Synthesis of the complex fluoride LiBaF3 and optical spectroscopy properties of LiBaF3 : M(M = Eu,Ce) through a solvothermal process

The complex fluoride LiBaF3 and LiBaF3:M(M = Eu, Ce) is solvothermally synthesized at 180 degreesC and characterized by means of X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis and infrared spectroscopy. In the solvothermal process, the solvents, molar ratios of initial mixtures and reaction temperature play important roles in the formation of products. The excitation and emission spectra of the LiBaF3:M(M= Eu,Ce) have been measured by fluorescence spectrophotometer. In the LiBaF3: Eu emission spectra, there is one sharp line emission located at 360 nm arising from f --> f transition of Eu2+ in the host lattice, and typical doublet 5d-4f emission of Ce3+ in LiBaF3 powder is shown.

Study of the interaction between lanthanide ions and a supported bilayer lipid membrane by cyclic voltammetry and ac impedance

The interaction of lanthanide ions with a supported bilayer lipid (1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine) membrane (sBLM) was investigated by cyclic voltammetry and ac impedance spectroscopy in this paper, Lanthanide can affect the conformation of the supported bilayer lipid membrane and cause pore formation. Through the pores, Fe(CN)(6)(3) (4) can reach the electrode surface and show its redox behaviour. Furthermore the redox currents or Fe(CN)(6)(3) (4) increased with increasing concentration of lanthanides and leveled off at 1.2 muM for Eu3+. The interaction ability of three lanthanides with sBLM follows the sequence: Eu3+ > Tb3+ > La3+.

Preparation of polymer/silica nanoscale hybrids through sol-gel method involving emulsion polymers (PMMA/SiO2)

The different poly (methyl methacrylate) (PMMA) /SiO2 hybrids were prepared through sol-gel method involving PMMA emulsion (emulsion method) and PMMA/THF solution (solution method). The samples were characterized by differential scanning calorimetry(DSC), thermogravimetry analysis(TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results showed that PMMA/SiO2 composites in nanoscale were prepared by emulsion method, and its size of phase heterogeneity was less than that of solution method. Meanwhile, the polymer emulsion as the reactive medium was more suitable for the formation of SiO2 network.

Polymer/silica nanoscale hybrids through sol-gel method involving emulsion polymers. 1. Morphology of poly(butyl methacrylate)/SiO2

In this article, we report on an approach of using an emulsion polymerized polymer in preparing organic-inorganic nanocomposites through a sol-gel technique. By mixing a polymer emulsion with prehydrolyzed tetraethoxysilane transparent poly(butyl methacrylate)/SiO2, nanocomposites were prepared as shown by TEM. AFM, FTIR, and XPS results show that there is a strong interaction between polymer latex particles and the SiO2 network. Comparison of the emulsion method with a traditional solution method shows that nanocomposites can be prepared by both methods, but there is some difference in their morphology and properties.

High PL quantum efficiency of poly(phenylene vinylene) systems through exciton confinement

Photoluminescence (PL) quantum efficiency is a key issue in designing successful light-emitting polymer systems. Exciton relaxation is strongly affected by exciton quenching at nonradiative trapping centers and the formation of excimers. These factors reduce the PL quantum yield of light-emitting polymers. In this work, we have systematically investigated the effects of exciton confinement on the PL quantum yield of an oligomer, polymer, and alternating block copolymer (ABC) PPV system. Time-resolved and temperature-dependent luminescence studies have been performed. The ABC design effectively confine photoexcitations within the chromophores, preventing exciton migration and excimer formation. An unusually high (PL) quantum yield (above 90%) in the solid state is reported for the alternating block copolymer PPV, as compared to that of similar to 30% of the polymer and oligomer model compounds. (C) 2000 Elsevier Science S.A. All rights reserved.

Formation of self-assembled monolayers on gold electrodes with inclusion complexes of cyclodextrins and viologens

A novel kind of electroactive self-assembled monolayer (SAM) has been successfully prepared through the following procedure: (1) formation of inclusion complexes (denoted as CD/C8VC10SH) between N-(n-octyl)-N'-(10-mercaptodecyl)-4,4'-bipyridinium dibromide (C8VC10SH) and alpha-, beta-cyclodextrin (CD) under a mild condition; (2) spontaneous formation of SAM of CD/C8VC10SH on gold electrodes at room temperature. High-resolution H-1-NMR spectrum was used to confirm the formation of CD/C8VC10SH. Cyclic voltammetry was used to characterize the redox behavior of the resulting monolayers and chronoamperometry and electrochemical impedance spectroscopy to characterize their electron transfer kinetics. It was found that the redox sites in SAM of CD/C8VC10SH are effectively diluted, with a larger electron transfer rate constant than that of SAM of C8VC10SH.

Formation and early development of tetraspores of Gracilaria lemaneiformis (Gracilaria, Gracilariaceae) under laboratory conditions

Morphological and culture studies of tetraspores of Gracilaria lemaneiformis were carried out under laboratory conditions. Relationships of germination rate, diameter and survival rate of tetraspores from 1st generation branches with grads of temperature and irradiance were determined, respectively. The result showed that 1st generation branches is in the majority of the tetraspores shedding and tetraspores from which had highest survival rates than other parts of the sporophytic plant. The time tetraspores used developing from giant unicells to diads, which both existed on the epidermis, then to tetraspores off the matrix, was only approximately 3 weeks all through. However, tetraspores spent more than two months developing into germlings of gametophytes. It was shown that temperature variation (10, 15, 25, 30 degrees C) with the light of 30 mu mol m(-2) s(-1) had significant effects on the germination rate and diameter, but had no apparent effect on survival rate (ANOVA, P < 0.01). Germination rates of tetraspores reached the maximum at 20 degrees C, which was significantly higher than those at other temperature levels (P < 0.01), whereas 15 degrees C seemed to be optimal temperature for the diameter. All the three growth parameters (germination rate, diameter and survival rate) yield highly significant variations with irradiance treatments at room temperature (ANOVA, P < 0.01). The optimal germination rate was detected at the irradiance of 30 mu mol m(-2) s(-1) (P < 0.01). The photon flux density which exceeds 480 nnol m(-2) s(-1) have apparently negative effect on diameter and survival rate. (c) 2005 Elsevier B.V. All rights reserved.

Transformation of accommodation space of the Cretaceous Qingshankou Formation, the Songliao Basin, NE China

Analysis of accommodation space variation during deposition of the Cretaceous Qingshankou Formation in the Songliao Basin, NE China, indicates that accommodation space changed both through time and across the basin as a seesaw movement. The mid-upper Qingshankou Formation is divided into three units. In each unit, changes of accommodation space differ in the southern and northern part of the basin. Increasing accommodation in the southern part is accompanied by a decrease in the northern part, and vice versa. Between the northern and southern basin, there was a neutral belt that is like a fulcrum, called the transformation belt here, where the accommodation did not change to any significant degree. We call this response 'accommodation transformation', whose characteristics are defined by tectonic subsidence analysis, palaeontological and sedimentary analyses. The accommodation increasing belt, decreasing belt, transformation belt and accommodation transformation boundary together constitute the accommodation transformation system. The recognition of accommodation transformation in the Songliao Basin provides a new insight into sequence stratigraphy and might be widely applicable.

高邮凹陷陈堡及陈堡东地区油气成藏规律研究

With the development of petroleum exploration in Gaoyou Depression, both old and new areas have been the active exploration targets, so the study of petroleum accumulation is significant to the petroleum exploration in the study area and the integrated oil and gas accumulation theory. Based on hydrocarbon accumulation theory and systematical research methods and combined with the structural characteristics of Gaoyou Depression, Chenbao and East of Chenbao were selected as the study areas in this dissertation, oil and gas migration pathways, accumulation periods, as well as accumulation models were studied, and favorable exploration targets were proposed. There develop three sets source rocks, which are Tai-2 Member, Fu-2 Member and Fu-4 Member respectively. Tai-2 Member is the predominant source rock in the eastern part. Fu-2 Member mainly occurs in the northern slope, while Fu-4 Member develops in the deep depression. In the study area, oil mainly comes from Fu-2 Member of Liuwushe subsag. The lower limit of TOC is 0.4%, and active source rock mostly distributed in the south fault-step zone. The source rock in Liuwushe subsag began to generate hydrocarbon in the late of Dainan depositional stage and the threshold was 2300m. The macro and micro characteristics of reservoirs and the reservoir heterogeneity characteristics of the Fu-1 Member were studied systematicly. The results show that Fu-1 Member, which has better reservoir properties, are medium porosity-medium permeability reservoir. The reservoir permeability has good correlation with porosity connectivity. The reservoirs have strong dissolution, pores are mainly thin to medium throat, and throat radii are distributed concentratedly, the sorting is good and pore structures are homogeneous. Sandstone reservoirs whether in the plan view, interlayer or in layers have a certain degree of heterogeneity, in particular, the heterogeneity in layers directly affect and control the oil and gas migration and accumulation. By analyzing the lithology correlation of the fault walls, shale smear, cross section stress, the configuration of fracture active periods and hydrocarbon generation and expulsion periods and fuzzy comprehensive evaluation, the main faults sealing were evaluated. The results show that the faults in Chenbao and East of Chenbao had poor sealing properties in Sanduo period and could be used as the migration pathways at that time. After Sanduo period, the tectonic stress fields in the area changed largely, and, consequently, the fault properties converted from tensional shear to compressive shear, the faults changed progressively from close to open, so the faults sealing became better and were conducive to the preservation of oil and gas reservoirs. According to the seismic event suspension modes and profile configurations above and under the unconformities, combined with tectonic evolutions of the study areas, the unconformity types can be classified into truncation unconformity, overlapped unconformity and parallel unconformity and the distribution characteristics of unconformities in the plan view was also studied. The unconformity structure was divided into basal conglomerate, weathered clay and semi-weathered layer vertically in the study area and this kind of structure make unconformities to be effective oil and gas migration pathways and is significant to hydrocarbon accumulation in a parts of areas. With the analyses of typical oil and gas reservoirs in the study area, combined with the research results of pathway systems, hydrocarbon accumulation models were established and the oil and gas accumulation laws in Chenbao and East of Chenbao analyzed. The oil and gas came from Liuwushe subsag and Liuliushe subsag. The oil and gas from Liuwushe subsag mainly migrated from the structural high parts into the fault-step zone along strata in northeast direction, a part of them migrated upward into the fault-step zone and the Wubao low uplift along Wu-1 Fault in northeast direction. The oil and gas from Liuliushe subsag mainly migrated into the upper reservoirs through Wu-2 fault, and lesser oil and gas migrated into the fault-step zone because of the controls of cross-section orientation, depression center and the hydrocarbon formation tendency. The favorable exploration targets in Chenbao and East of Chenbao have been concluded: the southern fault-step zone is a favorable oil and gas accumulation zone of Liuwushe subsag, and they are fault block reservoirs where fault acted as the barriers, the main target intervals are Fu-1 Member and Fu-3 Member in palaeocene; Oil and gas in the middle and northern fault-step zone mainly laterally migrated from the south areas, and the main target interval is Fu-3 Member in palaeocene; Fu-1 Member and the reserviors above the Wubao subsag are still the focuses in future explorations. The results of this study have important guiding significance for the future oil and gas exploration.

子洲—清涧地区上古生界储层综合研究

The exploration and study in recent years shows that the upper Paleozoic in the east of Ordos Basin possesses major exploration potential, so it is necessary to have a comprehensive and synthetic research in this area. Following the guideline of T.A. Cross’s high resolution sequences stratigraphy and combined with sedimentology, the strata and sequence in the research area are divided and correlated. This paper emphasizes on the reservoir in this area and its major fruits are: Firstly, form the framework of the high sequence stratigraphy through mainly studying on the data of core, well drilling and field section combining. Then, think that the best reservoir formation mainly appears in the middle or lower part of long arising semi-cycle, and focus on A type and C1 middle sequence cycle that contributes to the development of formation. Next, think the sedimentary source mainly comes from the epimetamorphic crystalline basement in the north of the Ordoes Basin through analyzing depositional background, researching on sandstone petrography, distribution characteristics of the sedimentary system as well as researching on heavy mineral combination characteristics. Fourthly, give priority to Zizhou-Qingjian area for the first time and gain seven lithofacies paleography maps in the No.2 member of Shanxi and the No.8 member of Shihezi through using the method of isochronal lithofacies paleogeography mapping, then bring forth that Sh2 is mainly developed a type I sequence under the margin of ramp lake-basin background. Fifthly, through researching on the characteristics of reservoir petrography and diagenesis, think that all researched areas experienced compaction and cementation, and there is different types of rocks, only little of the primary pores that are made up of litharenite and lithoclastic quartz sandstone is left, while in lithoclastic quartz sandstone, there are still many primary pores Sixthly, through studying on pore types, microstructure, as well as physical property on the key formation, think that the researched area mostly appears typical low pore, low porosity and permeability, which mainly result from sedimentary and diagenesis. Lastly, through researching on classified evaluation in the key formation, productivity analysis, and combing with reservoir distribution, the researched area is divided into three parts, and think that exploration should be emphasized on formation I and II. The characteristics of sandstones distribution in Sh23 member, gas formation distribution and open flow capacity of exploitation well are all consistent properly with the results of reservoir comprehensive evaluation in this thesis proved by the gas production development in 2006.

三峡库区巴东组泥灰岩溶蚀作用与岩体力学性质弱化研究

Abstract The karsrt erosion engineering geology became a highlight problem in recent years, in particularly, the karst erosion of marlite of Badong formation made the rock mechanics weaken in Three Gorges Reservoir area, which reduces the safety of slope. During the immigrant construction, many high slopes have been formed, whose instabilities problems pose serious threats to the safety of the people and properties. The accidents of the slope failure take place now and then. By testing, it has been found that the karst erosion pattern and dissolution rate of marlite are not weaker than that of the pure limestone. Furthermore, owning to the weathering and unloading, the karst erosion of the marlite will reach certain depth of the slope, which is named infiltrated karst erosion. The karst erosion made the rock mass quality of slope or foundation worse in a large scale. The karst erosion geological disasters, taken place or not, has become the main restrictive factors to the social stability and economic development. Thus the karst erosion process and mechanism of marlite of Badong formation are studied as the main content of this dissertation. The weakening characteristic of rock mass mechanics parameters are studied along with the rock mass structure deformation and failure processes in the course of the karst erosion. At first, the conditions and influencing factors of the karst erosion are analyzed in the investigative region, on the basis of different karst erosion phenomenon of the marlite and different failure modes of slope. Then via indoor the karst erosion tests, it is analyzed that the karst erosion will change the rock mass composition and its structure. Through test, the different karst erosion phenomena between micro and macro have been observed, and the karst erosion mechanism of the marlite has been summarized. Damage theory is introduced to explain the feature of dissolution pore and the law of crack propagation in the marlite. By microscope and the references data, it can be concluded that the karst erosion process can be divided into rock minerals damage and rock structural damage. And the percent of karst erosion volume is named damage factor, which can be used to describe the quantify karst erosion degree of marlite. Through test, the rock mechanical properties in the different period of karst erosion are studied. Based on the damage mechanics theory and the test result, the relation between the karst erosion degree of marlite and weakening degree of mechanical properties is summarized. By numerical simulations, the karst erosive rock mass mechanics is verified. The conclusion is drawn as below: to the rock mass of marlite, the karst erosion damage made mechanics parameters variation, the deformation modulus, cohesion, and inter friction angle reduce as the negative exponent with the increasing of the karst erosion volume, however, the Poisson ratio increases as the positive exponent with the karst erosion volume increasing. It should be noticed that the deduced formulations are limited to the test data and certain conditions. It is suitable to the rock mass parametric weakening process after the karst erosion of marlite in Three Gorges Reservoir area. Based on the failure types of marlite slope in the field, the karst erosion and weathering process of rock mass are analyzed. And the evolution law of deformation and failure of the marlite mass is studied. The main failure feature of the marlite slope is the karst erosive structure subsidence mode in Three Gorges Reservoir area. The karst erosive structure subsidence mode is explained as follows: the rock mass undergoes the synthetic influence, such as weathering, unloading, corrosion, and so on, many pores and cavities have been formed in the rock mass interior, the rock mass quality is worsen and the rock mass structure is changed, and then the inherent structure of rock mass is collapsed under its gravity, therefore, the failure mode of compaction and subsidence take place. Finally, two examples are used to verify the rock mass parameters in Three Gorges Reservoir area, and the relationship between the marlite slope stability and the time of karst erosion is proposed.

陕北地区石家湾-李家岔探区三叠系延长组石油成藏条件分析

Shijiawan –Lijiacha area, lying on the northeastern part of the Shanbei Slope of Ordos Basin, was selected as studying area. The previous explorations proved that the 2nd segment and 6th segment of the Yanchang Formation are the most important oil-bearing formations. It is indicated that the sedimentary facies and reservoir characteristics restricted the hydrocarbon accumulation regularity. Therefore, with petrology methodologies, such as outcrop observation, core description, geophysical logging interpretation, thin section determination, scanning electron microscope, as well as rock property analysis, the reservoirs was were systematically studied and characterized. The sedimentary micro-facies, seals, reservoir-seal combines, migration pathways and entrapping modes were taken into account. The author tempted to establish a base for further studies on reservoirs and on petroleum geology, and to provide some reliably geological evidences for later prospect activities. It was found that the sediments in the 2nd and 3rd segments of the Yanchang Formation in Shijiawan –Lijiacha area were deposited in braided rivers, and most sandy-bodies were identified as channel sandbars. The 4+5th and 6th segments were principally deposited in deltaic-plain environment, consisting of corresponding sub-facies such as distributary channels, natural levee, crevasse-splay and marsh. The skeleton sandy-bodies were identified as sandy sediments of distributary channels. The sand grains in reservoir in studied area possess generally low mineralogical maturity and moderate structural maturity, and the form of pores may be classified into intergranular types and dissolved types. Most reservoirs of Yanchang Formation in Shijiawan –Lijiacha area belong to extreme low-porosity low-permeability ones (type III), and the 2nd sediments belongs to low permeability one (type II) and the 6th segment belong to super low-permeability one(type Ⅳ). The reservoirs in the 2nd segment behave more heterogeneous than those in the 6th segment. The statistic analysis results show that, for 6th and 4+5th segments, the high quality reservoir-seal combines may be found everywhere in the studied area except in the northwest and the southwest parts; and for 1st and 2nd segments, in the northeast, central and southwest parts Petroleum migration happened in the duration of the Early Cretaceous period in both lateral and vertical directions. The migration paths were mainly constructed by permeable sandy-bodies. The superimposed channel sandy-bodies consist of the principal part of the system of carriers. the vertical fractures, that may travel through the seals between reservoirs, offered the vertical paths for migrating oil. It may be synthesized that oil coming from south kitchens migrated first laterally in carriers in the 6th segment. When arrived at the studied area, oil will migration laterally or/and vertical within both the sandy-bodies and fractures, in a climbing-stair way. The results demonstrate that the oil was entrapped in traps structure-lithology and/or lithology traps. In some cases, the hydrodynamic force may help to trap oil. Accumulation of oil in the area was mainly controlled by sedimentary facies, seals, structure, and heterogeneity of reservoir in the 2nd, 4+5th and 6th segments. Especially, the oil distributions in both the 2nd and 6th segments were obviously influenced by seals in the 4+5th segment. The existence of seals in 1st segment seems important for accumulation in the 2nd segment.

松辽盆地南部大情字井地区CO2埋存体地质格架及储层建模

Increasing attentions have been paid to the subsurface geological storage for CO2 in view of the huge storage capacity of subsurface reservoirs. The basic requirement for subsurface CO2 storage is that the CO2 should be sequestrated as supercritical fluids (physical trapping), which may also interact with ambient reservoir rocks and formation waters, forming new minerals (chemical trapping). In order to the effective, durable and safe storage for CO2, enough storage space and stable sealing caprock with strong sealing capacity are necessitated, in an appropriate geological framework. Up till now, hydrocarbon reservoirs are to the most valid and appropriate CO2 storage container, which is well proven as the favorable compartment with huge storage capacity and sealing condition. The thesis focuses on two principal issues related to the storage and sealing capacity of storage compartment for the Qingshankou and Yaojia formations in the Daqingzijing block, Southern Songliao Basin, which was selected as the pilot well site for CO2-EOR storage. In the operation area, three facies, including deltaic plain, deltaic front and subdeep-deep lake facies associations, are recognized, in which 11 subfacies such as subaqueous distributary channel, river- mouth bar, interdistributary bay, sheet sandbody, crevasse splay and overflooding plain are further identified. These subfacies are the basic genetic units in the reservoir and sealing rocks. These facies further comprise the retrogradational and progradational depositional cycles, which were formed base- level rise and fall, respectively. During the regressive or lake lowstand stage, various sands including some turbidites and fans occurred mostly at the bottom of the hinged slope. During the progradation stage, these sands became smaller in size and episodically stepped backwards upon the slope, with greatly expanded and deeped lake. However, most of Cretaceous strata in the study area, localized in the basin centre under this stage, are mainly composed of grey or grizzly siltstones and grey or dark grey mudstones intercalated with minor fine sandstones and purple mudstones. On the base of borehole and core data, these siltstones are widespread, thin from 10 to 50 m thick, good grain sorting, and have relative mature sedimentary structures with graded bedding and cross- lamination or crossbeds such as ripples, which reflect strong hydrodynamic causes. Due to late diagenesis, pores are not widespread in the reservoirs, especially the first member of Qingshankou formation. There are two types of pores: primary pore and secondary cores. The primary pores include intergranular pores and micropores, and the secondary pores include emposieus and fracture pores. Throat channels related to pores is also small and the radius of throat in the first, second and third member of Qingshankou formation is only 0.757 μm, 0.802 μm and 0.631 μm respectively. In addition, based on analyzing the probability plot according to frequency of occurrence of porosity and permeability, they appear single- peaked distribution, which reflects strong hetero- geneity. All these facts indicate that the conditions of physical property of reservoirs are not better. One reason may be provided to interpret this question is that physical property of reservoirs in the study area is strong controlled by the depositional microfacies. From the statistics, the average porosity and permeability of microfacies such as subaqueous distributary channel, channel mouth bar, turbidites, is more than 9 percent and 1md respectively. On the contrary, the average porosity and permeability of microfacies including sand sheet, flagstone and crevasse splay are less than 9 percent and 0.2md respectively. Basically, different hydrodynamic environment under different microfacies can decide different physical property. According to the reservoir models of the first member of Qingshankou formation in the No. well Hei47 block, the character of sedimentary according to the facies models is accord to regional disposition evolution. Meantime, the parameter models of physical property of reservoir indicate that low porosity and low permeability reservoirs widespread widely in the study area, but the sand reservoirs located in the channels are better than other places and they are the main sand reservoirs. The distribution and sealing ability of fault- fractures and caprock are the key aspects to evaluate the stable conditions of compartments to store CO2 in the study area. Based on the core observation, the fractures widespread in the study area, especially around the wells, and most of them are located in the first and second member of Qingshankou formation, almost very few in the third member of Qingshankou formation and Yaojia formation instead. In addition, analyzing the sealing ability of eleven faults in the three-dimensional area in the study area demonstrates that most of faults have strong sealing ability, especially in the No. well Hei56 and Qing90-27. To some extent, the sealing ability of faults in the No. well Hei49, Qing4-6 and Qing84-29 are worse than others. Besides, the deposition environment of most of formations in the study area belongs to moderately deep and deep lake facies, which undoubtedly take advantage to caprocks composed of mudstones widespread and large scale under this deposition environment. In the study area, these mudstones distribute widely in the third member of Qingshankou formation, Yaojia and Nenjiang formation. The effective thickness of mudstone is nearly ~550m on an average with few or simple faults and fractures. In addition, there are many reservoir beds with widely- developed insulated interbeds consist of mudstones or silty mudstone, which can be the valid barrier to CO2 upper movement or leakage through diffusion, dispersion and convection. Above all, the closed thick mud caprock with underdeveloped fractures and reservoir beds can be taken regard as the favorable caprocks to provide stable conditions to avoid CO2 leakage.

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts were investigated by the TPR (temperature programmed reaction) method, and the active sites were studied by CO-TPD, TPSR (temperature programmed surface reaction of preadsorbed CO by H-2) and XPS techniques. The TPR results indicated that ethanol and acetaldehyde might be formed through different intermediates, whereas ethanol and methanol might result from the same intermediate. Results of CO-TPD, TPSR, and XPS showed that on the Rh-based catalyst, the structure of the active sites for the formation of C-2-oxygenates is ((RhxRhy+)-Rh-0)-O-Mn+ (M=Mn or Zr, x>>y, 2 less than or equal ton less than or equal to4). The tilt-adsorbed CO species is the main precursor for CO dissociation and the precursor for the formation of ethanol and methanol. Most of the linear and geminal adsorbed CO species desorbed below 500 K. Based on the suggested model of the active sites, detailed mechanisms for the formation of acetaldehyde and ethanol are proposed. Ethanol is formed by direct hydrogenation of the tilt-adsorbed CO molecules, followed by CH2 insertion into the surface CH2-O species and the succeeding hydrogenation step. Acetaldehyde is formed through CO insertion into the surface CH3-Rh species followed by hydrogenation, and the role of the promoters was to stabilize the intermediate of the surface acetyl species. (C) 2000 Academic Press.