Structures and properties of zirconia-supported ruthenium oxide catalysts for the selective oxidation of methanol to methyl formate

The effects of RuO(x) structure on the selective oxidation of methanol to methyl formate (MF) at low temperatures were examined on ZrO(2)-supported RuO(x) catalysts with a range of Ru surface densities (0.2-3.8 Ru/nm(2)). Their structure was characterized using complementary methods (X-ray diffraction, Raman and X-ray photoelectron spectra, and reduction dynamics). The structure and reactivity of RuO(x) species change markedly with Ru surface density. RuO(x) existed preferentially as RuO(4)(2-) species below 0.4 Ru/nm(2), probably as isolated Zr(RuO(4))(2) interacting with ZrO(2) surfaces. At higher surface densities, highly dispersed RuO(2) domains coexisted with RuO(4)(2-) and ultimately formed small clusters and became the prevalent form of RuO(x) above 1.9 Ru/nm(2). CH(3)OH oxidation rates per Ru atom and per exposed Ru atom (turnover rates) decreased with increasing Ru surface density. This behavior reflects a decrease in intrinsic reactivity as RuO(x) evolved from RuO(4)(2-) to RuO(2), a conclusion confirmed by transient anaerobic reactions of CH(3)OH and by an excellent correlation between reaction rates and the number of RuO(4)(2-) species in RuO(x)/ZrO(2) catalysts. The high intrinsic reactivity of RuO(4)(2-) structures reflects their higher reducibility, which favors the reduction process required for the kinetically relevant C-H bond activation step in redox cycles using lattice oxygen atoms involved in CH(3)OH oxidation catalysis. These more reactive RuO(4)(2-) species and the more exposed ZrO(2) surfaces on samples with low Ru surface density led to high MF selectivities (e.g. approximately 96% at 0.2 Ru/nm(2)). These findings provide guidance for the design of more effective catalysts for the oxidation of alkanes, alkenes, and alcohols by the synthesis of denser Zr(RuO(4))(2) monolayers on ZrO(2) and other high surface area supports.     

负载Pd密偶催化剂的载体效应

采用尿素水解法或吸附沉淀法制备了金属氧化物载体,并用浸渍法负载0.5%Pd制得了Pd/Sn0.4Zr0.6O2,Pd/ZrO2,Pd/SnO2,Pd/SnO2-Al2O3和Pd/Al2O3催化剂.采用原位漫反射红外光谱、拉曼光谱、X射线光电子能谱和程序升温还原等方法对催化剂结构进行了表征,探讨了不同载体对表面PdOx物种化学吸附性质和氧化还原性能的影响,并与样品的丙烷氧化活性相关联.漫反射红外光谱表明,在Pd/SnO2-Al2O3中,Sn对Al2O3表面的Pd原子簇起到稀释作用,促进了Pd的分散,使得其CO线式吸附强度明显高于Pd/Al2O3,但Pd过高的分散度不仅减少了表面Pd-PdO活性位对的数目,而且使反应中间物种Pd-OH之间脱水困难,因而阻塞了活性位,降低了其循环氧化还原活性;而在Sn0.4Zr0.6O2复合氧化物载体中,SnO2有效地阻止了四方晶相ZrO2向稳态单斜晶相转变,且复合载体的比表面积较ZrO2和SnO2有所增加,其表面PdOx物种的分散度适中.此外,Sn0.4Zr0.6O2复合氧化物负载的Pd的价态介于Pd0与Pd2 之间,表面氧空位较多,促进了丙烷中C-H键的活化,使比表面积较低的Pd/Sn0.4Zr0.6O2具有最好的催化丙烷氧化能力,相反比表面积较高的Pd/SnO2-Al2O3活性很差,说明分散度适中且具有较低氧化态的PdOx(0相似文献   

ZrO_2晶相对MoO_x/ZrO_2催化剂结构及其甲醇选择氧化性能的影响

以纯的单斜氧化锆(m-ZrO2)和四方氧化锆(t-ZrO2)为载体,采用浸渍法分别合成了具有不同MoOx表面密度的MoOx/m-ZrO2和MoOx/t-ZrO2催化剂,并结合粉末X射线衍射,Raman光谱和H2程序升温还原等技术表征了不同ZrO2晶相对MoOx分散状态、结构以及甲醇氧化反应性能的影响.在低于锆表面MoOx的单层分散阈值(～5nm-2)时,m-ZrO2比t-ZrO2能够更有效地分散MoOx,形成高分散的孤立或二维结构的MoOx物种,避免了晶相MoO3的出现.当Mo表面密度超过单层分散阈值后,经过600℃焙烧,MoOx与ZrO2载体发生固相反应生成晶相ZrMo2O8,m-ZrO2比t-ZrO2更有利于ZrMo2O8的生成.提高Mo表面密度,催化剂表面的酸性随之增强,说明晶相ZrMo2O8比分散的MoOx物种具有更强的酸性.t-ZrO2与MoOx作用形成的强酸中心更有利于催化甲醇脱水生成二甲醚,但m-ZrO2使得MoOx具有更高的氧化还原能力和催化甲醇选择氧化反应的活性.ZrO2晶相对MoOx/ZrO2催化剂影响的研究结果将有助于研究VOx等其它金属氧化物催化剂以及发展酸性和氧化还原性双功能催化剂体系.     

Catalytic abatement of CO and volatile organic compounds in waste gases by gold catalysts supported on ceria-modified mesoporous titania and zirconia

Mesoporous oxides TiO2 and ZrO2, synthesized by surfactant templating via a neutral C13(EO)6–Zr(OC3H7)4 assembly pathway, and ceria‐modified TiO2 and ZrO2, prepared by a deposi‐tion–precipitation (DP) method, featuring high surface areas and uniform pore size distributions were used as supports for gold catalysts. The supported gold catalysts were assessed for the cata‐lytic abatement of air pollutants, i.e., CO, CH3OH, and (CH3)2O. The gold was supported on the mes‐oporous oxides by a DP method. The supports and catalysts were characterized by powder X‐ray diffraction, high‐resolution transmission electron microscopy, N2 adsorption–desorption analysis, and temperature‐programmed reduction technique. A high degree of synergistic interaction be‐tween ceria and mesoporous ZrO2 and TiO2 as well as a positive modification of the structural and catalytic properties by ceria was observed. The ceria additive interacts with the mesoporous oxides and induces a strong effect on the reducibility of the supports. The catalytic behavior of the catalysts was discussed to determine the role of the ceria modifying additive and possible interaction be‐tween the gold nanoparticles and ceria‐mesoporous oxide supports. The gold catalysts supported on ceria‐modified mesoporous ZrO2 displayed superior catalytic activity (~100%conversion of CO at 10 °C and CH3OH at 60 °C). The high catalytic activity can be attributed to the ability of the sup‐port to assist oxygen vacancies formation. The studies indicate that the ceria‐modified mesoporous oxide supports have potential as supports for gold‐based catalysts.     

ZrO2—SiO2负载Cu—Ni催化剂的CO2加氢反应性能

采用表面反应改性法,制备了ZrO2-SiO2（ZrSiO)表面复合物载体,用等体积浸渍法制备了ZrSiO担载的Cu-Ni双金属催化剂,借助BET、TPR、IR和微反等技术,研究了ZrSiO及其负载的Ni、Cu双金属催化剂的表面构造,化学吸附及催化CO2加氢的反应性能,结果表明,ZrSiO表面主要是价联型结构,ZrO2引入SiO2表面,可以有效地促进CuO和NiO的还原,在ZrSiO负载的Cu-Ni催化剂表面的Cu或Ni位,CO2发生化学 吸附形成线、剪式、卧式吸附态,在该催化剂上CO2的加氢反应产物主要是CH3OH3、CH4、CO和H2O生成CH3OH的选择性与催化剂组成及反应条件密切相关,在适当的条件,CH3OH的选择性大于90％。     

ReOxZrO2催化甲醇一步合成二甲氧基甲烷的研究

利用负载型ReOxZrO2催化剂，将甲醇选择性氧化并一步合成二甲氧基甲烷。考察了反应时间、反应温度以及铼负载量对反应的影响。并利用N2吸附/脱附、X射线光电子能谱、氨程序升温脱附(NH3-TPD)和氢程序升温还原(H2-TPR)等手段对催化剂进行了表征。结果表明，较高的反应温度有利于提高甲醇的转化率，但对二甲氧基甲烷的选择性不利；催化剂上所负载铼的质量分数对甲醇转化率影响较大，在铼的质量分数为1.64%时转化率达到最大值25.1%；负载于ZrO2上的ReOx 具有双功能催化性质：它既可作为氧化中心氧化甲醇，在还原后又可作为酸中心催化醇醛缩合。     

Breakthrough in the direct conversion of methane into c1-oxygenates

The partial oxidation of methane to CH3OH and HCHO (C1-oxygenates) was evaluated over a low surface area V2O5/SiO2 catalyst. The introduction of low amounts of NO (0-2.92% vol) to the reaction feed strongly enhanced both the conversion of methane and selectivity to C1-oxygenates. In the presence of NO, both the reaction temperature and the CH4/O2 ratio affected selectivity to CH3OH and HCHO. Selectivity values of C1-oxygenates as high as 40% at a methane conversion close to 40% were obtained.     

载体对担载Ni催化剂甲烷与二氧化碳重整反应活性的影响

制备了 Zr O2 、Mg O改性的 Al2 O3、Ti O2 复合载体 ,并应用 X-射线粉末衍射 (XRD)、比表面积测定、扫描电镜 (SEM)等手段进行了表征 .结果表明 ,这些氧化物在 Al2 O3上的晶粒尺寸小、比表面积大 ,分散较好 ,而在Ti O2 上的分散性较差 .对经 10 73K焙烧的 Mg O/ Ti O2 ,还发现部分 Ti O2 载体由锐钛矿变为金红石 ,同时生成Mg Ti O3 新相 .考察了载体对 Ni催化剂的 CH4与 CO2 重整反应活性的影响 ,其次序为 :Mg O/ Al2 O3>Zr O2 /Al2 O3>Al2 O3>Mg O >Zr O2 >Ti O2 >Mg O/ Ti O2 . Ti O2 及 Mg O/ Ti O2 担载 Ni催化剂的低活性可能与 Ti O2 本身的还原性有关     

Ni(OCH3)2/SiO2催化剂的制备及其合成碳酸二甲酯的反应性能

采用表面改性和离子交换相结合的方法，制备了负载型单核金属甲氧基配合物Ni(OCH3)2/SiO2催化剂。利用IR、TPD、TPSR和微反技术，考察了催化剂的表面结构以及CO2、CH3OH在催化剂表面上的化学吸附和反应性能。结果表明，负载型单核金属甲氧基配合物Ni(OCH3)2/SiO2中，Ni^2 与载体SiO2表面的O^2-以双齿形式配位；在催化剂表面存在CO2的桥式吸附态和甲氧碳酸酯基物种两种吸附态，CH3OH则只有一种分子吸附态。在373-473K条件下，CO2和CH3OH在催化剂上的反应物主要是DMC、H2O以及少量的CO、CH4和CH2O，催化剂的活性由表面甲氧碳酸酯基物种与分子吸附态甲醇的反应决定的。讨论了催化剂上CO2和CH3OH的活化过程及吸附态的形成机理。     

Using DFT in search for support effects during methanol oxidation on supported molybdenum oxides

The oxidation of methanol on supported molybdenum oxides was studied using DFT. Starting from a cluster model for a mono-oxo and di-oxo molybdenum oxide on a SiO(2) support, the reaction energies and rates for the oxidation of methanol were computed and interpreted with chemical reaction indices. This pointed out that the apparent barrier was significantly lower on the mono-oxide model, favoring it over the di-oxo species. Accordingly, we assumed similar behavior on Al(2)O(3), TiO(2) and ZrO(2) supports, so that we could compare characteristics over different supports. The obtained reaction energies and rates followed the experimental turn-over frequency (TOF) sequence.     

Ag/La0.6Sr0.4MnO3基催化剂上CH3OH和CO的完全氧化

合成了Ａｇ／Ｌａ０．６Ｓｒ０．４ＭｎＯ３、Ａｇ／Ｌａ０．６Ｓｒ０．４ＭｎＯ３／γ－ＡＩ２Ｏ３两毓催化剂,发现钙钛矿型Ｌａ０．６Ｓｒ０．４ＭｎＯ３对低浓度ＣＨ３ＯＨ或ＣＯ的完全氧化显示出相当高的催化活性,适量Ａｇ对钙钛矿型Ｌａ０．６Ｓ５０．４ＭｎＯ３基质的修使其对ＣＨ３ＯＨ或ＣＯ完全氧化催化活性获明显提高;在６％Ａｇ／２０％Ｌａ０．６Ｓｒ０．４ＭｎＯ３／γ－ＡＩ２Ｏ３催化剂 ,ＣＨ３ＯＨ完全氧化的Ｔ     

Atomic XAFS as a tool to probe the reactivity of metal oxide catalysts: quantifying metal oxide support effects

The potential of atomic XAFS (AXAFS) to directly probe the catalytic performances of a set of supported metal oxide catalysts has been explored for the first time. For this purpose, a series of 1 wt % supported vanadium oxide catalysts have been prepared differing in their oxidic support material (SiO2, Al2O3, Nb2O5, and ZrO2). Previous characterization results have shown that these catalysts contain the same molecular structure on all supports, i.e., a monomeric VO4 species. It was found that the catalytic activity for the selective oxidation of methanol to formaldehyde and the oxidative dehydrogenation of propane to propene increases in the order SiO2 < Al2O3 < Nb2O5 < ZrO2. The opposite trend was observed for the dehydrogenation of propane to propene in the absence of oxygen. Interestingly, the intensity of the Fourier transform AXAFS peak decreases in the same order. This can be interpreted by an increase in the binding energy of the vanadium valence orbitals when the ionicity of the support (increasing electron charge on the support oxygen atoms) increases. Moreover, detailed EXAFS analysis shows a systematic decrease of the V-Ob(-M(support)) and an increase of a the V-O(H) bond length, when going from SiO2 to ZrO2. This implies a more reactive OH group for ZrO2, in line with the catalytic data. These results show that the electronic structure and consequently the catalytic behavior of the VO4 cluster depend on the ionicity of the support oxide. These results demonstrate that AXAFS spectroscopy can be used to understand and predict the catalytic performances of supported metal oxide catalysts. Furthermore, it enables the user to gather quantitative insight in metal oxide support interactions.     

负载型纳米ZrO2-Al2O3复合载体中ZrO2的负载量对Ni基催化剂性能的影响

采用真空浸渍法在负载型纳米ZrO2-Al2O3复合载体上负载NiO,并用X射线衍射考察了NiO在复合载体上的分散周值.结果表明,该分散阈值与ZrO2-Al2O3复合载体中ZrO2的负载量有关,当ZrO2的负载量为0.60 g/g时,NiO的分散阈值达到最高值0.315 g/g.热重-微分热重和程序升温脱附结果表明,NiO在不同ZrO2负载量的复合载体表面形成不同的相互作用和分布状态,复合载体中ZrO2的负载量影响催化剂表面活性中心的种类和对CO2的吸附.同时考察了不同ZrO2负载量的复合载体Ni基催化剂在CO2重整CH4反应中的活性和稳定性.     

低浓度甲烷甲醇深度氧化Ag/La0.6Sr0.4MnO3催化剂

Ag-modified La0.6Sr0.4MnO3 catalysts were prepared and their catalytic performance for deep oxidation of CH4 and CH3OH at low concentrations were investigated. The results showed that the La0.6Sr0.4MnO3 host catalyst with the perovskite-type nano-crystallite structure displayed considerably high catalytic activity for deep oxidation of CH4 and CH3OH at low concentrations. Ag modification to the La0.6Sr0.4MnO3 host catalyst resulted in significant enhancement of the catalyst activity, making the T95 (the reaction temperature needed for conversion of 95%of CH4 or CH3OH) lowered down to 735K (for CH4) and 421K (for CH3OH) from 813 and 465 K over the Ag-free system under the reaction conditions:0.1MPa,CH4/O2/N2=2/12/86(molar ratio),GHSV=45000 h-1 and CH3OH/O2/N2= 0.2/1.0/98.8 (molar ratio),GHSV=58000 h-1,respectively.The carbon containing product was almost CO2 and the contents of HCHO and CO in the reaction exit gas were both under GC detectable limit in both cases.
The results of spectroscopic characterization indicated that modification by proper amount of Ag-dopant did not change the perovskite structure of the La0.6Sr0.4MnO3 host catalyst as a whole. Interaction of Ag-dopant with the surface of the host catalyst,La0.6Sr0.4MnO3,was in favor of high dispersion of the Ag component at the catalyst surface and led to the oxidation of part of the Mn3+species to Mn4+,resulting in an increase of amounts of the reducible Mnn+ species and a decrease of their reduction temperature. On the other hand, this interaction led also to enhancement of adsorption ability of the catalyst toward O2 at relatively low temperature. High activity of the Ag modified La0.6Sr0.4MnO3 catalyst for CH4 and CH3OH complete oxidation was closely related to high redox-activity of the catalyst and its prominent adsorption-activation ability to O2 at relatively low temperatures.     

低浓度甲烷甲醇深度氧化Ag/La0.6Sr0.4MnO3催化剂

用柠檬酸溶胶－凝胶法制备钙钛矿型Ｌａ０．６Ｓｒ０．４ＭｎＯ３氧化物,并用Ａｇ对其进行修饰,制得Ａｇ／Ｌａ０．６Ｓｒ０．４ＭｎＯ３系列催化剂。结果表明,６％Ａｇ／Ｌａ０．６Ｓｒ０．４ＭｎＯ３催化剂上甲烷或甲醇氧化转化９５％时的反应温度Ｔ９５可低至７３５Ｋ（对ＣＨ４）或４２１Ｋ（对ＣＨ３ＯＨ）;适量Ａｇ的负载修饰并不改变催化剂基质氧化物Ｌａ０．６Ｓｒ０．４ＭｎＯ３的纳米级钙钛矿型结构;Ａｇ的掺杂诱使催     

Analysis of HO2 and OH formation mechanisms using FM and UV spectroscopy in dimethyl ether oxidation

Product formation pathways in the photolytically initiated oxidation of CH3OCH3 have been investigated as a function of temperature (298-600 K) and pressure (20-90 Torr) through the detection of HO2 and OH using Near-infrared frequency modulation spectroscopy, as well as the detection of CH3OCH2O2 using UV absorption spectroscopy. The reaction was initiated by pulsed photolysis with a mixture of Cl2, O2, and CH3OCH3. The HO2 and OH yield is obtained by comparison with an established reference mixture, including CH3OH. The CH3OCH2O2 yield is also obtained through the procedure of estimating the CH3OCH2O2/HO2 ratio from their UV absorption. A notable finding is that the OH yield is 1 order of magnitude larger than those known in C2 and C3 alkanes, increasing from 10% to 40% with increasing temperature. The HO2 yield increases gradually until 500 K and sharply up to 40% over 500 K. The CH3OCH2O2 profile has a prompt rise, followed by a gradual decay whose time constant is consistent with slow HO2 formation. To predict species profiles and yields, simple chlorine-initiated oxidation model of DME under low-pressure condition was constructed based on the existing model and the new reaction pathways, which were derived from this study. To model rapid OH formation, OH direct formation from CH3OCH2 + O2 was required. We have also proposed that a new HCO formation pathway via QOOH isomerization to HOQO species and OH + CH3OCH2O2 --> HO2 + CH3OCH2O are to be considered, to account for the fast and slow HO2 formations, as well as the total yield. The constructed model including these new pathways has successfully predicted experimental results throughout the entire temperature and pressure ranges investigated. It was revealed that the HO2 formation mechanism changes at 500 K, i.e., HCO + O2 via HCHO + OH and the above proposed direct HCO formation dominates over 500 K, while a series of reactions following CH3OCH2O2 self-reaction and OH + CH3OCH2O2 reaction mainly contribute below 500 K. The pressure dependent rate constant of the CH3OCH2 thermal decomposition reaction has been separately measured since it has large negative sensitivity for HO2 formation and is essential to eliminate the ambiguity in the CH3OCH2 + O2 mechanism at higher temperature.     

负载型纳米ZrO2/Al2O3复合载体的制备和表征及其Ni/ZrO2/Al2O3催化性能的研究

以大孔Al2O3为基载体，采用沉积-沉淀法和溶胶-沉积法制备了负载型纳米ZrO2/Al2O3复合载体．用XRD、TEM和比表面与孔径测定等手段对载体进行了表征．结果表明，负载型纳米ZrO2/Al2O3复合载体具有较大的比表面积和适宜的孔径分布，纳米ZrO2在载体上呈单层均匀分布．以CH4-CO2重整制合成气为探针反应，考察了Ni/ZrO2/Al2O3催化剂的活性和选择性．     

ZrO2负载量对负载型纳米ZrO2/Al2O3复合载体的结构及性能影响

ZrO2在基载体Al2O3表面存在分散阈值(0.242 g/gAl2O3).在ZrO2/Al2O3复合载体中,ZrO2负载量不同其分布和粒度大小不同,当ZrO2负载量在0.242 g/gAl2O3-0.60 g/gAl2O3的范围内,ZrO2/Al2O3复合载体中纳米ZrO2的粒子的大小保持在4.2 nm,且单层分布在Al2O3的表面.当ZrO2负载量大于0.60 g/gAl2O3时,纳米粒子的粒径增大,并出现多层分布或堆积.XRD、DSC、HRTEM、XPS、H2-TPR结果表明,随着ZrO2负载量增大,复合载体中纳米ZrO2的分布由单层分布转化为多层或堆积分布,ZrO2负载量为0.60 g/gAl2O3时复合载体表面积最大(164.3 m2/g),ZrO2负载量的继续提高,复合载体的表面积明显下降.     

Fourier transform infrared spectroscopic study of surface acidity by pyridine adsorption on Mo/ZrO2-SiO2(Al2O3) catalysts

Acidity of the oxidic molybdenum catalysts supported on mixed ZrO2-SiO2 and ZrO2-Al2O3 carriers was investigated by Fourier transform infrared spectroscopy of pyridine adsorption. Deposition of molybdenum on ZrO2-SiO2 and ZrO2-Al2O3 supports leads to formation of surface Br?nsted acid sites. The number of the Br?nsted and Lewis acid sites in supported-molybdenum catalysts depends on both the ZrO2 content and the type of the support. With increasing ZrO2 content, the Lewis acid sites increase for both series of catalysts. The Br?nsted acid sites are higher for Mo/ZrO2-SiO2 samples compared to those for Mo/ZrO2-Al2O3 and also increase with zirconia.     

Ni／ZrO2-Al2O3制备表征及催化性能的研究

本文采用浸渍沉淀法制备了不同配比的ZrO2-Al2O3复合载体。并通过浸渍法制备Ni/ZrO2-Al2O3催化剂,以苯加氢制环己烷反应为探针,考察了ZrO2与Al2O3的配比对Ni催化剂催化加氢性能的影响;采用X射线衍射(XRD)、程序升温还原(TPR)、程序升温脱附(TPD)等技术考察复合载体对Ni催化剂的体相结构、还原性能以及表面吸附性能的影响。研究结果表明,ZrO2质量分数为20%的复合载体所负载的Ni催化剂有很好的加氢活性,优于单组分载体负载的Ni催化剂;采用浸渍沉淀法制备的ZrO2-Al2O3复合载体中ZrO2以非晶态形式存在,这是由于Al2O3的存在影响了ZrO2的内部结构;该载体负载的Ni催化剂较其他催化剂更容易被还原,吸附中心数量增加。