Activity and Adsorption Behavior of Oxygen on Rutile TiO_(2)(110)

The activity and adsorption behavior of oxygen on rutile TiO_(2)(110)(RTiO_(2)(110))were investigated using the temperature programmed desorption(TPD)method with methanol(CH_(3)OH)as the probe molecule.By controlling the coverage of molecular O_(2)on the surface via increasing or decreasing O_(2)exposure,two chemisorbed O_(2)species on the surface are confirmed,one at the bridging oxygen vacancy(Ov)site(O_(2)^(2-)/Ov)and the other at the five-fold coordinated titanium(Ti_(5c))site(O^(2-)/Ti_(5c)).At low O_(2)exposure,O^(2-)/Ov is the main species on the surface,which only leads to the O-H bond cleavage of CH_(3)OH,producing methoxy groups(CHgO).However,after the Ov sites are nearly filled by O_(2)at about 0.1 L O_(2)exposure,O_(2)/Tisc species begins to appear on R-TiO_(2)(110)surface,resulting in the formation of formaldehyde(CH_(2)O)via the reaction of O_(2)/Tisc species with CH_(3)OH or CH3O to break the C-H bond at low surface temperature.Moreover,the yield of CH_(2)O increases linearly with that of H_(2)O.In addition,when the 1 L O_(2)covered surface is irradiated with 355 nm UV irradiation to desorb and dissociate O_(2)/Ti_(5c)species,the yield of CH_(2)O decreases linearly with that of H_(2)O.Further analysis suggests that the charge state of O_(2)/Ti_(5c)may not change as the exposure of O_(2)changes on the R-TiO_(2)(110)surface,and O_(2)is most likely to adsorb on the Ti_(5c)sites in the form of O_(2)^(2-),not O_(2)^(-),The result not only advances our understanding on the adsorption state of O_(2)on TiO_(2),but also provides clues for low temperature C-H bond activation with O_(2)on TiO_(2).

Role of Reduced Defects for Coupling Reactions of Acetaldehyde on Anatase TiO2（001）-（1×4） Surface

The chemistry of acetaldehyde (CH3CHO) adsorbed on the anatase TiO2(001)-(1×4) surface has been investigated by temperature-programmed desorption (TPD) method. Our experimental results provide the direct evidence that the perfect lattice sites on the anatase TiO2(001)-(1×4) surface are quite inert for the reaction of CH3CHO, but the reduced defect sites on the surface are active for the thermally driven reductive carbon-carbon coupling reactions of CH3CHO to produce 2-butanone and butene. We propose that the coupling reactions of CH3CHO on the anatase TiO2(001)-(1×4) surface should undergo through the adsorption of paired CH3CHO molecules at the reduced defect sites, since the existing reduced Ti pairs provide the suitable adsorption sites.

Effects of Surface Defects on Adsorption of CO and Methyl Groups on Rutile TiO_(2)(110)

The interaction of reactants with catalysts has always been an important subject for catalytic reactions.As a promising catalyst with versatile applications,titania has been intensively studied for decades.In this work we have investigated the role of bridge bonded oxygen vacancy(O_(v))in methyl groups and carbon monoxide(CO)adsorption on rutile TiO_(2)(110)(R-TiO_(2)(110))with the temperature programmed desorption technique.The results show a clear different tendency of the desorption of methyl groups adsorbed on bridge bonded oxygen(O_(b)),and CO molecules on the five coordinate Ti^(4+)sites(Ti_(5c))as the Ovconcentration changes,suggesting that the surface defects may have crucial influence on the absorption of species on different sites of R-TiO_(2)(110).

Ammoxidation of 3-Picoline over V-Mo-P Oxide Catalyst Prepared from 11-Molybdo-l-Vanado Phosphoric Acid

V-Mo-P oxide catalyst system was directly prepared from ll-molybdo-l-vanado phosphoric acid by thermal decomposition. Supported V-Mo-P oxide catalysts were prepared by wet impregnation method. Catalysts were characterized by FTIR （Fourier transform infrared）, XRD （X-ray diffraction） and TPD （temperature programmed desorption）. The catalytic activity of V-Mo-P oxide catalysts were investigated for vapour phase ammoxidation of 3-picoline. The unsupported catalyst showed 92.1% yield where as V-Mo-P oxide/HZSM-5 showed the highest yield （80.4%） amongst the supported catalysts.

Novel synthesis of nickel oxide microsphere with high surface area and its catalytic application for carbon dioxide reforming of methane

Nickel oxide(NiO)microsphere with a large surface area was novelly synthesized through nickel bicarbonate(Ni(HCO3)2)precursor.The obtained nickel oxide(NiO)microsphere was characterized by X-ray pattern diffraction,scanning electron microscopy,CO2 temperature-programmed desorption,H2 temperature-programmed reduction,N2 adsorption/desorption and laser scattering particle size distribution analyzer.It was found that nickel oxide(NiO)synthesized by the thermal decomposition of Ni(HCO3)2through area hydrolysis,presented very nice microsphere with high surface area.The catalytic properties of obtained nickel oxide(NiO)microsphere were studied in the reaction of carbon dioxide reforming of methane where 91.3% conversion of CH4 with 93% conversion of CO2 was observed.Besides,the catalyst maintained high stability over 200 h on the stream.

Sr含量对La_(2-x)Sr_xNiO_4(x=0.0～1.2)上NO分解的影响

研究了Sr含量对La_(2-x)Sr_xNiO_4上氧化还原性能和NO分解的影响,发现活性在x=0.6时达到最大值.TPD和TPR等的表征结果说明样品在x=0.6时具有比较匹配的氧化、还原能力,从而使O_2的脱附和NO的吸附变的相对容易,提高了催化活性.研究结果说明在T<700℃时,O2的脱附比较困难,是NO分解反应的速控步骤;随着反应温度的增加(T>700℃),O2的脱附变的容易,NO的活化吸附(NO+Vo+Ni2+→NO--Ni3+)成为反应的速控步骤.氧空位的存在是NO分解的前提条件,但氧空位的量与反应活性并不是呈正比关系.

Preparation and characterization of spherical mesoporous ZrO_(2)-Al_(2)O_(3) composites with high thermal stability

Spherical mesoporous ZrO_(2)-Al_(2)O_(3) composites containing different zirconia content have been synthesized by an oil-column sol-gel method.A mixed alumina-zirconia hydrosol and hexamethylenetetramine solution were mixed together and added dropwise into a hot oil column.Due to the surface tension,spherical gel particles were formed in the oil column.The spherical gel particles were then aged and washed by deionized water and dried at 120 ℃ for 12 h and then calcined at 600 ℃ for 8 h,960 ℃ for 8 h or 1200 ℃ for 12 h.X-ray diffraction and nitrogen adsorption-desorption measurements indicated that the presence of zirconia prevents the sintering of alumina and the obtained ZrO_(2)-Al_(2)O_(3) composites have much larger surface areas than pure alumina.Temperature-programmed desorption of ammonia results illustrated that the addition of zirconia leads to an increase in the number of strong acid sites and the total number of acid sites compared with pure alumina.Thus,the spherical mesoporous ZrO_(2)-Al_(2)O_(3) composites prepared in this way were shown to be suitable for high temperature catalytic processes as a catalyst support.

Reaction heat-driven CO2 desorption during CO oxidation on Au(997) at low temperatures

Adsorption and reaction of CO and CO2 were studied on oxygen-covered Au（997） surfaces by means of temperature- programmed desorption/reaction spectroscopy. Oxygen atoms （O（a）） on Au（997） enhances the CO2 adsorption and stabilizes the adsorbed COe（a）, and the stabilization effect also depends on the CO2（a） coverage and involved Au sites. CO2（a） desorp- tion is the rate-limiting step for the CO＋O（a） reaction to produce CO2 on Au（997） at 105 K and exhibits complex behaviors, including the desorption of CO2（a） upon CO exposures at 105 K and the desorption of O（a）-stabilized CO2（a） at elevated temperatures. The desorption of CO2（a） from the surface upon CO exposures at 105 K to produce gaseous CO2 depends on the surface reaction extent and involves the reaction heat-driven CO2（a） desorption channel. CO＋O（a） reaction proceeds more easily with weakly-bound oxygen adatoms at the （111） terraces than strongly-bound oxygen adatoms at the （111） steps. These re- sults reveal complex rate-limiting COe（a） desorption behaviors during CO＋O（a） reaction on Au surfaces at low temperatures which provide novel information on the fundamental understanding of Au catalysis.