Nonlinear Behavior and Domain Feature at Oil/Water Interface

Studies on nonlinear behavior at oil/water interface membrane were performed. This system showed rhythmic oscillations and chaos of electrical potential in a given concentration domain. The nonlinear behavior response at the liquid membrane apparently resembled that of biological chemoreceptive membrane. The possibility of developing a new type of chemical sensor with the ability to simulate substance equilibrium in living organisms was suggested in the paper.

Influence of CO_2 Doubling on Water Transport Process at Root/Soil Interface of Pinus sylvestris var. sylvestriformis Seedlings

Water transport at the root/soil interface of 1 year old Pinus sylvestris Linn. var. sylvestriformis (Takenouchi) Cheng et C. D. Chu seedlings under CO 2 doubling was studied by measuring soil electric conductance to survey soil water profiles and comparing it with root distribution surveyed by soil coring and root harvesting in Changbai Mountain in 1999. The results were: (1) The profiles of soil water content were adjusted by root activity. The water content of the soil layer with abundant roots was higher. (2) When CO 2 concentration was doubled, water transport was more active at the root/soil interface and the roots were distributed into deeper layer. It was shown in this work that the method of measuring electric conductance is an inexpensive, non_destructive and relatively sensitive way for underground water transport process.

Prediction of curved oil–water interface in horizontal pipes using modified model with dynamic contact angle

In this study,interface shapes of horizontal oil–water two-phase flow are predicted by using Young-Laplace equation model and minimum energy model.Meanwhile,the interface shapes of horizontal oil–water twophase flow in a 20 mm inner diameter pipe are measured by a novel conductance parallel-wire array probe(CPAP).It is found that,for flow conditions with low water holdup,there is a large deviation between the model-predicted interface shape and the experimentally measured one.Since the variation of pipe wetting characteristics in the process of fluid flow can lead to the changes of the contact angle between the fluid and the pipe wall,the models mentioned above are modified by considering dynamic contact angle.The results indicate that the interface shapes predicted by the modified models present a good consistence with the ones measured by CPAP.

Probit Analysis of Carbamate-Pesticide-Toxicity at Soil-Water Interface to N_2-Fixing Cyanobacterium Cylindrospermum sp.

Toxicity-data of two carbamate insecticides, carbaryl and carbofuran, and three fungicides, ziram, zineb and mancozeb with rice-field N2-fixing cyanobacterium Cylindrospermum sp., obtained by in vitro growth and at soil-water interface, were analyzed by the probit method. Growth enhancing concentration, no-observed effective concentration, minimum inhibitory concentration, the highest permissive concentration and lethal concentration100 （LCloo） were determined experimentally. The LC^o values of carbaryl, carbofuran, ziram, zineb and mancozeb in N2-fixing liquid medium were 56.2, 588.8, 0.07, 4.2 and 3.4 IJg/mL, respectively, whereas the corresponding LCloo values were 100.0, 1500.0, 0.17, 25.0 and 9.0 IJg/mL, respectively. The LC50 values of these pesticides in succession in N2-fixing agar medium were 44.7, 239.9, 0.07, 1.8 and 2.3 IJg/mL, respectively, whereas the corresponding LC100 values were 100.0, 600.0, 0.17, 10.0 and 7.0 IJg/mL, respectively. Similar results with nitrate supplemented liquid and agar media indicated that nitrate supplementation had toxicity reducing effect. The LCso and LC^oo values of toxicity in the N2-fixing liquid medium at soil-water interface were 91.2 and 200.0 IJg/mL for carbaryl, 2 317 and 6 000 pg/mL for carbofuran, 0.15 and 0.50 pg/mL for ziram, 16.4 and 50.0 pg/mL for zineb, and 7.2 and 25.0 pg/mL for mancozeb, respectively. Each LC^oo value at soil- water interface with a pesticide was significantly higher than its corresponding LCloo value at liquid/agar media. It can be concluded that, under the N2-fixing conditions, the cyanobacterium tolerated higher levels of each pesticide at soil-water interface.

Formation of Uniform Oil-Soluble Fe_3O_4 Nanoparticles via Oil-Water Interface System

Nowadays,the novel oil water interface method has attracted a considerable attention owing to the advantages of mild reaction conditions,simple operation,low cost,and high efficiency.In this paper,uniform oil-soluble Fe_3O_4 nanoparticles(NPs) were synthesized by oil-water interface method from mixing iron tristearate of 0.067mol/L in cyclohexane with ferrous sulfate in water.The as-prepared products were characterized by X-ray diffraction(XRD),transmission electron microscopy(TEM),vibrating sample magnetometer(VSM),Fourier transform infrared spectroscopy(FT-IR) and thermogravimetric analyzer(TGA).TEM images and XRD profiles showed that the size of the oil-soluble products ranged in 1.7-6.9 nm.VSM indicated that the Fe_3O_4 NPs were superparamagetic.FT-IR and TGA proved that oleic acid was combined to the surface of Fe_3O_4 NPs closely.TEM images and XRD profiles revealed that the most suitable reaction concentration of NH_3·H_2O,oleic acid/water in volume,reaction temperature and reaction time were 4.5 mol/L,50:1 000,80℃ and 6 h,respectively.The formation mechanism of the nearly monodispersed Fe_3O_4 NPs was that the preformed Fe_3O_4 nuclei were capped by oleic acid as early as the nucleation occurred in oil-water interface and subsequently entered into oil phase to stop growing.

Surfactant Adsorbed at the Oil-Water Interface and Its Elimination

Surfactants are widely used in the petroleum industry as one kind of Enhanced Oil Recovery methods (EOR). The oil sands mines in Northern Alberta are the largest one in the world. Due to using sodium hydroxide in bitumen extraction process, there are a lot of surfactant molecules in the tailing water. The surfactants from oil sands industry have brought a potential threat to the environment and human health. Depending on the performance of surfactant at the interface, this work focuses on removing these harmful surfactants from the tailing water and not bringing other possible hazardous substances. Moreover, a mathematical model is built to calculate the removal efficiency of the surfactant. The time required for removing the surfactant is determined experimentally. In conclusion, most of surfactant molecules are adsorbed at the oil/water interface. The fraction of the surfactant staying at the oil/water interface is high. Most of the surfactants in tailing water can be eliminated. The time of surfactant migration can be used for setting up the update time of the oil film in the automatic instrument, which can be designed in the future.

The diffusive fluxes of inorganic nitrogen across the intertidal sediment-water interface of the Changjiang Estuary in China

Ammonium and nitrate concentrations were analyzed in near-bottom water and pore water collected from ten stations of the intertidal flat of the Changjiang Estuary during April, July, November and February. The magnitudes of the benthic exchange fluxes were determined on the basis of concentration gradients of ammonium and nitrate at the near-bottom water and interstitial water interface in combination with calculations of a modified Fick＇ s first law. Ammonium fluxes varied from - 5.05 to 1.43 μg/（ cm^2·d） and were greatly regulated by the production of ammonium in surface sediments, while nitrate fluxes ranged from - 0. 38 to 1.36 μg/ （ cm^2·d） and were dominated by nitrate concentrations in the tidal water. It was found that ammonium was mainly released from sediments into water columns at most of stations whereas nitrate was mostly diffused from overlying waters to intertidal sediments. In total, 823.75 t/a ammonium-N was passed from intertidal sediments to water while about 521.90 t/a nitrate-N was removed from overlying waters to intertidal sediments. This suggests that intertidal sediments had the significant influence on modulating inorganic nitrogen in the tidal water.

Photophysics and electrochemistry relevant to photocatalytic water splitting involved at solid–electrolyte interfaces

Direct photon to chemical energy conversion using semiconductor–electrocatalyst–electrolyte interfaces has been extensively investigated for more than a half century. Many studies have focused on screening materials for efficient photocatalysis. Photocatalytic efficiency has been improved during this period but is not sufficient for industrial commercialization. Detailed elucidation on the photocatalytic water splitting process leads to consecutive six reaction steps with the fundamental parameters involved: The photocatalysis is initiated involving photophysics derived from various semiconductor properties(1: photon absorption, 2: exciton separation). The generated charge carriers need to be transferred to surfaces effectively utilizing the interfaces(3: carrier diffusion, 4: carrier transport). Consequently, electrocatalysis finishes the process by producing products on the surface(5: catalytic efficiency, 6: mass transfer of reactants and products). Successful photocatalytic water splitting requires the enhancement of efficiency at each stage. Most critically, a fundamental understanding of the interfacial phenomena is highly desired for establishing 'photocatalysis by design' concepts, where the kinetic bottleneck within a process is identified by further improving the specific properties of photocatalytic materials as opposed to blind material screening. Theoretical modeling using the identified quantitative parameters can effectively predict the theoretically attainable photon-conversion yields. This article provides an overview of the state-of-the-art theoretical understanding of interfacial problems mainly developed in our laboratory.Photocatalytic water splitting(especially hydrogen evolution on metal surfaces) was selected as a topic,and the photophysical and electrochemical processes that occur at semiconductor–metal, semiconductor–electrolyte and metal–electrolyte interfaces are discussed.

Duplex Interpenetrating-Phase FeNiZn and FeNi_(3)Heterostructure with Low-Gibbs Free Energy Interface Coupling for Highly Efficient Overall Water Splitting

The sluggish kinetics of both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)generate the large overpotential in water electrolysis and thus high-cost hydrogen production.Here,multidimensional nanoporous interpenetrating-phase FeNiZn alloy and FeNi_(3)intermetallic heterostructure is in situ constructed on NiFe foam(FeNiZn/FeNi_(3)@NiFe)by dealloying protocol.Coupling with the eminent synergism among specific constituents and the highly efficient mass transport from integrated porous backbone,FeNiZn/FeNi_(3)@NiFe depicts exceptional bifunctional activities for water splitting with extremely low overpotentials toward OER and HER(η_(1000)=367/245 mV)as well as the robust durability during the 400 h testing in alkaline solution.The as-built water electrolyzer with FeNiZn/FeNi_(3)@NiFe as both anode and cathode exhibits record-high performances for sustainable hydrogen output in terms of much lower cell voltage of 1.759 and 1.919 V to deliver the current density of 500 and 1000 mA cm^(-2)as well long working lives.Density functional theory calculations disclose that the interface interaction between FeNiZn alloy and FeNi_(3)intermetallic generates the modulated electron structure state and optimized intermediate chemisorption,thus diminishing the energy barriers for hydrogen production in water splitting.With the merits of fine performances,scalable fabrication,and low cost,FeNiZn/FeNi_(3)@NiFe holds prospective application potential as the bifunctional electrocatalyst for water splitting.

Interface Engineering of NixSy@MnOxHy Nanorods to Efficiently Enhance Overall-Water-Splitting Activity and Stability

Exploring highly active and stable transition metal-based bifunctional electrocatalysts has recently attracted extensive research interests for achieving high inherent activity, abundant exposed active sites, rapid mass transfer, and strong structure stability for overall water splitting. Herein, an interface engineering coupled with shell-protection strategy was applied to construct three-dimensional(3D) core-shell NixSy@MnOxHy heterostructure nanorods grown on nickel foam(NixSy@MnOxHy/NF) as a bifunctional electrocatalyst. NixSy@MnOxHy/NF was synthesized via a facile hydrothermal reaction followed by an electrodeposition process. The X-ray absorption fine structure spectra reveal that abundant Mn-S bonds connect the heterostructure interfaces of N ixSy@MnOxHy, leading to a strong electronic interaction, which improves the intrinsic activities of hydrogen evolution reaction and oxygen evolution reaction(OER). Besides, as an efficient protective shell, the MnOxHy dramatically inhibits the electrochemical corrosion of the electrocatalyst at high current densities, which remarkably enhances the stability at high potentials. Furthermore, the 3D nanorod structure not only exposes enriched active sites, but also accelerates the electrolyte diffusion and bubble desorption. Therefore, NixSy@MnOxHy/NF exhibits exceptional bifunctional activity and stability for overall water splitting, with low overpotentials of 326 and 356 mV for OER at 100 and 500 mA cm^(–2), respectively, along with high stability of 150 h at 100 mA cm^(–2). Furthermore, for overall water splitting, it presents a low cell voltage of 1.529 V at 10 mA cm^(–2), accompanied by excellent stability at 100 mA cm^(–2) for 100 h. This work sheds a light on exploring highly active and stable bifunctional electrocatalysts by the interface engineering coupled with shell-protection strategy.

Interface-strengthened CoP nanosheet array with Co2P nanoparticles as efficient electrocatalysts for overall water splitting

Highly active and durable bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) play a pivotal role in overall water splitting. Herein, we demonstrate the construction of interface-strengthened CoP nanosheet array with Co2P nanoparticles as such an electrocatalyst through a facile hydrothermal reaction and the subsequent phosphorization process. The twodimensional (2D) nanosheets with thickness of^55 nm expose a great number of active sites. The surface chemical state indicates that the strongly coupled CoP/Co2P electrocatalysts can adsorb or generate more targeted intermediates (e.g. OH- or OOH*) for both HER/OER. As a result, the CoP/Co2P electrocatalysts exhibit small overpotentials of 68 and 256 mV to drive 10 mA cm^-2 for HER and OER, respectively, outperforming most of the recently reported Co-based electrocatalysts. Furthermore, an alkaline electrolyzer assembled by using CoP/Co2P as both cathode and anode can achieve a current density of 10 mA cm^-2 at a low voltage of 1.57 V and work continuously for over 58 h. This work provides a feasible structural design for transition metal phosphides electrocatalysts with efficient and stable overall water splitting.

Electronic modulation and interface engineering of electrospun nanomaterials‐based electrocatalysts toward water splitting

Nowdays,electrocatalytic water splitting has been regarded as one of the most efficient means to approach the urgent energy crisis and environmental issues.However,to speed up the electrocatalytic conversion efficiency of their half reactions including hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),electrocatalysts are usually essential to reduce their kinetic energy barriers.Electrospun nanomaterials possess a unique one‐dimensional structure for outstanding electron and mass transportation,large specific surface area,and the possibilities of flexibility with the porous feature,which are good candidates as efficient electrocatalysts for water splitting.In this review,we focus on the recent research progress on the electrospun nanomaterials‐based electrocatalysts for HER,OER,and overall water splitting reaction.Specifically,the insights of the influence of the electronic modulation and interface engineering of these electrocatalysts on their electrocatalytic activities will be deeply discussed and highlighted.Furthermore,the challenges and development opportunities of the electrospun nanomaterials‐based electrocatalysts for water splitting are featured.Based on the achievements of the significantly enhanced performance from the electronic modulation and interface engineering of these electrocatalysts,full utilization of these materials for practical energy conversion is anticipated.

Plasmonic Field Enhancement for Vibration Spectroscopy at Metal/Water Interfaces

Electrochemical （EC） reactions play vital roles in many disciplines, and its molecular-level understanding is highly desired, in particular under reactions. The vibration spectroscopy is a powerful in situ technique for chemical analysis, yet its application to EC reactions is hindered by the strong attenuation of infrared （IR） light in both electrodes and electrolytes. Here we demonstrate that by incorporating appropriate sub-wavelength plasmonic structures at the metal electrode, the IR field at the EC interface can be greatly enhanced via the excitation of surface plasmon. This scheme facilitates in situ vibrational spectroscopic studies, especially using the surface-specific sum-frequency generation technique.

Purification of Produced Water from a Sour Oilfield in South Kuwait. 1. Oil-Water Separation and Industrial Salt Production

Produced water from an oil extraction site in South Kuwait was sampled after primary oil – water separation had been carried out. The produced water was filtered through a mixture of activated charcoal and esterified cellulosic material gained from spent coffee grounds as a tertiary adsorption treatment. The earth-alkaline metal ions and heavy metals were separated from the de-oiled produced water by addition of either sodium or potassium hydroxide in the presence of carbon dioxide or by direct addition of solid sodium carbonate. The resulting filtrate gave salt of industrial purity upon selective crystallization on evaporation.

Influence of pore structure heterogeneity on channeling channels during hot water flooding in heavy oil reservoir based on CT scanning

Hot water flooding is an effective way to develop heavy oil reservoirs.However,local channeling channels may form,possibly leading to a low thermal utilization efficiency and high water cut in the reservoir.The pore structure heterogeneity is an important factor in forming these channels.This study proposes a method that mixes quartz sand with different particle sizes to prepare weakly heterogeneous and strongly heterogeneous models through which hot water flooding experiments are conducted.During the experiments,computer tomography(CT)scanning identifies the pore structure and micro remaining oil saturation distribution to analyze the influence of the pore structure heterogeneity on the channeling channels.The oil saturation reduction and average pore size are divided into three levels to quantitatively describe the relationship between the channeling channel distribution and pore structure heterogeneity.The zone where oil saturation reduction exceeds 20%is defined as a channeling channel.The scanning area is divided into 180 equally sized zones based on the CT scanning images,and threedimensional(3D)distributions of the channeling channels are developed.Four micro remaining oil distribution patterns are proposed,and the morphology characteristics of micro remaining oil inside and outside the channeling channels are analyzed.The results show that hot water flooding is more balanced in the weakly heterogeneous model,and the oil saturation decreases by more than 20%in most zones without narrow channeling channels forming.In the strongly heterogeneous model,hot water flooding is unbalanced,and three narrow channeling channels of different lengths form.In the weakly heterogeneous model,the oil saturation reduction is greater in zones with larger pores.The distribution range of the average pore size is larger in the strongly heterogeneous model.The network remaining oil inside the channeling channels is less than outside the channeling channels,and the hot water converts the network remaining oil into cluster,film,and droplet remaining oil.

Superhydrophobic melamine sponge prepared by radiation-induced grafting technology for efficient oil-water separation

This paper presents a superhydrophobic melamine(ME)sponge(ME-g-PLMA)prepared via high-energy radiation-induced in situ covalent grafting of long-alkyl-chain dodecyl methacrylate(LMA)onto an ME sponge for efficient oil–water separation.The obtained ME-g-PLMA sponge had an excellent pore structure with superhydrophobic(water contact angle of 154°)and superoleophilic properties.It can absorb various types of oils up to 66–168 times its mass.The ME-g-PLMA sponge can continuously separate oil slicks in water by connecting a pump or separating oil underwater with a gravity-driven device.In addition,it maintained its highly hydrophobic properties even after long-term immersion in different corrosive solutions and repeated oil adsorption.The modified ME-g-PLMA sponge exhibited excellent separation properties and potential for oil spill cleanup.

A CFD Model to Evaluate Near-Surface Oil Spill from a Broken Loading Pipe in Shallow Coastal Waters

Oil spills continue to generate various issues and concerns regarding their effect and behavior in the marine environment,owing to the related potential for detrimental environmental,economic and social implications.It is essential to have a solid understanding of the ways in which oil interacts with the water and the coastal ecosystems that are located nearby.This study proposes a simplified model for predicting the plume-like transport behavior of heavy Bunker C fuel oil discharging downward from an acutely-angled broken pipeline located on the water surface.The results show that the spill overall profile is articulated in three major flow areas.The first,is the source field,i.e.,a region near the origin of the initial jet,followed by the intermediate or transport field,namely,the region where the jet oil flow transitions into an underwater oil plume flow and starts to move horizontally,and finally,the far-field,where the oil re-surface and spreads onto the shore at a significant distance from the spill site.The behavior of the oil in the intermediate field is investigated using a simplified injection-type oil spill model capable of mimicking the undersea trapping and lateral migration of an oil plume originating from a negatively buoyant jet spill.A rectangular domain with proper boundary conditions is used to implement the model.The Projection approach is used to discretize a modified version of the Navier-Stokes equations in two dimensions.A benchmark fluid flow issue is used to verify the model and the results indicate a reasonable relationship between specific gravity and depth as well as agreement with the aerial data and a vertical temperature profile plot.

A Gasification Technology to Combine Oil Sludge with Coal-Water Slurry:CFD Analysis and Performance Determination

The development of more environment-friendly ways to dispose of oil sludge is currently regarded as a hot topic.In this context,gasification technologies are generally seen as a promising way to combine oil sludge with coal–water slurry(CWS)and generate resourceful fuel.In this study,a novel five-nozzle gasifier reactor was analyzed by means of a CFD(Computational fluid dynamic)method.Among several influential factors,special attention was paid to the height-to-diameter ratio of the gasifier and the mixing ratio of oil sludge,which are known to have a significant impact on the flow field,temperature distribution and gasifier performances.According to the numerical results,the optimal height-to-diameter ratio and oil mixing ratio are about 2.4:1 and 20%,respectively.Furthermore,the carbon conversion rate can become as high as 98.55%with the hydrolysis rate reaching a value of 53.88%.The consumption of raw coal and oxygen is generally reduced,while the effective gas production is increased to 50.93 mol/%.

Purification of Produced Water from a Sour Oilfield in South Kuwait. 2. Oil-Water Separation and Crystallization of Calcium Carbonate

Oil-water separation for produced water (PW) originating from an oil extraction site in South Kuwait was carried out using bleached, esterified cellulosic material from used coffee grounds. Thereafter, earth-alkaline metal ions, specifically calcium ions, of the de-oiled PW were removed by precipitation with sodium carbonate to give access to pure sodium chloride as industrial salt from the remaining PW. While the purity of the precipitated calcium carbonate (CaCO3) depends on the precipitation conditions, CaCO3 of up to 95.48% purity can be obtained, which makes it a salable product. The precipitation of CaCO3 decreases the amount of calcium ions in PW from 11,300 ppm to 84 ppm.

Mechanism study of reduction of CO_2 into formic acid by in-situ hydrogen produced from water splitting with Zn: Zn/ZnO interface autocatalytic role

We have previously developed a new process of highly efficient conversion of COand water into formic acid with metallic Zn without the addition of catalyst, however, its mechanism is not clear, particularly in the catalytic role of Zn/ZnO interface. Herein, the autocatalytic role of Zn/ZnO interface formed in situ during the reduction of COinto formic acid with Zn in water was studied by combining high resolution transmission electron microscopy（HRTEM）, X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS） techniques and experimental data. The electron microscope results show that possible defects or dislocations formed on Zn/ZnO interface, in which plays a key role for Zn H-formation. Further XPS analyses indicate that oxygen vacancies on Zn/ZnO interface increased at short reaction times（less than 10 min）. These analyses and experimental results suggest that a highly efficient and rapid conversion of COand water into formic acid should involve an autocatalytic role of the Zn/ZnO interface formed in situ, particularly at the beginning of the reaction.