In Situ Confocal Microprobe Raman Spectroscopy Study of the Oxygen Species over Cerium Oxide

Ｃｏ￣ｎｄｅｎｃｅａｕｔｈｏｒ．Ｏａｆ（（ｋ６＜ｌ）ａｄｓｐｅｃｉｅｓＰｅａｋｓｗｅｒｅｆｏｕｎｄｔｏｄｉｓａｐｐｅａｒａｔ５７３＇Ｋ．Ｄｕｒｉｎｇｔｈｅｔｅｍｐｅｒａｔｕｒｅｅｌｅｖａｔｉｏｎ，ｔｈｅＣｅＯＺＦＺｇａｎｄＯ２－Ｐｅａｋｓｗｅｒｅｆｏｕｎｄｔｏｂｒｏａｄｅｎａｎｄｓｈｉｆｔｔｏｌｏｗｅｒｗａｖｅｎｕｍｂｅｒｓ．ＴｈｅｆｈａｌｕｅｎｃｙｓｈｉｆｔｗｉｌｈｒｅｓｅｃｔｔｏｔｅｍｐｅｒａｔｕｒｅｉｓａｗｅｌｌｋｎｏｗｎｐｈｅｎｏｍｅｎｏｎｉｎＲａｍａｎｓｐｅｃｔｒｏｓｃｏｐｙｏｆｓｏｌｉｄｓａｎｄｉｔｉｓｒｅｌａｔｅｄｔｏｔｈｅｔｈｅｒｍａ］ｅｘｐａｎｓｉｏｎｏｆｌａｔｔｉｃｅｐａｒａｍｅｔｅｒｓ．Ａｔ１０２３＇Ｋ，ｔｈｅＯ２－ａｄｓｐｅｃｉｅｓ（ａｔ１１５９ｃｍ－ｌ）ａｎｄＣｅＯＺＦ２，（ａｔ４４９ｃｍ－ｌ）ｐｅａｋｓｗｅｒｅｆｏｕｎｄｔｏｒｅｍａｉｎｅｘｉｓｔｉｎｇｏｎｔｈｅｓｕｒｆａｃｅｏｆｃｅｒｉｕｍｏａｌｄｅ．ＷｈｅｎｔｈｅＯＺ－ｐｒｅｔｒｅａｔｅｄＣｅＯＺｓａｍｐｌｅｗａｓｗａｒｍｅｄｓｕｃｃｅｓｓｉｖｅｌｙｉｎａｆｌｏｗｏｆＣｄ，ｔｈｅｒｅａｃｈｏｎｓｏｆＣａｂｗｉｔｈｌａｎｉｃｅｏ     

The Investigation of Oxygen Absorption over LaOF by Means of Raman Spectroscopy

ＴｈｅＩｎｖｅｓｔｉｇａｔｉｏｎｏｆＯｘｙｇｅｎＡｂｓｏｒｐｔｉｏｎｏｖｅｒＬａＯＦｂｙＭｅａｎｓｏｆＲａｍａｎＳｐｅｃｔｒｏｓｃｏｐｙＺＨＯＵｍＸｉａｏ－ｐｉｎｇ,ＣＨＡＯＺｉ－ｓｈｅｎｇ,ＷＡＮＧＳｈｕｉ－ｊｕＷＡＮＨｕｉ－ｌｉｎａｎｄＴｓａｉＫ...     

Elucidating the Role of Oxygen Species in Oxidative Coupling of Methane over Supported MnOx−Na2WO4-containing Catalysts

The present study of oxidative coupling of methane (OCM) over MnO_x−Na₂WO₄/support catalysts demonstrated that the selectivity to C₂H₆ and C₂H₄ (C₂-hydrocarbons) is affected by the kind of support, co-fed water, and the kind of oxidant (O₂ vs. N₂O). In addition to previous studies with MnO_x−Na₂WO₄/SiO₂, an enhancing water effect was obtained using catalysts based on TiO₂- or ZrO₂-containing supports. However, a negative effect on methane conversion was established for SiO₂−Al₂O₃-supported catalysts. Temporal analysis of products with isotopic tracers suggests that the ability of MnO_x−Na₂WO₄ to generate diatomic adsorbed oxygen species depends on the kind of support and is the key property for the water effect. The strength of the water effect on the activity decreases with an increase in the surface area of working catalysts. The kind of support also affects products selectivity due to its influence on the mobility/releasability of lattice oxygen in supported MnO_x−Na₂WO₄. Among the prepared catalysts, MnO_x−Na₂WO₄/TiO₂ was found to be promising for H₂O-assisted OCM. The use of N₂O instead of O₂ further increases the selectivity to C₂-hydrocarbons to 84 % at 6.8 % CH₄ conversion due to the formation of predominantly monoatomic oxygen species from N₂O that selectively convert CH₄ into C₂H₆.     

Reaction Chemistry of W—Mn／SiO2 Catalyst for the Oxidative Coupling of Methane

Reaction chemistry of the OCM reaction on W-Mn/SiO2 catalyst has been reviewed in this account.Initial activity and selectivity,stability in a long-term reaction,reaction at elevated pressures and a modelling test in a stainless-steel fluidized-bed reactor show that W-Mn/SiO2 has promising performance for the development of an OCM process that directly produces ethylene from natural gas.A study on surface catalytic reaction kinetics and used cataly st structure characterization revealed a possible reason why C2 and COx selectivity changed during the long-term reaction.Further improvement of the catalyst composition and preparation metbod should be a future direction of study on OCM reaction over W-Mn/SiO2 catalyst.     

Oxidative Coupling of Methane over Na-W-Mn/Si0_2 Catalysts at Elevated Pressures

Na-Mn-W/SiO2 catalysts were studied for the oxidative coupling of methane (OCM) in a micro fixed bed reactor made of stainless steel reactor at elevated pressures. The effect of operating conditions, such as GHSV, pressure, temperature and CH4/O2 ratio on the catalytic performance of OCM was investigated. The C2+ selectivity of 80.3% was obtained at a CH4 conversion of 16.1% at 750℃, 1.5×105h-1 GHSV, and 0.6 MPa. Also, there is a small output of C3 and C4 hydrocarbons in the tail gas. The results show that unfavorable effects due to elevated pressure can be overcome by increasing GHSV, and the OCM reaction is strongly dependent on the operating conditions at elevated pressures, particularly GHSV and the CH4/O2 ratio.     

Metal-Free Formal Oxidative C−C Coupling by In Situ Generation of an Enolonium Species

Much contemporary organic synthesis relies on transformations that are driven by the intrinsic, so-called “natural”, polarity of chemical bonds and reactive centers. The design of unconventionally polarized synthons is a highly desirable strategy, as it generally enables unprecedented retrosynthetic disconnections for the synthesis of complex substances. Whereas the umpolung of carbonyl centers is a well-known strategy, polarity reversal at the α-position of a carbonyl group is much rarer. Herein, we report the design of a novel electrophilic enolonium species and its application in efficient and chemoselective, metal-free oxidative C−C coupling.     

Oxidative Coupling of Methane over Lithium Doped （Mn＋W）/SiO2 Catalysts

Modification and performance of Li induced silica phase transition of (Mn W)/SiO2 catalyst, under reaction conditions of oxidative coupling of methane (OCM), have been investigated employing textural characterizations and redox studies. Stability and precrystalline form of fresh Li induced silica phase transition catalyst depend on the Li loading. A catalyst, with high lithium loading, destabilizes on OCM stream. This destabilization is not due to Li evaporation at OCM reaction conditions.α-cristobalite is proposed to be an intermediate in the crystallization of amorphous silica into quartz in the Li-induced silica phase transition process. However, the type of crystalline structure was found to be unimportant with regard to the formation of a selective catalyst. Metal-metal interactions of Li-Mn, Li-W and Mn-W, which are affected during silica phase crystallization, are found to be critical parameters of the trimetallic catalyst and were studied by TPR. Role of lithium in Li doped (Mn W)/SiO2 catalyst is described as a moderator of the Mn-W interaction by involving W in silica phase transition. These interactions help in the improvement of transition metal redox properties, especially that of Mn, in favor of OCM selectivity.     

Screening of MgO- and CeO_2-Based Catalysts for Carbon Dioxide Oxidative Coupling of Methane to C_(2+) Hydrocarbons

The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may     

Co-activation of Methane and Ethane over W-Mn/SiO_2 Catalyst

Ｃｏ┐ａｃｔｉｖａｔｉｏｎｏｆＭｅｔｈａｎｅａｎｄＥｔｈａｎｅｏｖｅｒＷ┐Ｍｎ／ＳｉＯ２ＣａｔａｌｙｓｔＺＨＡＮＧＹｕｄｏｎｇＬＩＳｈｕｂｅｎ１）ＬＩＵＹｕＬＩＮＪｉｎｇｚｈｉ（ＳｔａｔｅＫｅｙＬａｂｏｒａｔｏｒｙｏｆＯｘｏＳｙｎｔｈｅｓｉｓａｎｄＳ...     

Pathways of Methane Transformation over Copper-Exchanged Mordenite as Revealed by In Situ NMR and IR Spectroscopy

The reaction of methane with copper-exchanged mordenite with two different Si/Al ratios was studied by means of in situ NMR and infrared spectroscopies. The detection of NMR signals was shown to be possible with high sensitivity and resolution, despite the presence of a considerable number of paramagnetic Cu^II species. Several types of surface-bonded compounds were found after reaction, namely molecular methanol, methoxy species, dimethyl ether, mono- and bidentate formates, Cu^I monocarbonyl as well as carbon monoxide and dioxide, which were present in the gas phase. The relative fractions of these species are strongly influenced by the reaction temperature and the structure of the copper sites and is governed by the Si/Al ratio. While methoxy species bonded to Brønsted acid sites, dimethyl ether and bidentate formate species are the main products over copper-exchange mordenite with a Si/Al ratio of 6; molecular methanol and monodentate formate species were observed mainly over the material with a Si/Al ratio of 46. These observations are important for understanding the methane partial oxidation mechanism and for the rational design of the active materials for this reaction.     

BaF2/La2O3催化剂上甲烷氧化偶联反应活性氧物种的原位红外光谱

用原位红外光谱研究了BaF2/La2O3催化剂上甲烷氧化偶联反应的活性氧物种.结果表明,催化剂经O2预吸附后,在1 108~1 118 cm-1处出现超氧物种O2-的O-O键伸缩振动峰.经18O2同位素交换实验后,原1 108~1 118 cm-1处谱峰的强度减弱,同时在1 086和1 051 cm-1处出现(O18O)-物种和18O2-物种的吸收峰.同位素交换实验进一步确证了1 108~1 118cm-1处谱峰确为O2-物种的吸收峰.在700℃下,O2-物种能够活化CH4生成C2H4,而且O2-物种的消耗量和C2H4的生成量呈很好的消长对应关系.超氧物种O2-是BaF2/La2O3催化剂上甲烷氧化偶联反应的活性氧物种.     

掺杂SrTiO3体系上甲烷氧化偶联反应的研究—活性氧物种的作用

本文采用循环氧化还原法,脉冲反应及TPD等实验手段对钙钛矿型氧化物掺杂SrTiO_3体系上甲烷氧化偶联反应中的活性氧物种的作用进行了研究.结果表明,催化剂由于掺杂产生的未被充分还原的氧物种(O~(α-)(0<α<2)是活化甲烷并促使其发生偶联反应的主要的活性中心,而表面晶格氧(O_L~(2-))则主要使甲烷深度氧化;消耗掉的未被充分还原的氧或晶格氧可以在高温下氧气氛中氧化复原.对于掺杂的SrTiO_3样品,体相中的氧在惰性气氛或还原气氛中可以向表面扩散.吸附氧可能不直接与甲烷作用而主要通过催化剂表面活性氧物种(O~(α-)或O_L~(2-))而起作用.     

甲烷氧化偶联Na-W-Mn/SiO2催化剂的喇曼光谱

Ｎａ Ｗ Ｍｎ／ＳｉＯ２ 是甲烷氧化偶联反应的最好催化剂之一．该体系不仅具有良好的活化甲烷能力和Ｃ２ 烃选择性,且具有较好的稳定性并适合于加压反应 ［１ -３］．对于该催化剂,我们用不同的表征手段做了大量的研究,对各组分的作用及甲烷的活化机理都有了较深入的认识．我们也曾用Ｒａｍａｎ光谱对该体系进行过研究［４,５］,但由于焙烧过程中载体结构及伴随的振动光谱变化,使谱峰的解析出现错误,将载体结构变化出现的新峰归属成了钨氧四面体的畸变．最近我们在确认载体振动光谱及其变化的基础上又对该体系进行了细致的研究,确…     

CaO／La2O3催化剂上的甲烷氧化偶联反应的研究

研究了不同配比的ＣａＯ／Ｌａ_２Ｏ_３催化剂对甲烷氧化偶联反应的催化性能。适当配比的ＣａＯ／Ｌａ_２Ｏ_３催化剂的性能明显优于纯Ｌａ_２Ｏ_３或ＣａＯ，在钙含量为２４％和８１％（Ｃａ／（ｃａ＋Ｌａ））处，Ｃ_２选择性和Ｃ_２收率分别出现两个峰值。同时还发现，１３％ＣａＯ／Ｌａ_２Ｏ_３样品显示出良好的低温催化性能，在５５０℃反应温度下获得了３１．５％的甲烷转化率和４５％的Ｃ_２选择性。并采用ＸＲＤ、ＸＰＳ和Ｃｏ_２ＴＰＤ等技术研究了催化剂的结构。结果表明，ＣａＯ／Ｌａ_２Ｏ_３体系催化剂上没有检测到新物相产生。但是，催化剂中ＣａＯ与Ｌａ_２Ｏ_３两组分之间存在着相互作用，有利于表面活性中心的形成。     

电解银表面氧物种转化的原位拉曼光谱表征

 首次采用原位共焦显微激光拉曼光谱研究了经纯氧预处理后电解银表面吸附的不同氧物种在升温过程中相互转化的情况. 结果发现,当温度低于423 K时, Ag-O2物种缓慢转化为超氧物种 Ag［O-O］-; 温度升高至423 K时, Ag［O-O］-物种将随着时间的延长转化为 Ag-O(α) 物种; 继续升高温度, Ag-O(α) 物种首先转化为 Ag-O-O-Ag 物种,再进一步转化为电解银表面最稳定的 Ag-O(γ) 次表层氧物种并保持至973 K以上. 结合实际反应体系,低温下电解银表面吸附的氧物种主要是分子氧,在类似乙烯环氧化反应的条件下这些分子氧将转化成 Ag-O(α) 物种,而在类似甲醇选择氧化制甲醛的反应条件下又转化为在高温下较稳定的 Ag-O(γ) 物种,根据具体的转化细节推测了可能的机理.     

甲烷氧化偶联Na-W-Mn/SiO2催化剂的喇曼光谱

By calcinating commercial silica gel at 1500℃or adding Na2C2O4 and then calcinating at 850℃,α-cristobalite was formed. On the basis of the vibration spectroscopy of silica support, Na-W-Mn/SiO2 catalyst was characterized by Raman spectroscopy. The results show that the structure of support and the interaction among metal components have significant effect on the dispersion and the structure of metal sites, and the tetrahedrally coordinated [WO4] formed on α-cristobalite surface is the most possible site of methane activation with high C2 selectivity.     

Oxidative Coupling of Methane over W‐Mn/SiO2 Catalyst

W‐Mn/SiO₂ catalyst has been developed in our laboratory (LICP), which is active, selective and stable for oxidative coupling of methane (OCM) in fixed bed and fluidized bed reactors. The research results have been reproduced at different reaction conditions by two groups of J. H. Lunsford (JH‐LL) from Texas A & M University and R. M. Lambert (RMLL) from University of Cambridge respectively. The basic research aspects on this catalyst systems, reaction performances, structure characterization and reaction mechanism were reviewed. A model on two active sites related to W^6+/5+ and Mn^3+/2+ has been suggested for activation of methane and oxygen respectively.     

甲烷氧化偶联反应稀土催化剂表面活性氧种的研究

有关甲烷氧化偶联（OCM）中活性氧种的研究已有许多报道[1~4]．本文利用XPS、O2－TPD、XRD等方法研究了高活性RE2O3体系催化剂上不同表面氧种对偶联反应的影响，并进行了氧种归属，探讨了对偶联反应起关键作用的活性氧种及作用机理．1实验部分1．1催化剂制备及活性评价将高温焙烧后的混合稀土氧化物粉末（Y2O3为主要成分）、MgO及P2O5按一定摩尔比混合研磨调匀、烘干，于950℃焙烧后压环粉碎，取0．38～0．75mm颗粒备用．活性评价在常压固定床流动体系中进行，采用内径为4．5mm的石英反应管，催化剂重量0．8g，反应温度780℃，空速…     

Methane Oxidative Coupling over Fluoride-Promoted Cerium Oxide Catalysts

Since the pioneer work of Keller and Bhasin on the oxidative coupling of methane, many catalyst systems, mostly based on the oxides or complex oxides of alkali metals, alkali earth metals and rare earth metals, have been developed. In some studies, halides, especially chlorides and bromides, have been added to these oxides in order to improve the catalvtic activitv and selectivity. howevek of     

甲烷氧化偶联Ti-La-Li系混合氧化物催化剂

研究了Ti-La-Li三元氧化物的组成、结构及其对甲烷氧化偶联反应的催化性能；用XRD、IR、XPS和SEM等方法对催化剂进行表征，结果表明：在LiTi_xLa_(1-x)O_2系列催化剂中，随x值的不同，可生成LaTi_(1－y)Li_yO_(3-λ)、Li_2TiO_3、La_(0.66)TiO_(2.993)、La_2O_3和Li_(1.33)Ti_(1.66)O_4几种物相，其中，钙钛矿到三元复合氧化物LaTi_(1-y)Li_yO_(3-λ)是甲烷氧化偶联反应的主要活性相，活性位Li~＋-O~－-Ti~(3＋)的形成是活性提高的主要原因．Li_2TiO_3和La_(0.66)TiO_(2.993)是深度氧化活性相，而Li_(1.33)Ti_(1.66)O_4既无偶联活性，也无深度氧化活性．