MoS^2^-~4在铜表面的配位化学反应

MoS^2^-~4与铜表面作用可以形成几种颜色的簇合物膜。FT-IR, XPS和AES结果表明, 膜中存在Cu-S-Mo键; 簇合物膜含Cu, Mo, S, O四种元素, 分别呈+1, +6,-2, -2价, 并含少量+4和+6价硫; 膜为多分子层的双层结构 . 反应时间越长, 膜越厚;加热后膜层仍含Cu, Mo, S, O 元素, Mo向内层渗透, S则在表面富集, Cu呈+1和+2价, S呈-2, +4, +6价, Mo和O价态不变;膜层是多组分的复杂体系; 其颜色是各化合物吸附、叠加的结果。     

MoS^2^-~4在铜表面的配位化学反应

MoS^2^-~4与铜表面作用可以形成几种颜色的簇合物膜。FT-IR, XPS和AES结果表明, 膜中存在Cu-S-Mo键; 簇合物膜含Cu, Mo, S, O四种元素, 分别呈+1, +6,-2, -2价, 并含少量+4和+6价硫; 膜为多分子层的双层结构 . 反应时间越长, 膜越厚;加热后膜层仍含Cu, Mo, S, O 元素, Mo向内层渗透, S则在表面富集, Cu呈+1和+2价, S呈-2, +4, +6价, Mo和O价态不变;膜层是多组分的复杂体系; 其颜色是各化合物吸附、叠加的结果。     

S2O2-8派生氧化法催化降解水中的甲基橙

 S2O2-8在Ag+的催化作用下可生成 SO-4· 和Ag2+, SO-4· 和Ag2+ 具有极强的氧化能力,其电极电位分别为E0Ag2+/Ag+=1.989 V, E0SO-4·/SO2-4=3.64 V. 本文研究了S2O2-8+Ag+体系中甲基橙的降解情况,并用紫外光谱、总有机碳(TOC)和高效液相色谱/质谱对降解过程进行了表征. 在pH=1的S2O2-8+Ag+体系中,反应8 min时, 5 μmol/L的甲基橙色度去除率达100%. 2 h后,水样中有悬浮物出现,过滤后样品TOC去除率为8.6%; 在同样条件下, Fenton法对甲基橙TOC去除率为10%. 在促使有机物矿化方面, S2O2-8+Ag+法与Fenton法的效果基本相同.     

O3分子在CuO(110)面吸附的密度泛函理论研究

应用密度泛函理论研究了O3分子在2×1 CuO(110)面(S1)和掺杂一个Fe原子的2×1 CuO(110)面(S2)的吸附过程和电子特性. 计算结果表明, O3分子与表面S1和S2有很强的相互作用, O3分子在表面吸附反应的活化能和反应能均为负值, 反应很容易进行. 态密度和电荷密度分析结果进一步证实了O3分子在S1上吸附是桥位化学吸附, 形成表面臭氧化物, 在S2上吸附分解为1个被吸附的表面氧原子和1个自由氧分子. 电子特性分析表明, O3分子与S1和S2相互作用的本质是O3分子的价轨道2p与CuO(110)表面杂化轨道的相互作用.     

担载型Co/ZSM-5催化剂表面Co组分结构与柴油车NO_x净化性能

在摸拟轻型柴油车尾气的反应装置上,结合多种物理化学手段研究了富氧条件下Co/ZSM-5催化剂上Co组分分散状态及其C3H8选择性催化还原NOx性能.结果表明,浸渍法制备的Co/ZSM-5催化剂,ZSM-5表面Co的分散容量约为4.5%,当Co担载量高于4.5%时,Co物种开始在分子筛表面聚集形成Co3O4晶体,发生在Co3O4晶体上强的NOx吸附脱附,对富氧条件下C3H8选择性催化还原NOx是不利的.催化剂上孔内的钴物种主要以Co2+离子形式存在,而孔外表面既存在Co3+物种,也存在Co2+物种,Co3+的相对量随Co担载量的增加而增大.在催化剂孔外表面形成的以Co3+和Co2+结合的含有Co-Co键的低聚态Co Ox物种具有较合适的NOx吸附脱附性能和较强的氧化还原性,是富氧条件下C3H8选择性催化还原NOx反应的主要活性中心,反应需要在相邻的两个Co2+和Co3+活性位上完成.     

室温离子液体电解液中尖晶石LiMn_2O_4的电化学性质

应用循环伏安、恒电流充放电和电化学阻抗技术研究了尖晶石L iMn2O4于室温离子液体电解液中的电化学性质.实验表明,以室温离子液体作电解液,L iMn2O4的首次放电容量可达108.2 mAh/g、循环效率高于90%,温度和电流密度显著影响电极的电化学性能.交流阻抗测定了L i+在电极/电解液相界面迁移的活化能,为55 kJ/mol.根据界面反应的高活化能解释了L iMn2O4在该离子液体电解液中低温性能和倍率充放电性能不佳的原因.     

投影实验之十四——氢碘酸的电解

电解氢碘酸时,在阳极产生碘： 2I-→I2+2e 在阴极有氢气生成： 2H2O+2e→2OH-+H2 利用投影装置可以很清楚地看到阳极上析出的碘晶体和阴极上产生的氢气气泡。一、电极和电解液 1. 阳极阳极为表面有铁锈的铁棒（或粗铁丝）。     

Na_2S_2O_8-Fe~(2+)对田菁胶的氧化降解行为研究

考察了Na2S2O8-Fe2+对田菁胶的氧化降解行为,系统研究了Na2S2O8和Fe2+用量、温度、降解时间和pH值对田菁胶粘度的影响。结果表明,Na2S2O8和Fe2+合适的体积比为3?1。在较低的温度(40℃)和较短的时间(20 min)内Na2S2O8-Fe2+就能使田菁胶粘度下降90%以上。另外,Na2S2O8-Fe2+氧化还原体系在酸性和中性条件下对田菁胶的降解都有良好的降解性能,考虑到在实际生产中的应用,我们认为中性条件下最合适。     

Cu(I)/SO2-4/ZnO和Cu(I)/S2O2-8/ZnO催化剂的制备与表征

采用浸渍法对无定形ZnO分别用稀H2SO4和(NH4)2S2O8溶液处理,制备了SO2-4/ZnO和S2O2-8/ZnO固体酸.通过固体离子交换法制备了Cu(Ⅰ)/SO2-4/ZnO和Cu(Ⅰ)/S2O2-8/ZnO两种催化剂,并采用XRD,FTIR,TPD和TPR等进行了表征.研究结果表明,用稀H2SO4和(NH4)2S2O8溶液分别浸渍处理无定形ZnO,经过500～600 ℃高温焙烧后得到的SO2-4/ZnO和S2O2-8/ZnO固体酸表面形成了Zn3O(SO4)2物种;py-FTIR结果表明,两者均具有B酸中心和L酸中心,进一步的NH3-TPD研究结果证明,制备的固体酸NH3脱附峰均出现在543 ℃附近,属于高强度固体酸.结构分析认为,由于SO2-4强烈的电子诱导作用,SO2-4和ZnO形成的桥式配位物种产生了B酸中心和L酸中心,而其螯合配位形成的物种没有酸性.SO2-4/ZnO和S2O2-8/ZnO固体酸与CuCl进行离子交换所制备的Cu(Ⅰ)/SO2-4/ZnO和Cu(Ⅰ)/S2O2-8/ZnO催化剂的Cu(Ⅰ)易于还原,对甲醇氧化羰基化合成碳酸二甲酯(DMC)表现出较高的活性和选择性,DMC选择性为98.3%,时空收率可达到1.9 g(g\5h).     

胺对锂电池电解液中小分子的稳定作用

用密度泛函理论(DFT)方法在PBE0/6-31+G(d, p)水平上对乙胺、乙二胺分别与电解液中的小分子H2O、HF分子间的相互作用进行理论计算, 并在PBE/TZP 水平上利用能量分解分析(EDA)方法对胺与HF、H2O 结合的II-1、II-2、III-1和III-2模型进行计算分析. 结果表明, 胺类物质都能与HF、H2O形成N…H—F(O)、F(O)…H—N或F(O)…H—C的稳定氢键. 但HF与胺类物质形成的氢键比H2O与胺形成的氢键强, 故胺类物质在电解液中优先稳定HF. 乙二胺与HF、H2O结合的稳定性比乙胺强. 乙胺、乙二胺与HF(H2O)形成的最稳定构型均由F(O)—H…N 和F(O)…H—C 氢键结合形成.     

New Process Simulation Procedure for High-Rate Plasma Jet Machining

Surface figuring using chemically reactive plasma jet machining (PJM) is a promising non-conventional technology for deterministic ultra-precision machining of optical components. Based on chemical reactions between plasma generated radicals and the surface atoms this technology is capable to fabricate complex shaped free form surfaces. Since the material removal rate during PJM depends strongly on the surface temperature which itself is influenced by the jet heat flux to the surface, the arising nonlinear effects on the etch result have to be regarded. Conventionally applied dwell time calculation algorithms do not consider those effects leading to significant machining errors in some cases. In order to improve the machining procedure with respect to deterministic material removal yielding predictable results a process simulation model has been developed. This model considers spatio-temporal variations of surface temperature and temperature dependent material removal and is able to predict the final workpiece topography after machining.     

Influence of machining process on the mechanical behaviour of injection-moulded specimens of talc-filled Polypropylene

The mechanical properties of injection-moulded components are usually obtained by conducting uniaxial tensile tests on dog bone specimens. Current standards do not regulate the machining process used to make the coupons and do not quantify an acceptance limit of the surface roughness. The surface qualities of milling, laser cutting and water jet cutting were examined in this study for 18% talc-filled Polypropylene using optical measurements. It shows that the machining processes influence the surface roughness of the specimen, leading to different strengths at failure of the same thermoplastic material. The specimens machined by the water jet technology produced the roughest sample edges and exhibited the lowest resistance to failure in tensile tests. On the contrary, the milling process generated the best edge quality, which showed repeatable testing results.     

SIMS Analysis of the wear of boron nitride tools for the machining of compacted graphite iron and grey cast iron

Cubic boron nitride (cBN) is a common material for tools for the machining of cast irons at high cutting speed. During the machining of compacted graphite iron (CGI) in continuous cutting the wear of the cBN tools was found to be significantly higher compared to the machining of grey cast iron. This is possibly a result of a heating of the tool surface during the cutting of CGI. One possible reason for the wear is diffusion of some elements from the cutting tool into the CGI or from the CGI into the cutting tool. SIMS measurements were carried out which prove the existence of such diffusion processes. A static model experiment has been performed by heating cBN tools to 700 °C while in contact with CGI or cast iron (CI). SIMS depth profiles of the cBN tools and of CGI/CI show that there is a diffusion of several elements in both directions (B, W and Ti from the cBN tools into the CGI or CI, Fe and Si from the CGI or CI samples into the cBN) up to a depth of 20 μm. Received: 18 March 1999 / Revised: 16 June 1999 / Accepted: 18 June 1999     

Modelling of micro-electrochemical machining parameters used for machining of holes on copper plate

The electrochemical machining is a non-conventional machining process based on the electrolysis principle. It is used to machine various features on conducting engineering materials with the required accuracy and precision. So an attempt has been made to machine micro-holes on a 300 μm thick copper plate as an anode and a hollow stainless steel tool electrode of 250 μm diameter as the cathode. The machining operation is performed on the in-house developed micro-ECM experimental setup with controlled machining parameters voltage, concentration, and duty factor varied in three levels. A full factorial experimental plan is used to study the output responses material removal rate (MRR), radial overcut (ROC), circularity, and taper angle (TA). Later an adaptive neuro-fuzzy inference system (ANFIS) model has been developed and shown the effectiveness of the developed model in the paper. The Sugeno fuzzy model has been used in ANFIS to generate the fuzzy rules required for the model. Out of 27 experiments, 22 machining data are used for training the model, and the remaining 5 machining data are used for testing the developed model. The average error observed between the ANFIS predicted values and experimental values of MRR is 12.56%, circularity is 43.09%, ROC is 13%, and TA is 27.53%, respectively.     

Three dimensional micromachining on aluminum surface by electrochemical wet stamping technique

We proposed an up–down working mode of electrochemical wet stamping technique (EC-WETS) for three dimensional (3D) micromachining on aluminum (Al) surface. 3D microstructures on a Si mold were transferred on to an agarose hydrogel containing 15% NaNO₃, 2% MgF₂, 1% NaOH and 5% glycerin, which acted as the quasi-solid electrolyte for the electrochemical micromachining. The transferred 3D microstructures on agarose hydrogel were then duplicated onto Al surface through anodic dissolution. The micromachining quality was improved by pulse-potential method dramatically with a machining tolerance lower than 200 nm and an average removal rate of 210 nm min^− 1 in the Z direction. This method was proved to be a highly efficient, low cost and green method for 3D micromachining on active metal surface, which would be valuable for the manufacture of microelectromechanical system (MEMS).     

Modifying the surface of TEOS xerogel by metal ion Zn(II)

The removal of 2,4-dichlorophenol from aqueous solution by modified TEOS xerogel has been studied in batch experiments at varying pH (2.0–8.0). Tetraethyl orthosilicate (TEOS) xerogel recently has been considered as an adsorbent which is more active. Surface of the adsorbent due to the outward oxygen atoms in the molecular structure, is negatively charged, so this solid, shows good ability to adsorb metal ions. But because of the negative charge on the surface of the adsorbent, the anions, particularly organic anion compounds are not absorbed. To fix this problem, it can set the metal ions on the surface of the solid. By placing Zn ions on the xerogel, a positive charge on the surface of the adsorbent is made, which increases the ability of the adsorbent to attract 2, 4-dichlorophenol from aqueous solutions. Results show an increase in the adsorption by about 17% on empty xerogel, by about 60% in xerogel modified with metal Zn (II) ion.

     

Measurements of H2S in the Atmosphere

Swamps and tidal flats are believed to he important natural sources of atmospheric H₂S, though it is very difficult to detect the low concentrations of this trace gas above the surface of these regions. In view of this problem an air sampling device has been developed for the sampling of atmospheric H₂S with chemically impregnated filters. The sulfide generated on the filter is analyzed in a washing solution employing a very sensitive fluorescence method. The quality of the method is demonstrated by comparative calibrations. The fluorescence method is calibrated in the liquid phase with standard solutions of sulfide. Furthermore the sampling and analyzing method is calibrated together by using H₂S calibration gases. The detection limit of the method is shown to he 10ng/m³ STP. Data of test-measurements in ambient air and some results of field-measurements in the lower troposphere are presented.     

Direct evaluation of meat spoilage and the progress of aging using biosensors

A direct sensing method for monitoring meat quality was developed. The sensor is composed of an Ag/AgCl electrode and a platinum electrode on which putrescine oxidase or xanthine oxidase were immobilized to estimate bacterial spoilage or the progress of aging, respectively. A potential-step chronoamperometric method was applied in which the potential was stepped from 300 mV to 600 mV. A linear relationship was obtained between 5 and 60 nmol g⁻¹ for putrescine (Put) and 0.05 and 1.0 μmol g⁻¹ for hypoxanthine (Hx). The coefficient of variation was 0.75% for 20 nmol ml⁻¹ Put solution and 2.2 for a meat sample using the putrescine sensor, and 1.09% for 0.25 μmol ml⁻¹ Hx solution and 2.6% for a meat sample using the xanthine sensor. The pH requirements and substrate selectivity were suitable for the direct measurement of substrates on the surface of meat. From the results of practical experiments, the direct sensing method was indicated to be useful with some modifications for the estimation of meat quality during aging.     

Study of the surface properties of a solid solution of vanadium in SnO2 by IR spectroscopy

IR spectroscopy has been used to study the surface properties of a solid solution of vanadium in SnO₂. Adsorption of ammonia and carbon monoxide showed that compounds are formed on the surface of the oxidized Sn/V-oxide sample, the composition of which differs significantly from the solid solution of vanadium. The acid properties of this compound have been studied. The presence of Lewis as well as strong Broensted sites on the surface of the investigated sample has been established.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 4, pp. 505–509, July–August, 1990.