Enhancement of the electrooxidation of ethanol on Pt-Sn-P/C catalysts prepared by chemical deposition process

In this paper, five Pt3Sn1/C catalysts have been prepared using three different methods. It was found that phosphorus deposited on the surface of carbon with Pt and Sn when sodium hypophosphite was used as reducing agent by optimization of synthetic conditions such as pH in the synthetic solution and temperature. The deposition of phosphorus should be effective on the size reduction and markedly reduces PtSn nanoparticle size, and raise electrochemical active surface (EAS) area of catalyst and improve the catalytic performance. TEM images show PtSnP nanoparticles are highly dispersed on the carbon surface with average diameters of 2 nm. The optimum composition is Pt3Sn1P2/C (note PtSn/C-3) catalyst in my work. With this composition, it shows very high activity for the electrooxidation of ethanol and exhibit enhanced performance compared with other two Pt3Sn1/C catalysts that prepared using ethylene glycol reduction method (note PtSn/C-EG) and borohydride reduction method (note PtSn/-B). The maximum power densities of direct ethanol fuel cell (DEFC) were 61 mW cm(-2) that is 150 and 170% higher than that of the PtSn/C-EG and PtSn/C-B catalyst.

The phase transitions of hetero atoms substituted molecular sieves Me-VPI-5(Me=Mg, Ti, Sn, Si) and their influence on spectra structures of Eu(III) ion

The hetero atom substituted aluminophosphate molecular sieves Me-VPI-5(Me = Mgt Ti, Sn, Si) were synthesized hydrothermally. Rare earth ions are originally doped into these microporous materials by aqueous solution ion exchange procedures. The phase transitions of the microporous materials are investigated by high-temperature and high-pressure experimental techniques. The influence of the phase transitions on the rare earth ions' spectral structures is discussed, With the increase of temperature, Eu(II)Mg-VPI-5 is converted into Eu(II)Mg-AIPO(4)-8, then into tridymite phase. The pressure has a notable influence on Eu(II) ion's spectral structures. The spectral structures have changed regularly with the increase of pressure.

杂原子Me－VPI－5（Me＝Mg，Ti，Sn，Si）相转变及其对Eu（Ⅲ）光谱结构的研究

用水热同晶置换法合成了杂原子磷酸铝分子筛Ｍｅ－ＶＰＩ－５（Ｍｅ＝Ｍｇ，Ｔｉ，Ｓｎ，Ｓｉ）．通过水相离子交换法掺杂稀土离子，考察了高温和高压下的相变行为．讨论了相变过程对稀土离子光谱的影响．随着温度升高，Ｅｕ（Ⅲ）Ｍｇ－ＶＰＩ－５先转变为Ｅｕ（Ⅲ）－ＡｌＰＯ４－８，然后又转变成致密的磷石英相．压力对Ｅｕ（Ⅲ）光谱结构具有显著影响．随着压力增加，Ｅｕ（Ⅲ）光谱结构发生规律性变化．

掺Sb、Sn和Cd的In_2O_3的电性研究

本文研究了掺杂Sb、S_n及Cd的In_2O_3的电性质,并与纯的In_2O_3进行比较,得到一些有意义的结果。IO的电导率及载流子浓度主要由氧缺位所致;ITO和ISO的电导率和载流子浓度,主要由掺杂元素所致;掺Sn的电导率、载流子浓度和迁移率高于掺Sb,其原因在于在同样掺杂浓度的条件下,ITO中的中性杂质浓度低于ISO及掺Sn后使电子离域程度增大。在掺Cd浓度高时,随着Cd浓度增加,电导率和载流子浓度均降低。

STUDIES ON DEFECT STRUCTURE AND CATALYTIC PROPERTIES OF SN-MO OXIDES

The present work is devoted to the studies on relationship of structure and activity of Sn-Mo oxides by using XRD, ESR, IR, XPS, TEM and SEM. Eight samples with Mo/(Mo + Sn) rations: 0.0, 0.1, 0.2, 0.4, 0.6, 0.8, 0.9, 1.0 were prepared. On the basis of structure characterization, Sn-Mo oxides can be divided into three groups: Catalysts I with Mo/(Mo + So) less-than-or-equal-to 0.2, Catalysts II with 0.2 < Mo/(Mo + Sn) < 0.8, and catalysts III with Mo/(Mo + Sn) greater-than-or-equal-to 0.8. The solid solution of Mo5+ in tin oxide was formed and the cation vacancy was formed in catalysts I. The solid solution of Sn4+ in molybdenum oxide was formed in catalysts III. The lattice oxygen in catalysts III has higher mobility and reactivity than that in catalysts I. The catalysts III showed higher activity but lower selectivity than that of catalysts I.

用ESR方法研究Sn-Mo氧化物固溶体形成的机理

本文研究了Sn-Mo混合氧化物催化剂的活性与焙烧温度的关系。对Sn_(0.975)Mo_(0.025)催化剂进行了不同焙烧温度的ESR研究,跟踪观察了Sn-Mo混合氧化物固溶体随焙烧温度变化的形成过程。结果表明,焙烧温度在100—300℃之间,钼以钼酸铵微晶高度分散在氧化锡表面;300—550℃时,随温度升高钼逐渐向氧化锡体相扩散;550℃时可能形成嵌入型固溶体,催化活性最好;600℃开始形成置换型固溶体,Mo以Mo~(5+)形式取代氧化锡晶格中的Sn~(4+),此时ESR信号gzz>gxx>gyy。

一种新型的铅钙板栅合金——Pb-Ca-Sn-Al-Na

钠加到Pb—Ca—Sn—Al合金中,可以改善它的延伸率和浇铸性能。对于Pb—Ca—Sn—Al合金来说,钠是有效的变晶剂,它的最佳含量是0.01～0.077％。

Sn-Mo混合氧化物的缺陷结构及催化性能的研究

本文以1-丁烯在水蒸汽存在下选择性氧化制甲乙酮为典型反应,利用 XRD,ESR,IR,XPS,TEM 和 SEM 研究了 Sn-Mo 氧化物的结构与活性的关系.制备了8个样品,A,B,C,D,E,F,G 和 H 的 Mo/(Mo+Sn)分别为0,0.1,0.2,0.4,0.6,0.8,0.9,1.0.根据结构特征,可将 Sn-Mo 氧化物分为三组:第Ⅰ组 Mo/(Mo+Sn)≤0.2;第Ⅱ组0.2

渤海湾地区前第三系构造特征及其演化研究

Based on fine structural interpretation on seismic profiles of buried-hills in Huanghua depression, structural interpretation and balanced cross-section restoration of regional seismic profiles, drawing structural maps of main seismic interfaces, residual strata distribution of different ages in the Bohai Bay region and structural survey in the western Shandong uplifted area and the intracontinental orogeny of Yanshan mountain, the paper has studied pre-tertiary structural styles and tectonic evolution of the Bohai Bay region. There mainly develop 5 types of pre-tertiary structural style that are extension structure, compression structure, strike-slip structure, negative inversion structure and sliding structure in the Bohai Bay region. Among these 5 types of structural style, extension structure develops detachment fault and its controlling fault terrain structure and fault break slop; compression structure develops reverted fold, fault propagation fold, fault bent fold, imbricate thrust structure and triangle zone; strike-slip structure develops positive flower structure, negative flower structure, en-echelon structure and brush structure; negative reversion structure develops Indosinian compression and Yanshanian extension negative reversion structure, late Yanshanian compression and Cenozoic extension negative reversion structure; sliding structure develops interlayer sliding structure and detachment structure. According to Cangdong fault of SN direction, Zhangjiakou – Penglai fault and Qihe – Guangrao fault of NWW direction, the Bohai Bay region can be divided into 6 sub-regions in which structural direction and style is different from each other. Structural maps of bottom boundary of Cenozoic and upper Paleozoic manifest that main NNE structural direction is formed from late Yanshanian to Himalayan movement and minor NWW structural direction and a string of area more than 8000m are mainly suggest that Indosinian tectonic pattern strongly influence on Yanshanian and Himalayan movement. Residual strata distribution characteristics of middle to upper Neoproterozoic in the Bohai Bay region manifest that middle- to neo- aulacogen position may be corresponding to late Mesozoic uplifted zone. Residual Paleozoic distribution characteristics of main ENN suggest that structural alteration should be resulted from late Yanshanian to Himalayan movement while which of minor NWW structures suggest that deeper structure should restrict shallower structure. Structural patterns of main EW fold direction in the Bohai Bay region and thrust structure in eastern part are formed late Triassic in studied area. Granite magma intrusion of early to middle Jurassic mainly develops Yanshan mountain zone. Late Mesozoic rifting basins of NEE direction are widely distributed in the Bohai Bay region and granite magma intrusions are mainly distributed in Tancheng – Rongcheng zone. Mesozoic structural evolution in the Bohai Bay region is related to scissor convergent from east to west between North China plate and Yangtze plate and gradually reinforcing of the west circum-pacific tectonic tract while basin and range province of late Jurassic and early Cretaceous may be mainly related to lithospheric thinning of North China craton in late Mesozoic.

济阳坳陷深层地质构造与演化

Based on geophysical and geological data in Jiyang depression, the paper has identified main unconformity surfaces (main movement surfaces) and tectonic sequences and established tectonic and strata framework for correlation between different sags. Based on different sorts of structural styles and characteristics of typical structures, the paper summarized characteristics and distribution of deep structures, discussed evolution sequence of structure, analyzed the relation between tectonic evolution and generation of petroleum. The major developments are as following: Six tectonic sequences could be divided from bottom to top in the deep zone of Jiyang depression. These tectonic sequences are Cambrian to Ordovician, Carboniferous to Permian, lower to middle Jurassic, upper Jurassic to lower Cretaceous, upper Cretaceous and Kongdian formation to the fourth member of Shahejie formation. The center of sedimentation and subsidence of tectonic sequences distinguished from each other in seismic profiles is controlled by tectonic movements. Six tectonic evolution stages could be summarized in the deep zone in Jiyang depression. Among these stages, Paleozoic stage is croton sedimentation basin; Indosinian stage, open folds of EW direction are controlled by compression of nearly SN direction in early Indosinian (early to middle Triassic) while fold thrust fault of EW – NWW direction and arch protruding to NNE direction are controlled by strong compression in late Indosinian (latter Triassic); early Yanshanian stage (early to middle Jurassic), in relatively weak movement after Indosinian compressional orogeny, fluviolacustrine is deposited in intermontane basins in the beginning of early Yanshanian and then extensively denudated in the main orogenic phase; middle Yanshanian (late Jurassic to early Cretaceous), strike-slipping basins are wide distribution with extension (negative reversion) of NW – SE direction; latter Yanshanian (late Cretaceous), fold and thrust of NE – NNE direction and positive reversion structure of late Jurassic to early Cretaceous strike-slipping basin are formed by strong compression of NW–SE direction; sedimentation stage of Kongdian formation to the fourth member of Shahejie formation of Cenozoic, half graben basins are formed by extension of SN direction early while uplift is resulted from compression of nearly EW direction latterly. Compression system, extension system and strike-slip system are formed in deep zone of Jiyang depression. According to identifying flower structure of seismic profiles and analysis of leveling layer slice of 3D seismic data and tectonic map of deep tectonic interface, strike-slip structures of deep zone in Jiyang depression are distinguished. In the middle of the Jiyang depression, strike-slip structures extend as SN direction, NNW direction in Huimin sag, but NNE in Zhandong area. Based on map of relict strata thickness, main faults activity and regional tectonic setting, dynamic mechanisms of deep structure are preliminary determination. The main reason is the difference of direction and character of the plate’s movement. Development and rework of multi-stage tectonic effects are benefit for favorable reservoir and structural trap. Based on tectonic development, accumulation conditions of deep sub-sags and exploration achievements in recent years, potential zones of oil-gas reservoir are put forward, such as Dongying sag and Bonan sag.

地震层析成像与天山地区的壳幔深部结构研究

The Tien Shan is the most prominent intracontinental mountain belt on the earth. The active crustal deformation and earthquake activities provide an excellent place to study the continental geodynamics of intracontinental mountain belt. The studies of deep structures in crust and upper mantle are significantly meaningful for understanding the geological evolution and geodynamics of global intracontinental mountain belts. This dissertation focuses on the deep structures and geodynamics in the crust and upper mantle in the Tien Shan mountain belt. With the arrival time data from permanent and temporal seismic stations located in the western and central Tien Shan, using seismic travel time tomographic method, we inversed the P-wave velocity and Vp/Vs structures in the crust and uppermost mantle, the Pn and Sn velocities and Pn anisotropic structures in the uppermost mantle, and the P-wave velocity structures in the crust and mantle deep to 690km depth beneath the Tien Shan. The tomographic results suggest that the deep structures and geodynamics have significant impacts not only on the deformations and earthquake activities in the crust, but also on the mountain building, collision, and dynamics of the whole Tien Shan mountain belt. With the strongly collision and deformations in the crust, the 3-D P-wave velocity and Vp/Vs ratio structures are highly complex. The Pn and Sn velocities in the uppermost mantle beneath the Tien Shan, specially beneath the central Tien Shan, are significantly lower than the seismic wavespeed beneath geological stable regions. We infer that the hot upper mantle from the small-scale convection could elevate the temperature in the lower crust and uppermost mantle, and partially melt the materials in the lower crust. The observations of low P-wave and S-wave velocities, high Vp/Vs ratios near the Moho and the absences of earthquake activities in the lower crust are consistent with this inference. Based on teleseismic tomography images of the upper mantle beneath the Tien Shan, we infer that the lithosphere beneath the Tarim basin has subducted under the Tien Shan to depths as great as 500 km. The lithosphere beneath the Kazakh shield may have subducted to similar depths in the opposite direction, but the limited resolution of this data set makes this inference less certain. These images support the plate boundary model of converge for the Tien Shan, as the lithospheres to the north and south of the range both appear to behave as plates.

西江流域环境河水地球化学研究

River is a major component of the global surface water and CO2 cycles. The chemistry of river waters reveals the nature of weathering on a basin-wide scale and helps us understand the exogenic cycles of elements in the continent-river-ocean system. In particular, geochemical investigation of large river gives important information on the biogeochemical cycles of the elements, chemical weathering rates, physical erosion rates and CO2 consumption during the weathering of the rocks within the drainage basin. Its importance has led to a number of detailed geochemical studies on some of the world's large and medium-size river systems. Flowing in the south of China, the Xijiang River is the second largest river in the China with respect to its discharge, after the Yangtze River. Its headwaters drain the YunGui Plateau, where altitude is approximately 2000 meters. Geologically, the carbonate rocks are widely spread in the river drainage basin, which covers an area of about 0.17xl06 km2, i.e., 39% of the whole drainage basin. This study focuses on the chemistry of the Xijiang river system and constitutes the first geochemical investigation into major and trace elements concentrations for both suspended and dissolved loads of this river and its main tributaries, and Sr isotopic composition of the dissolved load is also investigated, in order to determine both chemical weathering and mechanical erosion rates. As compared with the other large rivers of the world, the Xijiang River is characterized by higher major element concentration. The dissolved major cations average 1.17, 0.33, 0.15, and 0.04 mmol I"1 for Ca, Mg, Na, and K, respectively. The total cation concentrations (TZ+) in these rivers vary between 2.2 and 4.4 meq I'1. The high concentration of Ca and Mg, high (Ca+Mg)/(Na+K) ratio (7.9), enormous alkalinity and low dissolved SiO2/HCO3 ratio (0.05) in river waters reveal the importance of carbonate weathering and relatively weak silicate weathering over the river drainage basin. The major elements in river water, such as the alkalis and alkaline-earths, are of different origins: from rain water, silicate weathering, carbonate and evaporite weathering. A mixing model based on mass budget equation is used in this study, which allows the proportions of each element derived from the different source to be calculated. The carbonate weathering is the main source of these elements in the Xijiang drainage basin. The contribution of rainwater, especially for Na, reaches to approximately 50% in some tributaries. Dissolved elemental concentration of the river waters are corrected for rain inputs (mainly oceanic salts), the elemental concentrations derived from the different rock weathering are calculated. As a consequence, silicate, carbonate and total rock weathering rates, together with the consumption rates of atmospheric CO2 by weathering of each of these lithologies have been estimated. They provide specific chemical erosion rates varying between 5.1~17.8 t/km2/yr for silicate, 95.5~157.2 t/km2/yr for carbonate, and 100.6-169.1 t/km2/yr for total rock, respectively. CO2 consumptions by silicate and carbonate weathering approach 13><109and 270.5x10 mol/yr. Mechanical denudation rates deduced from the multi-year average of suspended load concentrations range from 92-874 t/km2/yr. The high denudation rates are mainly attributable to high relief and heavy rainfall, and acid rain is very frequent in the drainage basin, may exceed 50% and the pH value of rainwater may be <4.0, result from SO2 pollution in the atmosphere, results in the dissolution of carbonates and aluminosilicates and hence accelerates the chemical erosion rate. The compositions of minerals and elements of suspended particulate matter are also investigated. The most soluble elements (e.g. Ca, Na, Sr, Mg) are strongly depleted in the suspended phase with respect to upper continent crust, which reflects the high intensity of rock weathering in the drainage basin. Some elements (e.g. Pb, Cu, Co, Cr) show positive anomalies, Pb/Th ratios in suspended matter approach 7 times (Liu Jiang) to 10 times (Nanpan Jiang) the crustal value. The enrichment of these elements in suspended matter reflects the intensity both of anthropogenic pollution and adsorption processes onto particles. The contents of the soluble fraction of rare earth elements (REE) in the river are low, and REE mainly reside in particulate phase. In dissolved phase, the PAAS-normalized distribution patterns show significant HREE enrichment with (La/Yb) SN=0.26~0.94 and Ce depletion with (Ce/Ce*) SN=0.31-0.98, and the most pronounced negative Ce anomalies occur in rivers of high pH. In the suspended phase, the rivers have LREE-enriched patterns relative to PAAS, with (La/Yb) SN=1 -00-1 .40. The results suggest that pH is a major factor controlling both the absolute abundances of REE in solution and the fractionation of REE of dissolved phase. Ce depletion in river waters with high pH values results probably from both preferential removal of Ce onto Fe-Mn oxide coating of particles and CeC^ sedimentation. This process is known to occur in the marine environment and may also occur in high pH rivers. Positive correlations are also observed between La/Yb ratio and DOC, HCO3", PO4", suggesting that colloids and (or) adsorption processes play an important role in the control of these elements.

青藏高原壳幔形变与层圈耦合数值模拟

Based on multi-principle (such as structures, tectonics and kinematics) exploratory data and related results of continental dynamics in the Tibetan plateau, the author reconstructed the geological-geophysical model of lithospherical structure and tectonic deformation, and the kinetics boundary conditions for the model. Then, the author used the numerical scheme of Fast Lagrangian Analysis of Continua (FLAC), to stimulate the possible process of the stress field and deformational field in the Tibetan plateau and its adjacent area, since the convergence-collision between the Indian continent and Eurasia continent about 50Ma ago. With the above-mentioned results, the author discussed the relationship between crustal movement in shallow layer and the deformational process in interior layers, and its possible dynamic constraints in deep. At the end of the paper, an integrative model has been put forward to explain the outline images of crust-mantle deformation and coupling in the Tibetan Plateau. (1) The characteristics of crust-mantle structure of the Tibetan plateau have been shown to be very complex, and vertical and horizontal difference is significant. The general characteristics of crust-mantle of the Tibetan plateau may be that it's layering in depth direction, and shows blocking from south to north and belting from east to west, mainly according to the results of about 20 seismic sections, such as wide-angle seismic profiles, CMP, seismic tomography and so on. (2) The crust had shortened about 2200km, while the shortening is different for different block from south to north in the Tibetan plateau. It is about 11.5mm/a in Himalayan block, about 9.0mm/a in Lhas-Gangdese block, about 7.0mm/a in Qiangtang block and Songpan-Ganzi-Kekexili block, about 8.0mm/a in Kunlun-Qaidam, and about ll.Omm/a in Qilian block, since the convergence-collision between the Indian continent and Eurasia continent about 50Ma ago. Which - in demonstrates the shortening rate decreases from south to north, but this rate increases near the north edge of the Tibetan plateau. The crust thickening rate is about 0.4mm/a in the whole Tibetan plateau; and this rate is about 0.5mm/a in Himalayan block, about 0.4mm/a in Lhas-Gangdese block, about 0.3mm/a in Qiangtang block, about 0.2mm/a in Songpan-Ganzi-Kekexili block and about O.lmm/a in Kunlun-Qaidam-Qilian block, since the convergence-collision between the Indian continent and Eurasia continent about 50Ma ago. This implies that the thickening rate decreases in the blocks of the Tibetan plateau. From south to north, the displacement of eastern boundary in the Tibetan plateau is about 37mm/a in Himalayan block, about 45mm/a in Lhas-Gangdese block, about 47mm/a in Qiangtang block, about 43mm/a in Songpan-Ganzi-Kekexili block, and about 35mm/a in Kunlun-Qaidam-Qilian block, since the collision-matching between the Indian continent and Eurasia continent had happened about 50Ma ago. This implies that the rate of eastward displacement is biggest in the middle of plateau, and decreases to both sides. The transition of S-N compression stress field in Tibetan Plateau, since about 28Ma+ ago, may be caused by two reasons: On one hand, the movement direction of Eurasia continent changed from northward to southward about 28Ma± ago in the northern plateau. On the other hand, the front belt that is located between India continent's and Eurasia continent's convergence-collision, had moved southward to high Himalayan from Indus-Brahmaputra suture almost at the same time in southern plateau. Affected by the stress field, the earlier tectonics rotated clockwise, NE and NW conjugate strike-slip faults developed, and the SN rift formed. This indicated that the EW movement started. The ratio between upper crust and lower crust of different blocks from south to north in the Tibetan plateau during the process of deformation are as following: about 3.5~5:1 in Himalayan block, about 1~5: 3-4 (which is about 1:3o--4 in south and about 4~5:3 in north) in Lhas-Gangdese block, about 1:3~447mm/a in these blocks: Which is located to the north of Banggong-nujiang suture.