Surface acidity study of Mn+-montmorillonite clay catalysts by FT-IR spectroscopy: Correlation with esterification activity

A simple method for evaluating the surface acidity of different cation-exchanged montmorillonite (mont) clay catalysts, Mⁿ⁺-mont (Mⁿ⁺=Al³⁺, Fe³⁺, Cr³⁺, Zn²⁺, Ni²⁺, Cu²⁺, and H⁺), involving treatment with pyridine is described. After treating with pyridine, the samples were heated at 120 °C and the FT-IR spectra were directly recorded in the region 1650 and 1350 cm⁻¹. The data obtained show the presence of both Lewis and Brønsted acid sites. The activities of the catalysts to bring about Brønsted acid catalysed esterification of succinic acid with iso-butanol to yield di-(iso-butyl) succinate have been studied. The Brønsted acidity data obtained for Mⁿ⁺-mont correlated well with activity in the esterification reaction. The activities of the catalysts were found to decrease in the order of exchange ions Al³⁺ > Fe³⁺ > Cr³⁺ > Zn²⁺ > Ni²⁺ > Cu²⁺ > Na⁺-mont. They also correlated well with the charge to radius ratio of the cations. The catalysts exchanged with trivalent cations showed stronger absorption bands attributed to Brønsted acidity (1540 cm⁻¹) whereas those exchanged with divalent cations showed an increased Lewis acidity (1450 cm⁻¹) and reduced Brønsted acidity along with charge to radius ratio. Zn²⁺-, Cu²⁺- and Ni²⁺-exchanged clays showed an additional peak around 1605 cm⁻¹ which is attributed to the pyridine adsorption on surface sites through its π electrons. The method suggested here to evaluate the acidity is suitable for active sites which are thermally unstable such as water molecules in the hydration shell of a cation in exchanged clay.     

Competitive Reaction During Decomposition of Hexachlorobenzene Over Ultrafine Ca–Fe Composite Oxide Catalyst

The decomposition of hexachlorobenzene (HCB) has been investigated over ultrafine Ca–Fe composite oxide catalyst (Ca/Fe atomic ratio was 3.4), CaO and α-Fe₂O₃ by using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Adsorption experiments on the surface of oxides monitored by in situ DRIFTS showed that partial oxidation products, i.e., phenolate and acetate species were formed on the surface of Ca–Fe composite oxide. The further studies indicated that Ca–Fe composite oxide catalyst was easier to induce the rupture of C–Cl bond and C–C bond of aromatic rings. The best catalytic activity of Ca–Fe composite oxide may be related to the acidity, which was determined by NH₃–TPD. The products after reaction have been analyzed by XRD and chloride selective electrode. Ca–Fe composite oxide exhibited the highest extent of mineralization for organic chlorine among the different oxides tested. The combined results of current and previous experiments demonstrated that two competitive reactions took place during the decomposition process of HCB: (1) hydrodechlorination resulting in the formation of lower chlorinated benzenes and (2) oxidation of aromatic rings leading to the rupture of aromaticity and the formation of oxidation products. The latter is the major process in the coexisted competitive reaction. A possible decomposition pathway was discussed.     

浮游植物现存量表征指标间相关性研究Ⅰ:叶绿素a与生物量

收集国内、外有关资料,并结合潘家口水库现场围隔实验,主要从实验室内研究水体、野外围隔水体及天然水体三个方面,对浮游植物叶绿素a含量与生物量间的相关性进行探讨。结果表明:在实验室条件下,叶绿素a与生物量一般呈显著正相关关系,但当优势藻种发生明显变更时,二者相关性不明显甚至不相关;现有资料显示,野外围隔实验水中,叶绿素a与生物量一般呈显著正相关。在天然水体中,叶绿素a与生物量可能相关或不相关。叶绿素a与藻密度的关系将在续文中予以讨论。     

A novel coupled biokinetic-equilibrium model to capture oyster metal bioaccumulation in a contaminated estuary (Sydney estuary,Australia)

Enriched concentrations of metal contaminants have been reported in surficial sediments and tissues of aquatic organisms in Sydney estuary, New South Wales, Australia. Dietary ingestion of contaminated, suspended sediments is potentially a major route of metal exposure to the filter-feeder Saccostrea glomerata. A dynamically coupled biokinetic-equilibrium bioaccumulation model was developed to explore sediment-oyster-metal uptake interactions. The biokinetic component simulated the sediment dynamics and oyster uptake and loss kinetics while the ion equilibrium model accounted for the metal speciation reactions. Results of a laboratory-based mesocosm experiment as well as data from the literature were used to parameterise the model. The model demonstrated a good fit of the experimental data and indicated that dissolved and particulate organic matter were important determinants of metal bioavailability to this species. The model served also as a unique tool to formulate testable hypotheses and help to better explain the bioaccumulation patterns observed from the experiment.     

In situ electrodeposition of nickel cobalt selenides on FTO as an efficient counter electrode for dye-sensitized solar cells

Construction of transition metal selenides with high electrocatalytic performance is of significant importance, but it is still a challenge to develop the corresponding counter electrodes (CEs) by an electrodeposition technique. In the present work, nickel cobalt selenide (Ni_xCo_ySe) films are prepared in situ on fluorine-doped tin oxide (FTO) glasses through a potential reversal electrodeposition technique. The morphology and electronic structure of Ni_xCo_ySe films can be tuned by controlling the Ni/Co molar ratio in electroplating solution. Specially, Ni_xCo_ySe-6 film (the Ni/Co molar ratio of 1:1) with the optimized interaction between the Ni and Co elements displays numerous particles composed of sheets attached with nanocrystals, resulting in the more electrocatalytic active sites. Benefiting from the unique morphology and optimized synergistic effect, Ni_xCo_ySe-6 CE exhibits superior electrocatalytic activity for the triiodide reduction. Then, the dye-sensitized solar cell (DSC) fabricated by Ni_xCo_ySe-6 CE has demonstrated a power conversion efficiency (PCE) over 7.40%, which is higher than that of platinum (Pt)-based device (6.32%). Furthermore, Ni_xCo_ySe-6 array CE is also prepared by using polystyrene array as template. The PCE of the DSC with Ni_xCo_ySe-6 array CE reaches its maximum value of 7.64% and 20.9% larger than that of Pt-based device.     

Causes and Effects of a Water Spill from the Underground Pit of the Dashu Pyrite Mine,Southern Sichuan Basin,Southwest China

Mine Water and the Environment - In March 2019, a well was drilled in the north of the Dashu pyrite mining area in southwest China to extract shale gas from below the pyritic layer. This well...     

Identifying the sources and fate of anthropogenically impacted dissolved organic matter (DOM) in urbanized rivers

Anthropogenic activities have dramatically changed the loads and compositions of dissolved organic matter (DOM) in urbanized streams. In this study, the spatial and temporal variations of DOM in the anthropogenically impacted Zhujiang River were investigated by analyzing the water samples in an upstream, urbanized area and downstream of the rivers on different days of one year. The results indicated that the levels of dissolved organic carbon (DOC) and total phosphorus (TP) were unaffected by seasonal changes, but the specific UV₂₅₄ absorbance (SUVA) values and the total nitrogen (TN) content were greater in the winter than those in the summer. Parallel factor (PARAFAC) analysis of the excitation emission matrices (EEM) revealed the presence of three anthropogenically derived components [tryptophan-like (C1) and tyrosine-like proteins (C3) and anthropogenic humic substances (C5)] in the urbanized rivers, and they had greater seasonal and spatial variability than the terrestrial and microbial humic substances (C2 and C4). Cluster analysis revealed that treated wastewater was an important source of DOM in the urbanized streams. Photodegradation experiments indicated that the DOM in the populous area of the rivers had greater photodegradation potentials than that in the downstream region or in the natural waters. Interestingly, that the anthropogenic humic substances (C5) were considerably more photoreactive than the other four PARAFAC components, which exhibited a decrease of 80% after exposure to sunlight for 0.5 d. This study suggests that the treated wastewater could be an important input to the DOM in the urbanized rivers and the naturally occurring photodegradation could help in eliminating the anthropogenic DOM during their transport.     

Synthesis of a perfluorooctanoic acid molecularly imprinted polymer for the selective removal of perfluorooctanoic acid in an aqueous environment

Perfluorooctanoic acid (PFOA) contamination in the environment is a global problem. The aqueous phase is the main medium for PFOA because of its moderate solubility. Adsorption is a feasible way to remove PFOA because of its chemical and biological stability. In this study, a new type of molecularly imprinted polymer (MIP) for the selective adsorption of PFOA in aqueous solutions was synthesized by the precipitation polymerization method with PFOA as the template molecule after optimization. The adsorption kinetics and isotherms of the MIP adsorbent toward PFOA were studied, and the effects of the pH and cations on the adsorption were investigated with batch experiments. The results show that acrylamide (AAM) was the best functional monomer, and the optimal molar ratio of PFOA to AAM to ethylene glycol dimethacrylate (crosslinker) was 1:6:25. The optimized MIP adsorbent had a high affinity for PFOA, and the uptake percentage by the MIP adsorbent was 1.3–2.5 times that of the nonimprinted polymer (NIP) when PFOA existed alone. A maximum PFOA sorption capacity of 5.45 mg/g based on the Langmuir isotherm model was achieved with the MIP adsorbent. The MIP adsorbent exhibited a high selectivity for PFOA over competitive compounds (other perfluorinated alkyl carboxylic and sulfonic acids), whereas the NIP did not. Approximately 90% of the PFOA in the mixture was removed by the MIP adsorbent; this was 18 times that of the NIP. Moreover, the regenerability of the MIP adsorbent was confirmed in five sequential adsorption–desorption cycles without a significant reduction in the PFOA uptake. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43192.