Comparison between granular pillared, organo- and inorgano-organo-bentonites for hydrocarbon and metal ion adsorption

Granular reactive materials have higher permeability and are therefore desirable for in situ groundwater pollution control. Three granular bentonites were prepared: an Al-pillared bentonite (PBg), an organo-bentonite (OBg) using a quaternary ammonium cation (QAC), and an inorgano-organo-bentonite (IOBg), using both the pillaring agent and the QAC. Powdered IOB (IOBp) was also prepared to test the effect of particle size. The modified bentonites were characterised with X-ray diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA) and uniaxial compression tests. The d-spacing increased only with QAC intercalation. The Young's modulus of IOBg was twice as high as OBg. Batch adsorption tests were performed with aqueous multimetal solutions of Pb2+, Cu2+, Cd2+, Zn2+ and Ni2+ ions, with liquid dodecane and with aqueous dodecane solutions. Metal adsorption fit the Langmuir isotherm. Adsorption occurred within 30min for PBg, while the granular organo-bentonite needed at least 12h to reach equilibrium. IOBp had the maximum adsorption capacity at higher metal concentration and lower adsorbent content (Cu2+: 2.2, Ni2+: 1.7, Zn2+: 1.4, Cd2+: 0.9 and Pb2+: 0.7 all in mmolg-1). The dual pillaring of the QAC and Al hydroxide increased the adsorption. The adsorption of liquid dodecane was in the order IOBg>OBg>PBg (3.2>2.7>1.7mmolg-1). Therefore IOBg has potential for the removal of toxic compounds found in soil, groundwater, storm water and wastewater. © 2012 Elsevier B.V.

Kinetic control of catalytic CVD for high-quality graphene at low temperatures.

Low-temperature (∼600 °C), scalable chemical vapor deposition of high-quality, uniform monolayer graphene is demonstrated with a mapped Raman 2D/G ratio of >3.2, D/G ratio ≤0.08, and carrier mobilities of ≥3000 cm(2) V(-1) s(-1) on SiO(2) support. A kinetic growth model for graphene CVD based on flux balances is established, which is well supported by a systematic study of Ni-based polycrystalline catalysts. A finite carbon solubility of the catalyst is thereby a key advantage, as it allows the catalyst bulk to act as a mediating carbon sink while optimized graphene growth occurs by only locally saturating the catalyst surface with carbon. This also enables a route to the controlled formation of Bernal stacked bi- and few-layered graphene. The model is relevant to all catalyst materials and can readily serve as a general process rationale for optimized graphene CVD.

The parameter space of graphene chemical vapor deposition on polycrystalline Cu

A systematic study of the parameter space of graphene chemical vapor deposition (CVD) on polycrystalline Cu foils is presented, aiming at a more fundamental process rationale in particular regarding the choice of carbon precursor and mitigation of Cu sublimation. CH 4 as precursor requires H 2 dilution and temperatures ≥1000 °C to keep the Cu surface reduced and yield a high-quality, complete monolayer graphene coverage. The H 2 atmosphere etches as-grown graphene; hence, maintaining a balanced CH 4/H 2 ratio is critical. Such balance is more easily achieved at low-pressure conditions, at which however Cu sublimation reaches deleterious levels. In contrast, C 6H 6 as precursor requires no reactive diluent and consistently gives similar graphene quality at 100-150 °C lower temperatures. The lower process temperature and more robust processing conditions allow the problem of Cu sublimation to be effectively addressed. Graphene formation is not inherently self-limited to a monolayer for any of the precursors. Rather, the higher the supplied carbon chemical potential, the higher the likelihood of film inhomogeneity and primary and secondary multilayer graphene nucleation. For the latter, domain boundaries of the inherently polycrystalline CVD graphene offer pathways for a continued carbon supply to the catalyst. Graphene formation is significantly affected by the Cu crystallography; i.e., the evolution of microstructure and texture of the catalyst template form an integral part of the CVD process. © 2012 American Chemical Society.

A comprehensive study of lysozyme adsorption using dual polarization interferometry and quartz crystal microbalance with dissipation.

Protein adsorption plays a crucial role in biomaterial surface science as it is directly linked to the biocompatibility of artificial biomaterial devices. Here, elucidation of protein adsorption mechanism is effected using dual polarization interferometry and a quartz crystal microbalance to characterize lysozyme layer properties on a silica surface at different coverage values. Lysozyme is observed to adsorb from sparse monolayer to multilayer coverage. At low coverage an irreversibly adsorbed layer is formed with slight deformation consistent with side-on orientation. At higher coverage values dynamic re-orientation effects are observed which lead to monolayer surface coverages of 2-3 ng/mm² corresponding to edge-on or/and end-on orientations. These monolayer thickness values ranged between 3 and 4.5 nm with a protein density value of 0.60 g/mL and with 50 wt% solvent mass. Further increase of coverage results formation of a multilayer structure. Using the hydration content and other physical layer properties a tentative model lysozyme adsorption is proposed.

A comprehensive study of lysozyme adsorption using dual polarization interferometry and quartz crystal microbalance with dissipation

Protein adsorption plays a crucial role in biomaterial surface science as it is directly linked to the biocompatibility of artificial biomaterial devices. Here, elucidation of protein adsorption mechanism is effected using dual polarization interferometry and a quartz crystal microbalance to characterize lysozyme layer properties on a silica surface at different coverage values. Lysozyme is observed to adsorb from sparse monolayer to multilayer coverage. At low coverage an irreversibly adsorbed layer is formed with slight deformation consistent with side-on orientation. At higher coverage values dynamic re-orientation effects are observed which lead to monolayer surface coverages of 2-3 ng/mm2 corresponding to edge-on or/and end-on orientations. These monolayer thickness values ranged between 3 and 4.5 nm with a protein density value of 0.60 g/mL and with 50 wt% solvent mass. Further increase of coverage results formation of a multilayer structure. Using the hydration content and other physical layer properties a tentative model lysozyme adsorption is proposed. © 2012 Elsevier Ltd.

汉江下游武汉段河漫滩沉积物吸附磷的特征

研究了汉江下游武汉段河漫滩7个沉积物的吸附特征及温度和扰动强度对磷吸附等温线的影响,用改进的Langmuir模型和Freundlish模型对实验吸附数据进行拟合,可得到最大吸附容量(Qmax)、原有吸附可交换态磷(NAP)、临界磷平衡浓度(EPC0)和固-液分配系数(Kp)的值.结果表明,改进的Langmuir模型更适用于描述汉江河漫滩沉积物的吸附特征,其物理意义更明确;Kp与Qmax呈较好的线性关系;沉积物吸附和解吸磷能力与温度变化一致;沉积物在等温吸附磷过程中,固体浓度效应在强扰动强度(200 r/m

菹草对湖泊沉积物磷状态的影响

武昌野芷湖湾菹草(PotamogetoncrispusL.)生物量较高位置的沉积物显示明显较高的磷吸附指数,以及据Langmuir方程:C/X=C/Xm+K×1/Xm导出的最大吸附量与吸附强度,这一结果在不同时期与不同采样深度均有体现,故提高沉积物磷的吸附能力应为菹草维持水体较低营养水平的重要机制。铁结合态磷是沉积物磷的主要存在形式,吸附能力的提高可由有机质及其与铁的相互作用部分地得到解释。不同时期菹草生物量较高的沉积物表现明显较低的碱性磷酸酶活性与最大反应速度,降低沉积物有机磷的酶促分解速率应为菹草维持

Polymer gate dielectrics with self-assembled monolayers for high-mobility organic thin-film transistors based on copper phthalocyanine

Organic thin-film transistors based on polycrystalline copper phthalocyanine (CuPc) were fabricated by using poly(vinyl alcohol) as gate dielectric. After treatment of the gate dielectric using an octadecyltrichlorosilane self-assembled monolayer, a mobility of up to 0.11 cm2/V∈s was achieved, which is comparable to that of single-crystal CuPc devices (0.1-1 cm2/V∈s). The surface morphology was analyzed and the possible reasons for the enhanced mobility are discussed. © 2009 Springer-Verlag.

Mechanics of capillary forming of aligned carbon nanotube assemblies.

Elastocapillary self-assembly is emerging as a versatile technique to manufacture three-dimensional (3D) microstructures and complex surface textures from arrangements of micro- and nanoscale filaments. Understanding the mechanics of capillary self-assembly is essential to engineering of properties such as shape-directed actuation, anisotropic wetting and adhesion, and mechanical energy transfer and dissipation. We study elastocapillary self-assembly (herein called "capillary forming") of carbon nanotube (CNT) microstructures, combining in situ optical imaging, micromechanical testing, and finite element modeling. By imaging, we identify sequential stages of liquid infiltration, evaporation, and solid shrinkage, whose kinetics relate to the size and shape of the CNT microstructure. We couple these observations with measurements of the orthotropic elastic moduli of CNT forests to understand how the dynamic of shrinkage of the vapor-liquid interface is coupled to the compression of the forest. We compare the kinetics of shrinkage to the rate of evporation from liquid droplets having the same size and geometry. Moreover, we show that the amount of shrinkage during evaporation is governed by the ability of the CNTs to slip against one another, which can be manipulated by the deposition of thin conformal coatings on the CNTs by atomic layer deposition (ALD). This insight is confirmed by finite element modeling of pairs of CNTs as corrugated beams in contact and highlights the coupled role of elasticity and friction in shrinkage and stability of nanoporous solids. Overall, this study shows that nanoscale porosity can be tailored via the filament density and adhesion at contact points, which is important to the development of lightweight multifunctional materials.

Structurally programmed capillary folding of carbon nanotube assemblies.

We demonstrate the fabrication of horizontally aligned carbon nanotube (HA-CNT) networks by spatially programmable folding, which is induced by self-directed liquid infiltration of vertical CNTs. Folding is caused by a capillary buckling instability and is predicted by the elastocapillary buckling height, which scales with the wall thickness as t(3/2). The folding direction is controlled by incorporating folding initiators at the ends of the CNT walls, and the initiators cause a tilt during densification which precedes buckling. By patterning these initiators and specifying the wall geometry, we control the dimensions of HA-CNT patches over 2 orders of magnitude and realize multilayered and multidirectional assemblies. Multidirectional HA-CNT patterns are building blocks for custom design of nanotextured surfaces and flexible circuits.

网箱养殖对东湖沉积物有机质含量以及磷的酶促水解与吸附行为的影响

东湖养殖罗非鱼(Oreochromisniloticus)的网箱下沉积物中有机质和可酶解磷(PHP)含量以及碱性磷酸酶活性(APA)均显示增高,间隙水中的PHP较低,而APA与正磷酸盐的浓度均高,这种现象在垂直与水平两个尺度上均有体现,故由有机物的富集到正磷酸盐的剧增可能受控于酶学机制。Langmuir单分子等温度吸附模型的分析结果表明网箱下表层沉积物的最大吸附量明显较高,而吸附强度明显降低,此亦为正磷酸盐相应剧增的另一重要原因。不同深度间隙水中APA的动力学行为表现出明显的季节性。

河湖沉积物中酸挥发性硫化物对重金属吸附及释放的影响

通过吸附、释放实验研究了河流及湖泊沉积物酸挥发性硫化物对上覆水中重金属元素的影响 .采用兼具Langmuir及Freundlish等温线方程两种方程特征的Sips表达式及无机离子分级交换理论 ,较好地对重金属元素在沉积物或颗粒物上的吸附及释放特征进行了描述 .结果表明 ,存在于水溶液中的重金属可以不断地与沉积物结合 ,从而使水溶液中的重金属浓度维持在一很低的水平上 ;并且 ,一旦与沉积物结合 ,重金属就很难再释放出来 .酸挥发性硫化物的存在增加了沉积物的吸附容量 ,但酸挥发性硫化物经过酸化被除去后 ,沉积

水体悬移质对重金属吸附规律研究——以长江宜昌段为例

随着长江三峡工程的建设 ,上游来水的流速在此减缓 ,随江水而下的大量泥沙在此沉淀 ,将使坝下 (长江中下游 )水中的悬移质浓度降低、粒径改变 ,从而改变水环境容量。利用长江宜昌江段的周年悬移质样及水样 ,研究了悬移质对重金属 (铜、锌、铅、镉及铬 )的吸附特征。结果表明 ,悬移质对上述金属的吸附可用Freundlich型及Langmuir型等温式较好进行拟合 ;当较高浓度的金属污染物排入江水后 ,在吸附及沉淀的共同作用下 ,浓度明显降低 ;单位悬移质的吸附量随悬移质浓度降低而上升 ,但总吸附量降低 ,从而

Palm frond biochar production and characterisation

Palm oil has been the world's main source of oil and fats since 2004, producing over 45 million tonnes in 2009. Malaysia alone has over 4·5 million hectares planted with oil palm and, based on common practice, ~300 palm fronds are pruned per hectare per year. This agricultural waste is currently either being used as roughage feed or, more frequently, being left between rows of palm trees to prevent soil erosion, or for nutrient recycling purposes. This paper proposes an alternative use for palm frond as a source of biochar. A traditional method commonly use by gardeners in Malaysia to improve soil fertility was used to produce the biochar. A shallow earth pit was dug in the ground for the carbonisation process. The process is described and the impact of carbonisation on the earth wall is analysed and presented. The process was later re-assessed by using TGA-FTIR. Most of the hemicelluloses had fully disintegrated, but the depolymerisation of the cellulose was still incomplete at the carbonisation temperature. Most of the lignin aromatic structure was still present in the biochar. The carbonisation process was repeated in the laboratory and biochar was characterised by using BET, SEM and FTIR. An adsorption isotherm study was conducted and the experimental data were fitted to the Langmuir model. The model predicted Pb2+ adsorption rates of 83·3 mg/g, Cu2+ 41·4 mg/g, Ni2+ 13·0 mg/g and Zn2+ 19·7 mg/g. Copyright © The Royal Society of Edinburgh 2012.

Using mesoscopic models to design strong and tough biomimetic polymer networks

Using computational modeling, we investigate the mechanical properties of polymeric materials composed of coiled chains, or "globules", which encompass a folded secondary structure and are cross-linked by labile bonds to form a macroscopic network. In the presence of an applied force, the globules can unfold into linear chains and thereby dissipate energy as the network is deformed; the latter attribute can contribute to the toughness of the material. Our goal is to determine how to tailor the labile intra- and intermolecular bonds within the network to produce material exhibiting both toughness and strength. Herein, we use the lattice spring model (LSM) to simulate the globules and the cross-linked network. We also utilize our modified Hierarchical Bell model (MHBM) to simulate the rupture and reforming of N parallel bonds. By applying a tensile deformation, we demonstrate that the mechanical properties of the system are sensitive to the values of N in and N out, the respective values of N for the intra- and intermolecular bonds. We find that the strength of the material is mainly controlled by the value of N out, with the higher value of N out providing a stronger material. We also find that, if N in is smaller than N out, the globules can unfold under the tensile load before the sample fractures and, in this manner, can increase the ductility of the sample. Our results provide effective strategies for exploiting relatively weak, labile interactions (e.g., hydrogen bonding or the thiol/disulfide exchange reaction) in both the intra- and intermolecular bonds to tailor the macroscopic performance of the materials. © 2011 American Chemical Society.