分级纳米多孔铋电化学传感器用于镉离子的检测

采用电化学方法实现对水溶液中重金属离子的超灵敏检测是分子生物学、环境学和医学等领域长期研究的课题,而如何制备具有高比表面积和快速响应特性的电极则是电化学痕量检测的关键。以双相合金Mg₇₉Bi₂₁条带为前驱体,通过一步脱合金法制备了分级纳米多孔铋（hierarchical nanoporous bismuth, HNBi）电极,结合方波阳极溶出伏安法,实现了对水溶液中Cd²⁺的快速检测,检测极限低于10⁻⁹ mol/L,线性动态响应范围介于10⁻⁸ mol/L和10⁻⁶ mol/L之间。HNBi电极绿色环保,在电化学检测领域显示出巨大的应用潜力。     

生物法同时脱除高温烟气中SO2和NOx的实验研究

 对采用生物膜填料塔处理高温烟气中的SO₂和NO_x进行了实验研究,结果表明,生物膜填料塔能够有效地同时去除高温烟气中的SO₂和NO_x.在65 ℃,循环液流量4.0~7.0 L/h,pH=1.5,停留时间150 s,SO₂进气质量浓度2 000~3 000 mg/m³,NO_x进气质量浓度500~1 000 mg/m³的操作条件下,生物膜填料塔对SO₂的去除率可达99.9%以上,对NO_x的去除率为60.2%.     

阳极氧化Ti-6Al-4V合金表面TiO2多孔膜的制备及研究

在一定浓度的H₂SO₄溶液中对Ti-6Al-4V合金表面进行阳极氧化处理,通过改变阳极氧化处理的电压、氧化时间和电解液浓度,研究了预处理工艺参数对钛合金表面形貌、物相、润湿性及粗糙度的影响.试验结果表明：钛合金经过阳极氧化处理后,表面出现了二氧化钛（TiO₂）纳米多孔结构,多孔氧化膜由锐钛矿型和金红石型TiO₂组成;在0.5 mol·L^-1 H₂SO₄溶液中,随着阳极氧化电压的增加,多孔膜的孔径逐渐增大,基体表面与模拟体液（SBF）的接触角明显降低,经120 V氧化处理的试样表面接触角由预处理前的52.8°降至16.9°左右,具有良好的润湿性;并且试样表面的粗糙度明显增加,在电压为120 V时粗糙度达到0.56 μm.在电压120 V时,随着阳极氧化时间或电解液浓度的增加,TiO₂多孔膜的含量和孔径尺寸逐渐增大,试样表面的润湿性和粗糙度也不断增加,在氧化时间10 min或电解液浓度0.5 mol·L^-1时达到最大,氧化时间大于10 min或电解液浓度高于0.5 mol·L^-1时,试样表面出现裂纹,多孔结构被破坏.     

固体超强酸SO2－4／ZrO2形成机理的研究

The formation of SO^2－₄／ZrO₂ solid superacid is studied with FT-IR、XRD and SEM techniques．Subtractive FT-IR measurement indicates the existence of chemical bonds between ZrO₂  and H₂SO₄,XRD determination reveals that the strength of SO^2－₄／ZrO₂ superacid strongly depends on temperature of calcination and reaches a maximum as the ZrO₂ transforms into tetragonal crystal phase.SEM analysis shows that the morphology of ZrO₂ surface is changed due to treatment of H₂SO₄.This catalyst shows higher esterification activity for synthesis of dibutyl moleate which is excellently related with the results of surface analysis.     

金属离子对钢在没食子酸/硫酸介质中的腐蚀行为研究

 用失重法研究了4种金属离子(Na⁺,Zn²⁺,Cu²⁺,Fe³⁺)在0.5 mol/L H₂SO₄以及500 mg/L没食子酸+0.5 mol/L H₂SO₄介质中在20℃对冷轧钢腐蚀行为的影响.结果表明:Cu²⁺对钢的腐蚀起抑制作用;而其余3种金属离子(Na⁺,Zn²⁺,Fe³⁺)对钢的腐蚀起加速作用.在相同条件下,冷轧钢在0.5 mol/L H₂SO₄溶液中的腐蚀速率顺序为:Cu²⁺2++3+;而在500 mg/L没食子酸+0.5 mol/L H₂SO₄介质中,腐蚀速率顺序为:Cu²⁺2+3++.     

Ni-W-Co三元合金镀层电镀工艺的研究

采用电化学沉积法在316L不锈钢基体材料上制备Ni—W—Co三元合金镀层。利用正交试验初步确定电镀液的配方。通过拉伸试验和电化学腐蚀试验分别测试镀层的结合性能和耐腐蚀性能。另外,测试了镀层的显微硬度。结果表明,镀液主要成分对镀层粗糙度影响程度大小为：硫酸镍 > 柠檬酸钠 > 光亮剂1 > 光亮剂2。镀液pH为5.0～5.5、电流密度为3 A·dm^—2时,镀层抗拉强度可达21 MPa。镀液的pH为5.0时,镀层硬度值最高。Na₂WO₄含量为30 g·L^—1时,镀层硬度高达590（HV）。CoSO₄含量为30 g·L^—1时,镀层的耐蚀性能最佳。     

Mg-Zn-Ce非晶合金力学与耐蚀性能的研究

镁合金作为生物可降解材料具有很多优势,但传统多晶镁合金腐蚀速率过快的问题限制了其更广泛的应用。与多晶镁合金相比,非晶态镁合金因具有独特的无定形结构,使其耐腐蚀能力比多晶镁合金的要好。采用铜辊甩带法制备得到了新型Mg_70−xZn₃₀Ce_x（x=2, 4, 6和8）非晶镁合金,并对其进行了力学性能和耐腐蚀性能的研究。结果表明：x为4和6时,Mg-Zn-Ce非晶合金的非晶形成能力最好;Ce的添加可以有效改善镁基非晶合金的脆性,使其弹性模量低于60 MPa,与人骨相似,从而能有效避免植入后因弹性模量过大导致的应力遮蔽效应的产生;同时,Ce的添加显著地提高了合金的耐腐蚀性,使其开路电位达到-0.2 V,腐蚀电流密度低至10^-6 A/cm²。     

燃煤电厂锅炉PM2.5现场实测与排放特征研究

采用自设固定源PM_2.5稀释采集系统对陕西省关中地区多个燃煤电厂烟气中的颗粒物开展了现场实测与样品化学源组分分析。结果表明：4个燃煤电厂PM_2.5、PM₁₀占颗粒物比重差异较大（PM_2.5占比范围为6.92%~54.34%,PM₁₀占比范围为36.36%~73.02%）;4个燃煤电厂数浓度水平最高值（2.0×10⁴~4.0×10⁵个/cm³）差异较大,相差约1个数量级;燃煤电厂PM_2.5小粒径段颗粒物质量浓度占比大多较低,但其对PM_2.5数浓度贡献却很大（最小值>95%）,大粒径段颗粒物则相反;煤粉炉PM₁/PM_2.5较大,占比范围为35.29%~51.35%,循环流化床锅炉PM₁/PM_2.5较小,占比范围为16.62%~21.47%;SO₄^2-是燃煤电厂PM_2.5中最丰富的离子成分,各电厂SO₄^2-占总离子浓度比重范围为50.02~65.52%,Na⁺和Ca²⁺位于第2或第3位;各燃煤电厂主要检出无机元素是Si、Al、Ca、Na、Fe、Na等地壳元素;燃煤电厂PM_2.5、PM₁₀和颗粒物的排放因子范围分别为0.001~0.028 kg/t、0.002~0.086 kg/t、0.003~0.236 kg/t;除尘设施组合越复杂先进,排放因子就可能越小。     

3种观赏性石斛的光合特性比较研究

为探明3种观赏性石斛属Dendrobium Sw.植物在光合生理方面的差异,为其栽培及规模化种植提供理论依据。本研究以3种观赏性石斛(叠鞘石斛D.denneanum Kerr.、流苏石斛D.fimbriatum Hook.和束花石斛D.chrysanthum Wall.ex Lindl.)为材料,测定其叶片的光响应曲线、CO₂响应曲线及叶绿素相对含量(SPAD值),探究其光合特性。结果表明,叠鞘石斛、流苏石斛和束花石斛3种石斛属植物的光补偿点(LCP)分别为2.15 μmol·m^-2·s^-1、3.74 μmol·m^-2·s^-1、1.79 μmol·m^-2·s^-1,光饱和点(LSP)分别为995.09 μmol·m^-2·s^-1、679.44 μmol·m^-2·s^-1、712.28 μmol·m^-2·s^-1,LCP均低于5 μmol·m^-2·s^-1,LSP均低于1 000 μmol·m^-2·s^-1,属于典型的阴生植物,具有较强的耐阴性;3种石斛的最大净光合速率(P_max)分别为3.54 μmol·m^-2·s^-1、3.86 μmol·m^-2·s^-1、4.03 μmol·m^-2·s^-1,表观量子效率(AQY)分别为0.042,0.044和0.051,束花石斛的P_max和AQY最大,光合作用能力较强。3种石斛的CO₂响应曲线中,最大净光合速率(A_max)大小依次为叠鞘石斛(11.99 μmol·m^-2·s^-1)、流苏石斛(10.87 μmol·m^-2·s^-1)、束花石斛(4.75 μmol·m^-2·s^-1),叠鞘石斛利用CO₂进行光合作用的能力最强;3种石斛的CO₂饱和点(CSP)无显著性差异,在CO₂浓度不大于2 000 μmol·mol^-1时均未到达饱和点;CO₂补偿点(CCP)具有显著性差异,CCP分别为100.12 μmol·m^-2·s^-1、158.02 μmol·m^-2·s^-1、134.44 μmol·m^-2·s^-1,其中叠鞘石斛的CCP最低,对低浓度CO₂的利用能力最强。3种石斛叶片的SPAD值分别为51.09,56.93和58.06,其高低与其净光合速率的大小有一定程度的相关性。在3种石斛中,束花石斛的光合作用能力最强,对弱光的利用能力较强;流苏石斛对弱光的利用能力较弱,光照适应范围狭窄;叠鞘石斛对强光的利用能力较强,光合作用适应范围较广。此外,3种石斛均具有较强的耐阴性,对CO₂的耐受性也较强,在种植时应提供适当的遮阴和增加CO₂浓度来提高石斛的光合作用能力。     

一个单核三价铬配合物的晶体结构、发光性质及热稳定性

我们重新合成了曾经报道过的反式K[Cr(C₂O₄)_2·(H₂O)₂]_2·3H₂O三价铬配合物, 并借助先进的单晶衍射仪和更先进的解析手段得到了该配合物更加精确的结构模型,该配合物属于单斜晶系,P2/n（No. 13）空间群,晶胞相关参数为：a = 7.8827 (4) Å,b = 5.7296(3) Å,c = 13.6447(7) Å,β= 103.506(5)°,Z = 2,Dc =1.980 Mg/m³,V = 599.22(5) ų。热重测试结果显示该配合物在357 K以前是稳定的,在410 nm最有效的紫外光光源的激发下,配合物在610 nm处有一个尖锐的发射峰。     

Effects of anions on the biosorption of microelement cations by macroalga <Emphasis Type="Italic">Enteromorpha prolifera</Emphasis> in single- and multi-metal systems

The results of research on the effects of anions on the biosorption of microelement cations by the edible marine macroalga Enteromorpha prolifera in singleand multi-metal systems are discussed in this paper. It was shown that the maximum biosorption capacity (qmax) in a single-metal system of Co(II) ions decreased in the following sequence: Cl- (46.0 mg g-1) > SO42- (42.8 mg g-1) > NO3- (41.9 mg g-1). In multi-metal systems, in which the ratios of Cl-, NO3-, and SO42- were 0:0:4, 1:1:2, 3:0:1, and 4:0:0, there were clear differences among the biosorption capacities. In all the examined systems (other than the 0:0:4 system), inhibition of the binding of microelement cations by the macroalga was observed. In all the systems, the highest value of qmax was obtained for Cu(II) cations; the value ranged from 31.9 mg g-1 in 0:0:4 (SO42- only) to 18.2 mg g-1 in 4:0:0 (Cl-only).     

The synergistic effect of quaternary ammonium cations on the corrosion inhibition of Fe by inorganic anions

The synergistic effect of tetrabutylammonium cation (TBA⁺) or N-hexadecylpyridinium cation (HDP⁺) and SCN⁻ or I⁻ in 0.5 mol·L⁻¹ H₂SO₄ solution on the corrosion inhibition of Armco iron was investigated by potentiodynamic polarization and polarization resistance measurements. The results show that the synergistic effect of HDP⁺ containing π-electron and anion is stronger than that of TBA⁺ and anion. The joint adsorption models of cation and anion at electrode-solution interface are related to the structure and property of both ions by analyzing the desorption behaviours of both ions when the electrode is polarized anodically. Supported by the national scientific foundation of China Zou Jinyun: born in Aug. 1936. Prof.     

Structure of aqueous sodium sulfate solutions derived from X-ray diffraction

A rapid liquid X-ray diffractometer was used to study the time-averaged and space-averaged structure of aqueous sodium sulfate solutions at 298 and 323 K. Difference radial distribution functions of the solutions were obtained from accurate diffraction data. The interaction distances of Na^＋-OH2 and S-H2O in solutions were found to be 0.235 and 0.385 nm, respectively, after deconvolution of superposition peaks by Gaussian multi-peak fitting program. The characteristic distance of the NaSO; contact ion pairs in higher concentration solutions was determined to be 0.345 nm, suggesting that the Na^＋ ions coordinated with SO4^2- ions in the mono-dentate form. Effects of concentration and temperature on the hydration structure of the solutions were discussed in the present paper. With a decrease in concentration, the contributions of the H2O to the diffraction pattern increase, the average coordination number of the Na^＋ ions hardly changes, while the hydration number of SO4^2- ions increases slightly. The formation of NaSO; contact ion pairs becomes easier at higher temperature. The structure of hydrogen bond in dilute solutions is broken to a considerable extent with rising temperature, and the peak at 0.290 nm splits into two peaks at 0.275 and 0.305 nm, respectively.     

Characteristics of gas geochemistry in Yangbajing geothermal field, Tibet

CO 2 is a main component of gases in the Yangbajing geothermal field, usually higher than 85 in volume; others are N 2, H 2S, H 2, CH 4, etc. Helium R/R a ratios, ranging from 0.14 to 0.46, indicate a crustal component to be dominant in the gases. δ 13C-CO 2 values and δ 34S-H 2S values are in the range -7.72‰--11.33‰ and 0.2‰-8.3‰, respectively. The gases are inferred to mostly derive from the partial melting of the Nyainqentanglha core complex. The gases of shallow and deep reservoirs are distinctive in chemical compositions and δ 34S-H 2S values, which shows their different flowing paths and physical-chemical processes. Sulphur does not approach isotopic equilibrium between H 2S and SO 2- 4 species in both reservoirs. Significance of steam chemical monitoring is also discussed.     

冷凝液硫含量对SUS444铁素体不锈钢腐蚀行为的影响

利用冷凝液浸蚀-高温氧化循环腐蚀法模拟汽车排气系统内部服役环境,借助失重分析、腐蚀形貌观察及腐蚀产物分析,研究了SUS444不锈钢在不同硫含量的冷凝液中的腐蚀行为。结果表明,随着腐蚀循环次数的增加,不锈钢表面不断沉积的FeSO_4·7H_2O、Fe(NH_4)(SO_4)_2及Fe_4(SO_4)_5(OH)_2·18H_2O等硫酸盐物质加速了不锈钢的腐蚀进程,其点蚀深度及腐蚀速率均随冷凝液中硫含量的升高而增加。     

Photocatalytic activity of ferric oxide/titanium dioxide nanocomposite films on stainless steel fabricated by anodization and ion implantation

A simple surface treatment was used to develop photocatalytic activity for stainless steel. AISI 304 stainless steel specimens after anodization were implanted by Ti ions at an extracting voltage of 50 kV with an implantation dose of 3 × 1015 atoms·cm?2 and then annealed in air at 450℃ for 2 h. The morphology was observed by scanning electron microscopy. The microstructure was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The photocatalytic degradation of methylene blue solution was carried out under ultraviolet light. The corrosion resistance of the stainless steel was evaluated in NaCl solution (3.5 wt%) by electrochemical polarization curves. It is found that the Ti ions depth profile resembles a Gaussian distribution in the implanted layer. The nanostructured Fe₂O₃/TiO₂ composite film exhibits a remarkable enhancement in photocatalytic activity referenced to the mechanically polished specimen and anodized specimen. Meanwhile, the annealed Ti-implanted specimen remains good corrosion resistance.     

The seasonal variations of δ~(18)O , Cl~- , Na~+ , NO_3~- and Ca~(2+) in the snow and firn recovered from Princess Elizabeth Land, Antarctica

Snow and firn samples recovered from two snow pits (2.5 and 4.5m deep) and one 50-m firn core along the route of the 1996/1997 Chinese First Antarctic Inland Traverse Expedition in Princess Elizabeth Land, East Antarctica, have been measured for chemical composition and oxygen isotope ratio. In the two snow pits, the variations of NO3- are partly in phase with that of δ18O, while the variations of Cl~ and Na+ are in inverse phase with that of δ18O. The variations of CI- , Na+ , NO3- and δ18O show obvious seasonal variations and annual stratag-raphy. However, with the depth increasing, the seasonal variations of δ18O are gradually smoothed below 3 m (corresponding to about 10-year mass accumulation) in depth while the seasonal variations of Cl- , Na+ and NO3- are kept fairly well in the whole profile of the 50-m firn core (corresponding to about 250-year mass accumulation). The results provide a useful tool for dating the snow stratum in this region. On the contrary, no obvious seasonal variations of Ca2 + are found in the profiles.     

Experimental investigation of incremental reactivity of di-tert-butyl peroxide

Large quantities of di-tert-butyl peroxide (DTBP) have been emitted into the troposphere due to human activities. Its role in the atmospheric photochemical reaction has not been understood. This study presents the results of the photochemical reactions of DTBP and NOx, which have been simulated in a self-made smog chamber under the temperature of (29±1)℃. Both the wall decays of ozone and NO2 could be neglected, compared to the results in simulative experiments. The effective intensity of UV light used in the experiments was 1.28×10-3 s-1, which was expressed by the rate constant of NO2 photolysis in purified air. The reaction mechanism was proposed according to our results and reports of other researchers. The maximum values of incremental reactivity (IR) in the three simulative ex- periments were 9.53×10-2, 5.23×10-2 and 3.78×10-2, respectively. The incremental reactivity decreased with the increase of initial concentrations of DTBP. The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research.     

Ice core dust particulate by XPS-SEM/EDAX

The ice core dust particulate sampled from Mt. Xixabangma has been analyzed by means of X-ray photoelectron spectrometer (XPS) and scanning electron microscope with energy dispersion X-ray analysis (SEM/EDAX). The results show that the contents of SO ₄ ²⁻ and SO ₄ ²⁻ in the surface layer of the dust are significantly higher than those in the subsurface layer (with the exception of organic sulfide). This difference indicates that the surface SO_x has been captured and then chemically converted by the atmospheric dust particulate before its deposition with snow, which is obviously different from those inner layer sulfates and sulfites contained by dust itself. In addition, it has been determined by SEM/EDAX that the dust contains relatively high concentrations of transition metal elements such as Fe and Ti oxides which could function as photocatalysts to the conversion of SO_x adhered on the surface of the dust, and consequently accelerate the deposition of SO_x to snow. Our research also demonstrates that the adsorptive carrying and the catalytic performance of the dust to the atmospheric SO_x are most important causes of the positive correlation between SO ₄ ²⁻ and dust concentration records in ice cores.