球粒状和棒状纳米赤铁矿光电化学特性研究

本文以乙二醇为诱导剂通过电化学沉积法成功合成了球粒状及棒状纳米赤铁矿。X射线衍射光谱(XRD)和Raman光谱结果表明,球粒状赤铁矿粒径20±5 nm;棒状赤铁矿截面直径约20 nm,长90±10 nm;二者物相皆为单一均匀的赤铁矿。紫外-可见吸收光谱显示两种赤铁矿在300~550 nm范围内均有较好吸收,Tauc方程计算球粒状和棒状赤铁矿禁带宽度分别为2.00 e V和1.99 e V。Mott-Schottky拟合结果表明1 M KOH溶液体系中,棒状赤铁矿载流子浓度为1.95×1021cm-3,高于球粒状赤铁矿(3.16×1020cm-3)。进一步的光电化学实验表明:0.6 V(vs.Ag/Ag Cl)电势下棒状赤铁矿光照下电流密度较暗电流提升550%,球粒状赤铁矿电流密度提升77%。研究证实,赤铁矿形貌对其半导体特性及光电化学特性有影响,且棒状赤铁矿电极表现出更好的可见光响应特性,具有更佳的光电催化潜力。     

纳米水钠锰矿可见光光电化学响应与甲基橙降解活性

伴随环境污染问题日益加剧,光能的光电转化在催化及环境领域引起广泛关注。水钠锰矿是地表常见锰矿物之一,本文借助电化学电量控制法快速高效制备了纳米水钠锰矿电极。X射线衍射(XRD)、Raman光谱测试表明物相单一为水钠锰矿;原子力显微镜(AFM)观察电极微观形貌可见表面分布有不规则多边形格子状空隙,测定沉积电量为0.5、1.0、1.5 C水钠锰矿厚度分别约为30、200、450 nm。紫外可见漫反射吸收谱显示电极可显著吸收300~600 nm波长可见光,Tauc方程计算电极间接带隙约0.8~1.3 eV,直接带隙约2.0~2.3 eV,Mott-Schottky曲线计算平带电位约1.15 V,三电极载流子浓度分别为3.26×10~(19)、4.63×10~(19)、2.70×1020 cm~(-3)。光电流密度-时间曲线及线性扫描伏安曲线表明电极有良好光电化学响应活性Evs.SCE=1.0 V(饱和甘汞电极)恒电势光照条件下,150 min后0.5、1.0、1.5 C水钠锰矿电极对5 mg/L甲基橙降解率分别为66.3%,70.0%,67.5%,拟合反应速率常数k分别为0.44 h~(-1)、0.48 h~(-1)、0.46 h~(-1)(R20.996)。综上,本文研究表明纳米水钠锰矿电极能有效可见光光电催化降解甲基橙等有机污染物。     

太阳能电池协同强化水钠锰矿光电催化染料降解研究

电催化、光催化、光电催化等电化学技术以其高效、廉价、环保等特点被认为是一种极具前途的环境污染深度净化技术,在有机废水处理等方面得以广泛应用。本文借助电化学电量控制法制备了水钠锰矿电极,通过X射线衍射(XRD)、扫描电镜(SEM)表征其物相形貌,UV-Vis漫反射吸收谱结果表明水钠锰矿对300~600 nm波长范围可见光表现出良好吸收能力,计算其直接带隙约为2.14 e V,Mott-Schottky曲线计算其平带电位约1.15 V,0.1 mol/L Na2SO4介质中载流子浓度约为3.3×1019cm-3,是良好的可见光激发n型半导体材料。同时,本文以廉价高效的太阳能电池板取代了传统电化学工作站等外加电场设备,成功实现了协同强化水钠锰矿光电催化降解作用。协同作用下甲基橙60 min降解率为90.2%,效率远高于水钠锰矿光催化(2.2%)与电极电催化(33.6%)作用,强化了水钠锰矿光电催化降解反应,节省能耗的同时显著提高了降解效率。批次循环降解实验表明第4轮降解率(86.8%)较之第1轮(90.3%)降低程度5%,表明其具有良好长时间运行稳定性。     

地表“矿物膜”中锐钛矿-β-胡萝卜素协同增强日光响应特性研究

为探究"矿物膜"中半导体矿物与光合色素间的日光响应协同作用,对采自安徽潜山市郊的"矿物膜"样品进行了矿物组成和色素组成分析。同步辐射X射线粉末衍射测定表明,样品富含锐钛矿、赤铁矿等半导体矿物;拉曼光谱证实其中存在地表广泛分布的光合色素:β-胡萝卜素。在此基础上开展锐钛矿-β-胡萝卜素协同增强日光响应模拟实验。合成锐钛矿电极并对其进行系统的矿物学表征,紫外-可见漫反射吸收谱计算其禁带宽度约为3.07 eV;莫特-肖特基计算得到的平带电位约为-0.16 V,载流子浓度约为3.25×1026 cm-3;光电化学测试结果显示其具有一定可见光光电转化能力。经β-胡萝卜素敏化处理后,锐钛矿电极平均光电流密度提升了400%,在425~550 nm间光吸收值提高,该波段位于日光辐射能量集中的波长范围内,且与β-胡萝卜素吸收范围吻合,表明二者间存在日光吸收及光电响应协同增强作用。     

天然赤铁矿促进红壤微生物胞外电子传递机制研究

为了研究天然赤铁矿对微生物胞外电子传递机制,以长沙和海口红壤为例,构建了双室反应体系对红壤微生物与天然赤铁矿间氧化还原作用及胞外电子传递过程进行表征。研究显示,增加赤铁矿作为电子受体后,长沙与海口红壤体系开路电压由425.28、414.64 m V提升至511.46、532.52 m V,最大输出功率由221.5、171.0 m W/m~3提升至431.4、260.2 m W/m~3。电化学循环伏安测试显示在0.43、0.55 V(相对于饱和甘汞电极;vs.SCE)处出现Fe(Ⅲ)还原峰及Fe(Ⅱ)氧化峰,指证新氧化还原反应的引入。电化学阻抗谱(EIS)拟合结果显示赤铁矿电极极化内阻R_p自44840Ω降至665Ω,从动力学层面表明电极反应导致的电势降低有利于电子转移。实验研究结果表明,红壤环境中以赤铁矿为代表的铁氧化物能够有效参与并促进微生物胞外电子传递。     

氧化铁矿物催化分解苯酚的动力学速率及其产物特征

本文研究了针铁矿、纤铁矿、赤铁矿和磁铁矿在过氧化氢参与下催化分解苯酚的动力学速率与溶液pH值的关系,并用紫外吸收谱测定了反应产物的谱学特征。结果表明,纤铁矿反应体系催化分解苯酚的速率常数(k)最大,其余依次为磁铁矿、针铁矿和赤铁矿。在纤铁矿反应体系中又以pH=3.8时反应速率常数最大。除赤铁矿反应体系外,当溶液pH=3~4时苯酚被完全分解,并有50%~65%的有机碳(TOC)被矿化。在pH=3.25的赤铁矿反应体系中,苯酚大多仅被转化为多酚,小部分苯环被打开形成己烯酸。当溶液pH=4~5时,苯酚一般仅被转化为多酚类化合物,但TOC基本不变。当溶液pH>5时,苯酚没有发生明显的转化和矿化现象。     

Mn2+和Fe3+的致色作用:来自意大利白垩纪远洋红色灰岩的启示

本文首先详细研究了含Mn2 和Fe3 的致色矿物菱锰矿、鲕状赤铁矿、云母赤铁矿和镜铁矿的可见光吸收光谱及其一阶导数谱,鲕状赤铁矿、云母赤铁矿和镜铁矿的可见光吸收一阶导数谱的红光区的吸收谷的位置的变化表明随赤铁矿结晶度的降低,吸收谷由586.4nm移至577.4nm,而菱锰矿展示出了Mn2 的因电子跃迁产生的四个典型吸收及其一阶导数谱上577nm的吸收谷的强度比赤铁矿相应谷的强度低一个数量级,表明其电子跃迁的致色机理与赤铁矿的染色机理完全不同。依据赤铁矿的结晶度和鲕状赤铁矿与大洋红层中赤铁矿的沉积成因相似的原则遴选出鲕状赤铁矿为含Fe3 致色矿物,依据菱锰矿是和方解石具有相似结构且为红色的原则选取菱锰矿为含锰致色矿物,并佐以化学纯氧化镁为基体配制了一系列的含菱锰矿、鲕状赤铁矿和菱锰矿及鲕状赤铁矿的两相或三相混合物。详细研究了三类混合物的可见光吸收光谱的一阶导数谱,发现含菱锰矿和含鲕状赤铁矿在573nm附近均存在一吸收谷,鲕状赤铁矿的重量分数低至0.05%时仍可见一明显吸收谷且该吸收谷移至565nm附近,菱锰矿在低至0.50%时也可见这一吸收且在低至0.11%时仍可显示出菱锰矿的信息,其575nm的吸收峰未见偏移;混合物可见光一阶导数吸收谱上鲕状赤铁矿的575nm附近的吸收谷的强度随鲕状赤铁矿的重量分数的升高而增强,而所有的配制混合物中该吸收谷的位置低于577.4nm的事实也表明为使致色矿物和氧化镁混合均匀的研磨降低了赤铁矿的结晶度。本研究表明Mn2 的电子跃迁激发和细小、结晶差的赤铁矿的染色共同造就了意大利白垩纪远洋红色灰岩的红色。     

不同涂层的二氧化铅电极催化性能的比较

研究了热分解法和电沉积法制备二氧化铅电极的工艺,通过对苯酚的电解和生成羟基自由基的量,比较了两种方法制得的电极的催化性能,并比较了采用电沉积法制备电极时掺杂铋或镧对电极的催化性能的影响。实验结果表明,这4种电极都具有良好的电催化性能,并且明显降低了槽电压,且对苯酚的降解均符合一级反应动力学,电沉积法制得的电极的催化性能优于热分解法制得的电极,掺镧的电极优于无掺杂和掺铋的电极。     

微生物电化学体系中金红石可见光还原降解偶氮染料的实验研究

利用双室微生物电化学装置对微生物和半导体矿物协同作用下偶氮类染料废水的还原脱色降解进行了系统的实验研究.不同光照条件及不同阴极电极材料的对比实验结果显示,偶氮染料甲基橙(MO)可作为终端电子受体直接从固体电极上获得电子被还原脱色;各对比实验中,在微生物催化与半导体矿物光催化协同作用条件下,MO还原脱色效率最高.电化学交流阻抗谱(EIS)的拟合结果显示金红石涂布阴极电极光照下极化内阻(Rp)为443.4 Ω,较无光条件下的1378 Ω显著降低,证明光照下金红石阴极的电子转移过程受其光催化作用的驱动.不同初始浓度下MO的生物-半导体催化还原反应符合准一级动力学模型,其反应速率随MO初始浓度降低而增加.通过对脱色产物的进一步分析,推测该实验中MO的还原脱色反应机制为: 阳极初始电子供体在微生物的催化作用下将电子通过阳极电极和外电路传递给阴极半导体矿物电极,进而在半导体矿物的光催化作用下通过光生电子还原终端电子受体MO,使MO中的偶氮键断裂,生成无色的联氨类衍生物.     

天然锰氧化物矿物氧化废水中苯酚的动力学研究

利用天然锰氧化物矿物在酸性条件下的强氧化性,研究其氧化水中苯酚的动力学,模拟锰氧化物矿物氧化苯酚的反应过程。通过测定初始浓度为100~1000 mg/L,pH值为1~2,温度为293~333 K时不同氧化时间锰氧化物矿物对苯酚的氧化结果,比较伪一级和伪二级反应方程的线性拟合情况;结果表明,该反应动力学曲线用伪二级反应模型拟合时相关系数高于用伪一级反应方程线性的拟合,所以这个反应可用来模拟伪二级反应。根据动力学数据得出Arrhenius反应活化能Ea为11.62 kJ/mol,说明温度对该反应影响不显著,且是一个扩散控制反应。     

Degradation of phenol and trichlorophenol by heterogeneous photo-Fenton process using Granular Ferric Hydroxide<Superscript>®</Superscript>: comparison with homogeneous system

The decomposition of phenol and trichlorophenol (TCP) by using granular ferric hydroxide (GFH) as a photo-Fenton catalyst was investigated and compared with homogeneous photo-Fenton process. Experiments were conducted in a batch mode, duplicate for the degradation of phenol and TCP in the presence of solar light for both the processes. The effect of operating variables for heterogeneous photo-Fenton process like pH, peroxide concentration and GFH concentration on the degradation of the model compounds was optimized by univariate approach. The optimum conditions for the degradation of phenol and TCP were pH 3.0 ± 0.2, peroxide concentration 29.4 mM for phenol and 14.7 mM for TCP at GFH concentration of 0.5 g/500 mL. At optimum conditions, the mineralization efficiency of phenol and TCP by heterogeneous process was compared with homogeneous process. The mineralization efficiency for phenol and TCP was 96 and 86 %, respectively, for heterogeneous photo-Fenton process, while almost complete mineralization (~96 %) was observed for homogeneous process. In heterogeneous photo-Fenton process, longer reaction time was witnessed for complete mineralization of the compounds studied. Low molecular weight aliphatic acids like oxalic acid, acetic acid and inorganic chloride ion (in case of TCP) were observed during both the processes. In these processes, the reaction proceeds by hydroxyl radical (·OH) abstraction of the model compound studied. The mineralization of phenol and TCP obeys pseudo-first-order kinetics irrespective of the processes studied. The results indicate that GFH can be an effective heterogeneous photo-Fenton catalyst for the degradation of phenol and TCP.     

The Kinetics of the Interaction Between Iron(III)-Ethylenediaminetetraacetate and Peroxynitrite

The kinetics of the formation of the purple-colored species between Fe^III-EDTA and peroxynitrite were studied as a function of pH (10.4–12.3) at 22°C in aqueous solutions using a stopped-flow technique. A purple-colored species was immediately formed upon mixing, which had an absorbance maximum at 520 nm. The increase in absorbance with time could be fit empirically by a power function with two parameters a and b. The power equation determined was absorbance = a*t ^b , where a increased linearly with pH and the concentration of peroxynitrite, while b almost remained constant with a value of ~0.25. The molar extinction coefficient ε_520 nm for the colored species was determined as 13 M⁻¹cm⁻¹, which is much lower than ε_520 nm = 520 M⁻¹ cm⁻¹ for the [Fe^III(EDTA)O₂]³⁻, a purple species observed in the Fe^III–EDTA–H₂O₂ system. The results of kinetics and spectral measurements of the present study are briefly discussed and compared with those of the reaction between Fe(III)-EDTA and hydrogen peroxide.     

铁锰氧化物对苯酚氧化降解的实验研究

为了考察铁锰氧化物对酚类污染物的氧化降解能力,采用天然以及合成的铁锰氧化物对苯酚的氧化降解进行对比实验研究。土壤中铁锰氧化物样品分别为天然针铁矿及氧化锰,合成铁锰氧化物样品分别为合成针铁矿及软锰矿。结果表明：苯酚与铁锰氧化物发生氧化还原作用时,还可能与土壤中杂质发生吸附等作用;铁锰氧化物还原反应强度随着反应介质pH值的升高而迅速下降;可用零级反应动力学方程拟合铁氧化物还原溶解反应,针铁矿溶解反应的强度与介质的pH值呈负相关关系;天然针铁矿对酚类污染物的氧化降解能力明显高于合成针铁矿,pH值对天然针铁矿溶解反应影响较大;可用一级指数衰减方程拟合锰氧化物还原溶解反应,锰氧化物溶解反应的强度与介质的pH值呈指数衰减关系;pH值对软锰矿还原溶解反应的影响大于对土壤中氧化锰的影响,pH值越小,影响越显著;对比pH值对铁和锰还原作用的影响发现,在pH=6.5时,锰氧化物仍有较强的氧化性能。     

In situ push-pull tests for the determination of TCE degradation and permanganate consumption rates

A simple, single-well push-pull test was conducted at a TCE-contaminated site to estimate the site-specific TCE degradation and permanganate (MnO₄⁻) consumption rate. Known quantities of a conservative tracer (Br⁻) and permanganate were rapidly injected into a saturated aquifer then periodically sampled during extraction from the same well. Concentrations of Br⁻, TCE, and MnO₄⁻ were measured; breakthrough curves (BTCs) for all species of solute were determined. Data analysis of BTCs for bromide and TCE showed that the first-order rate constant of TCE degradation by MnO₄⁻ is 1.67 ± 0.152 h⁻¹. Further, the in situ MnO₄⁻ demand rate by TCE and aquifer materials is estimated to be 0.54 ± 0.371 h⁻¹. This study demonstrates that in situ push-pull tests are useful and economical tools for field investigations to determine contaminant reaction and oxidant consumption rates, which may then be used to optimize groundwater remediation designs.     

Cadmium (II)-selective electrode based on palm shell activated carbon modified with task-specific ionic liquid: kinetics and analytical applications

In this study, palm shell activated carbon modified with task-specific ionic liquid was used as a novel electrode component for the potentiometric determination of cadmium ions in water samples. The proposed potentiometric sensor has good operating characteristics, including relatively high selectivity towards the Cd (II) ion, a Nernstian response to Cd (II) ions in a working concentration range of 1.0 × 10^?9–1.0 × 10^?2 M, with a reasonable detection limit of 1 × 10^?10 M and a slope of 30.90 ± 1.0 mV/decade. No significant changes in electrode potential were observed when the pH was varied over the range of 4–9. A direct technique based on the use of ion-selective electrode potentiometry has been developed in our laboratory for the study of reaction kinetics and kinetic methods of analysis by continuous monitoring of the rate of production or consumption of an ion. The apparent adsorption rate constant was estimated assuming pseudo-second-order kinetics. Additionally, the proposed electrode has been successfully used for the determination of the cadmium content in real samples without a significant interaction from other cationic or anionic species.     

Substrate inhibition kinetics of phenol degradation by Pseudomonas fluorescence from steady state and wash-out data

The present study investigated the phenol utilization kinetics of a pure culture of an indigenous Pseudomonas fluorescence under steady state and non-steady state (washout) conditions. Steady states of a continuous culture with an inhibitory substrate was used to estimate kinetic parameters under substrate limitation (chemo stat operation) Pure cultures of an indigenous Pseudomonas fluorescence were grown in continuous culture on phenol as the sole source of carbon and energy at dilution rates of 0.010 - 0.20/h. Using different dilution rates, several steady states were investigated and the specific phenol consumption rates were calculated. In addition, phenol degradation was investigated by increasing the dilution rate above the critical dilution rate (washout cultivation). The results showed that the specific phenol consumption rate increased with increased dilution rate at steady state and phenol degradation by Pseudomonas fluorescence can be described by simple substrate inhibition kinetics under substrate limitation but cannot be described by simple substrate inhibition kinetics under washout cultivation. Fitting of the steady state data from continuous cultivation to various inhibition models resulted in the best fit for Haldane, Yano and Koga (2), Aiba and Teissier kinetic inhibition models. The r_smax value of 0.229 mg/mg/h obtained from the inhibition model equations was comparable to the experimentally calculated r_smax value of 0.246 mg/mg/h obtained under washout cultivation. Therefore, the biokinetic constants evaluated using these models showed good tolerance and growth of the indigenous organism.     

西藏洞错埃达克质火山岩LA-ICP-MS锆石U-Pb年龄及其构造意义

班公湖-怒江缝合带是青藏高原的主要缝合带之一,其闭合时限还存在争议,制约了班公湖-怒江特提斯洋演化历史的研究。在班公湖-怒江缝合带洞错地区新识别出一套早白垩世晚期的粗安岩,LA-ICP-MS测得其锆石~(206)Pb/~(238)U年龄为102.0±1.9Ma,岩石高SiO_2、Al_2O_3、富Na及高的Sr/Y值(25.2~42.2),贫Nb(11.1×10~(-6)~16.6×10~(-6))、Y(11.7×10~(-6)~18.3×10~(-6))和Yb(1.06×10~(-6)~1.77×10~(-6)),轻、重稀土元素分异明显,具有与埃达克质岩相似的地球化学特征,同时具有高Mg~#的特点(Mg~#=50.0~54.1)。认为洞错高Mg~#埃达克质岩很可能是残留洋壳部分熔融上升过程中交代地幔的产物,形成于板内构造环境。由此推测,洞错早白垩世晚期埃达克质岩的形成与班公湖-怒江洋盆闭合后拉萨地块与羌塘地块碰撞有关,结合区域地质资料,认为班公湖-怒江特提斯洋闭合时限应该在102Ma之前。     

The breakdown of potassium feldspar at high water pressures

The equilibrium position of the reaction between sanidine and water to form “sanidine hydrate” has been determined by reversal experiments on well characterised synthetic starting materials in a piston cylinder apparatus. The reaction was found to lie between four reversed brackets of 2.35 and 2.50 GPa at 450 °C, 2.40 and 2.59 GPa at 550 °C, 2.67 and 2.74 GPa at 650 °C, and 2.70 and 2.72 GPa at 680 °C. Infrared spectroscopy showed that the dominant water species in sanidine hydrate was structural H₂O. The minimum quantity of this structural H₂O, measured by thermogravimetric analysis, varied between 4.42 and 5.85 wt% over the pressure range of 2.7 to 3.2 GPa and the temperature range of 450 to 680 °C. Systematic variation in water content with pressure and temperature was not clearly established. The maximum value was below 6.07 wt%, the equivalent of 1 molecule of H₂O per formula unit. The water could be removed entirely by heating at atmospheric pressure to produce a metastable, anhydrous, hexagonal KAlSi₃O₈ phase (“hexasanidine”) implying that the structural H₂O content of sanidine hydrate can vary. The unit cell parameters for sanidine hydrate, measured by powder X-ray diffraction, were a = 0.53366 (±0.00022) nm and c = 0.77141 (±0.00052) nm, and those for hexasanidine were a = 0.52893 (±0.00016) nm and c = 0.78185 (±0.00036) nm. The behaviour and properties of sanidine hydrate appear to be analogous to those of the hydrate phase cymrite in the equivalent barium system. The occurrence of sanidine hydrate in the Earth would be limited to high pressure but very low temperature conditions and hence it could be a potential reservoir for water in cold subduction zones. However, sanidine hydrate would probably be constrained to granitic rock compositions at these pressures and temperatures. Received: 6 May 1997 / Accepted: 2 October 1997     

东构造结那木拉断裂带上新世以来强烈活动的年代学证据

为揭示东喜马拉雅构造结那木拉断裂带上新世以来强烈活动特征,对采集自那木拉断裂带的三件基岩样品进行黑云母40Ar/39Ar、磷灰石裂变径迹两种热年代学方法测年;并利用"Pecube"软件对测得年龄数据及断裂带两侧已发表年龄数据进行定量模拟计算。测试结果显示黑云母40Ar/39Ar年龄范围为4.44±0.71 Ma~3.45±0.24 Ma,磷灰石裂变径迹年龄范围为3.7±0.4 Ma~1.8±0.2 Ma。年龄数据及其模拟计算结果表明,约3 Ma以前那木拉断裂带南侧地壳隆升最快,隆升速率约2.5 km/Ma,断裂带以正断层运动特征为主;约3 Ma以来那木拉断裂带北侧地壳隆升最快,约为1.3 km/Ma,断裂带以逆断层运动特征为主。那木拉断裂带运动特征变化可能与约8 Ma以来东喜马拉雅构造结快速地壳隆升剥露区域由南向北逐渐迁移有关。