-step method

To enhance the photocatalytic activity of B-BiVO4,Ni-doped B?BiVO4photocatalyst(Ni-B-BiVO4)was synthesized through sol-gel and impregnation method.The photocatalysts were characterized by XPS,XRD,SEM,EDS,BET and UV-Vis DRS techniques.The results showed that single or double doping did not change the crystalline structure and morphology,but the particle size decreased with Ni doping.The band gap energy absorption edge of Ni-B-BiVO4shifted to a longer wavelength compared with undoped,B or Ni single doped BiVO4.More V4+and surface hydroxyl oxygen were observed in BiVO4after Ni-B co-doping.When the optimal mass fraction of Ni is0.30%,the degradation rate of MO in50min is95%for0.3Ni-B-BiVO4sample which also can effectively degrade methyl blue(MB),acid orange(AOII)II and rhodamine B(RhB).The enhanced photocatalytic activity is attributed to the synergistic effects of B and Ni doping.

Selective catalytic reduction of NO with NH_3 over sol-gel-derived CuO-CeO_2-MnO_x/γ-Al_2O_3 catalysts

Granular CuO-CeO2-MnOx/γ-Al2O3 catalysts were synthesized by the sol-gel method. The performance of the CuO-CeO2-MnOx/γ-Al2O3 catalysts for the selective catalytic reduction (SCR) was studied in a fixed bed system. Preliminary tests were carried out to analyze the behavior of NH3 and NO over catalyst in the presence of oxygen. The optimum temperature range for SCR over the CuO-CeO2-MnOx/γ-Al2O3 catalysts is 300-400 ℃ . The catalysts maintain nearly 100% NO conversion at 350 ℃. The NH3 oxidation experiments show that both NO and N2O are produced gradually with the increase of temperature. The catalysts in this experiment have a stronger oxidation property on NH3, which improves the denitrification activity at low temperature. The over-oxidation of NH3 at high temperature is the main cause leading to a decrease in the NO conversion. The NH3 and NO desorption experiments show that NH3 and NO can be adsorbed on CuO-CeO2-MnOx/γ-Al2O3 granular catalysts. The transient response of NH3 and NO indicates that the SCR reaction proceeds in accordance with the Eley-Rideal mechanism. The adsorbed NO has little influence on the denitrification activity in SCR process.

A new solid acid SO_4^(2-)/TiO_2 catalyst modified with tin to synthesize 1,6-hexanediol diacrylate

A new solid acid catalyst,SO4^2-/TiO2 modified with tin,was prepared using a sol-gel method and its physicochemical properties were revealed by nitrogen adsorption-desorption,X-ray powder diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,infrared spectroscopy of adsorbed pyridine,temperature-programmed desorption of ammonia and thermal gravimetric analysis.The structure,acidity and thermal stability of the SO4^2-/TiO2-SnO2 catalyst were studied.Incorporating tin enlarged the specific surface area and decreased crystallite size of the SO4^2-/TiO2 catalyst.The total acid sites of the modified catalyst increased and Bronsted acid strength remarkably increased with increasing tin content.The decomposition temperature of sulfate radical in the modified catalyst was 100 ℃ greater and its mass loss was more than twice that of the SO4^2-/TiO2 catalyst.The SO4^2-/TiO2-SnO2 catalyst was designed to synthesize 1,6-hexanediol diacrylate by esterification of 1,6-hexanediol with crylic acid.The yield of 1,6-hexanediol diacrylate exceeded 87% under the optimal reaction conditions：crylic acid to 1,6-hexanediol molar ratio = 3.5,catalyst loading = 7%,reaction temperature = 130 ℃ and reaction time = 3 h.The modified catalyst exhibited excellent reusability and after 10 cycles the conversion of 1,6-hexanediol was above 81%.

Structure,morphology and opto-magnetic properties of Bi_2MoO_6 nano-photocatalyst synthesized by sol-gel method

Bismuth molybdate （Bi2MoO6） nano-particles （NPs） were synthesized using bismuth nitrate, ammonium molybdate, citric acid and ethyl cellulose by a simple sol-gel method. The structure, morphology, opto-magnetic and photocatalytic properties of the obtained powder were characterized by X-ray diffraction （XRD）, Fourier transform infrared （FT-IR） spectra, high resolution scanning electron microscopy （HRSEM）, energy dispersive X-ray （EDX）, ultraviolet-visible diffuse reflectance spectra （DRS）, photoluminescence （PL） spectra and vibrating sample magnetometer （VSM） techniques. The XRD, FT-IR and EDX results indicate that the resultant powder is pure and single phase crystalline Bi2MoO6 with orthorhombic structure. The HRSEM image shows that the morphology of obtained powder consists with well defined nano-particles structure. The VSM results show superparamagnetic behavior of the obtained nano-particles. The photocatalytic activity of Bi2MoO6 nano-particles was performed. The addition of TiO2 catalyst enhances the photocatalytic activity of Bi2MoO6 nano-particles. The catalysts Bi2MoO6, TiO2 and mixed oxide catalyst Bi2MoO6-TiO2 nano-composites （NCs） were tested for the photocatalytic degradation （PCD） of 4-chlorophenol （4-CP）. It is found that the PCD efficiency of Bi2MoO6-TiO2 NCs is higher than that of pure Bi2MoO6 and TiO2 catalysts.

Oxidative Coupling of Methane over Li/MgO： Catalyst and Nanocatalyst Performance

The Li/MgO catalyst and nanocatalyst were prepared by the incipient wetness impregnation and sol-gel method, respectively. The catalytic performance of the Li/MgO catalyst and nanocatalyst on oxidative coupling of methane was compared. The catalysts prepared in two ways were characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface and transmission electron microscope. The catalyst was tested at temperature of 973-1073 K with constant total pressure of 101 kPa. Experimental results showed that Li/MgO nanocatalyst in the oxidative coupling of methane would result in higher conversion of methane, higher selectivity, and higher yield of main products （ethane and ethylene） compared to ordinary catalyst. The results show the improved influence of nanoscale Li/MgO catalyst performance on oxidative coupling of methane.