Development of Superhydrophobic Nano-SiO_(2)and Its Field Application in Low-permeability,High-temperature,and High-salinity Oil Reservoirs

In this study,to meet the stringent requirements on the hydrophobicity of nano-SiO_(2)particles for use in depressurization and enhanced injection operations in high-temperature and high-salinity oil reservoirs,secondary chemical grafting modification of nano-SiO_(2)is performed using a silane coupling agent to prepare superhydrophobic nano-SiO_(2) particles.Using these superhydrophobic nano-SiO_(2)particles as the core agent,and liquid paraffin or diesel as the dispersion medium,a uniform dispersion of nano-SiO_(2)particles is achieved under high-speed stirring,and a chemically enhanced water injection system with colloidal stability that can be maintained for more than 60 d is successfully developed.Using this system,a field test of depressurization and enhanced injection is carried out on six wells in an oilfield,and the daily oil production level is increased by 11 t.The cumulative increased water injection is 58784 m^(3),the effective rate of the measures was 100%,and the average validity period is 661 d.

Reconcile the contradictory wettability requirements for the reduction and oxidation half-reactions in overall CO_(2) photoreduction via alternately hydrophobic surfaces

The overall photocatalytic CO_(2) reduction reaction(OPCRR)that can directly convert CO_(2) and H_(2)O into fuels represents a promising renewable energy conversion technology.As a typical redox reaction,the OPCRR involves two half-reactions:the CO_(2) reduction half-reaction(CRHR)and the water oxidation half-reaction(WOHR).Generally,both half-reactions can be promoted by adjusting the wettability of catalysts.However,there is a contradiction in wettability requirements for the two half-reactions.Specifically,CRHR prefers a hydrophobic surface that can accumulate more CO_(2) molecules on the active sites,ensuring the appropriate ratio of gas-phase(CO_(2))to liquid-phase(H_(2)O)reactants.Conversely,the WOHR prefers a hydrophilic surface that can promote the departure of the gaseous product(O_(2))from the catalyst surface,preventing isolation between active sites and the reactant(H_(2)O).Here,we successfully reconciled the contradictory wettability requirements for the CRHR and WOHR by creating an alternately hydrophobic catalyst.This was achieved through a selectively hydrophobic modification method and a charge-transfer-control strategy.Consequently,the collaboratively promoted CRHR and WOHR led to a significantly enhanced OPCRR with a solar-to-fuel conversion efficiency of 0.186%.Notably,in ethanol production,the catalyst exhibited a 10.64-fold increase in generation rate(271.44μmol g^(-1)h~(-1))and a 4-fold increase in selectivity(55.77%)compared to the benchmark catalyst.This innovative approach holds great potential for application in universal overall reactions involving gas participation.

Preparation and Adsorption Property of Hydrophobic SiO_2 Aerogels Modif ied by Methyl Triethoxysilane

The hydrophobic SiO2 aerogels were prepared by in-situ polymerization sol-gel method and supercritical drying of ethanol method with tetraethylorthosilicate（TEOS） as silica source, methyl triethoxysilane （MTMS） as modifier, ethanol as solvent. Moreover, the structure and adsorption property of SiO2 aerogels were also studied. As results, the surface area of SiO2 aerogels was 863.59 m2/g, the pore volume was 3.57 cm3/g, and the contact angle was 150 °. Adsorption intensity of silica aerogels for organic liquid （alkanes, benzene compounds, and nitro-compounds） is bigger than that of activated carbon. The mass of the liquid absorbed increased linearly with the surface tension of the liquid. The lower surface tension and boiling point are, the shorter desorption time is. After regenerating 10 times, nitromethane regeneration rate remain the same, and almost more than 94%. So SiO2 aerogels have good absorption and regeneration property.

Reduced graphene oxide aerogel decorated with Mo_(2)C nanoparticles toward multifunctional properties of hydrophobicity,thermal insulation and microwave absorption

Reduced graphene oxide(rGO)aerogels are emerging as very attractive scaffolds for high-performance electromagnetic wave absorption materials(EWAMs)due to their intrinsic conductive networks and intricate interior microstructure,as well as good compatibility with other electromagnetic(EM)components.Herein,we realized the decoration of rGO aerogel with Mo_(2)C nanoparticles by sequential hydrothermal assembly,freeze-drying,and high-temperature pyrolysis.Results show that Mo_(2)C nanoparticle loading can be easily controlled by the ammonium molybdate to glucose molar ratio.The hydrophobicity and thermal insulation of the rGO aerogel are effectively improved upon the introduction of Mo_(2)C nanoparticles,and more importantly,these nanoparticles regulate the EM properties of the rGO aerogel to a large extent.Although more Mo_(2)C nanoparticles may decrease the overall attenuation ability of the rGO aerogel,they bring much better impedance matching.At a molar ratio of 1:1,a desirable balance between attenuation ability and impedance matching is observed.In this context,the Mo_(2)C/r GO aerogel displays strong reflection loss and broad response bandwidth,even with a small applied thickness(1.7 mm)and low filler loading(9.0wt%).The positive effects of Mo_(2)C nanoparticles on multifunctional properties may render Mo_(2)C/r GO aerogels promising candidates for high-performance EWAMs under harsh conditions.

Surface hydrophobic modification of MXene to promote the electrochemical conversion of N_(2) to NH_(3)

Hydrophobic treatment of the catalyst surfaces can suppress the competitive hydrogen evolution reaction(HER) during the nitrogen reduction reaction(NRR).In this work,the surface of Ti_(3)C_(2)Ti_(x) MXene is modified by cetyltrimethylammonium bromide(CTAB) and trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-trideca fluorooctyl) silane(FOTS) to increase the hydrophobicity of MXenes.The ammonia(NH_(3)) production rate and faradaic efficiency(FE) are improved from 37.62 to 54.01 μg h^(-1)mg_(cat)^(-1).and 5.5% to 18.1% at-0.7 V vs.RHE,respectively after surface modification.^(15)N isotopic labeling experiment confirms that nitrogen in produced ammonia originates from N_(2) in the electrolyte.The excellent NRR activity of surface hydrophobic MXenes is mainly due to surfactant molecules,which inhibit the entry of water molecules and the competitive HER,which have been verified by in situ FT-IR,DFT and molecular dynamics calculations.This strategy provides an ingenious method to design more active NRR electrocatalysts.

Enhancing hydrophobicity via core-shell metal organic frameworks for high-humidity flue gas CO_(2) capture

Developing metal-organic framework(MOF)materials with the moisture-resistant feature is highly desirable for CO_(2)capture from highly humid flue gas.In this work,a new core-shell MOF@MOF composite using Mg-MOF-74 with high CO_(2)capture capacity as a functional core and hydrophobic zeolitic imidazolate framework-8(ZIF-8)as a protective shell is fabricated by the epitaxial growth method.Experimental results show that the CO_(2)adsorption performance of the core-shell structured Mg-MOF-74@ZIF-8 composites from water-containing flue gas is enhanced along with their improved hydrophobicity.The dynamic breakthrough results show that the Mg-MOF-74@ZIF-8 with three assembled layers(Mg-MOF-74@ZIF-8-3)can capture 3.56 mmol-g^(-1)CO_(2)from wet CO_(2)/N_(2)(VCO_(2):V_(N_(2))=15:85)mixtures,which outperforms Mg-MOF-74(0.37 mmol·g^(-1))and most of the reported physisorbents.

CeO_(2)/PTFE涂层微粗糙结构的构筑及其超疏水性能

采用熔盐法制备呈八面体状、粒径尺寸分布在300~500 nm的CeO_(2)颗粒,借助喷涂法制备CeO_(2)/PTFE涂层,目的是通过CeO_(2)颗粒的加入填充或者嵌入在PTFE的网络结构上,以此构筑CeO_(2)/PTFE涂层微粗糙结构提高其疏水性能.探讨不同的CeO_(2)颗粒含量在不同硬度铝基底上(Al 3003和Al 3004)对CeO_(2)/PTFE涂层疏水性能的影响,进而从“CeO_(2)颗粒的显微结构”和“微粗糙结构的构筑”两个方面阐明CeO_(2)/PTFE涂层的超疏水机理.结果表明:当CeO_(2)颗粒含量为0.5 wt%时,从SEM图中看出CeO_(2)/PTFE涂层的表面出现大量突起且呈现密集均匀排布即构筑出“单层连续网络结构”;CeO_(2)颗粒嵌入PTFE涂层的网络结构中CeO_(2)/PTFE涂层疏水性能最佳,从润湿性分析得到在Al 3003和Al 3004接触角分别为154.7°和153.3°.当CeO_(2)颗粒含量小于0.5 wt%时,构筑涂层表面呈现“孤岛状结构”;大于0.5 wt%时,构筑涂层表面呈现“多层不连续网络结构”.

SiO_(2)高效节能气凝胶隔热材料的制备及性能研究

以N,N-二甲基甲酰胺为干燥剂,通过常压干燥法制备了SiO_(2)气凝胶隔热材料,研究了正硅酸乙酯和水的摩尔比对SiO_(2)气凝胶形貌、物相结构、孔径分布、力学性能和导热性能的影响。结果表明,SiO_(2)气凝胶隔热材料为典型的非晶结构,具有有序的介孔孔道,随着水摩尔比的增大,气凝胶的孔道结构有序度逐渐提高,宏观形貌更加完整且致密,摩尔比n(TEOS)∶n(水)=1∶30制备出的气凝胶的多孔网格结构最为致密。随着水摩尔比的增大,SiO_(2)气凝胶的比表面积、抗压强度先增大后降低,导热系数先降低后增大。当摩尔比n(TEOS)∶n(水)=1∶30时,气凝胶比表面积最大为441 m^(2)/g,对应的孔体积为0.414 cm^(3)/g,孔径分布为3.75 nm,抗压强度最大为29.79 kPa,导热系数最低为0.022 W/(m·K),保温性能最优。以TMCS和正己烷对SiO_(2)气凝胶进行疏水改性,体积比V(TMCS)∶V(正己烷)=1∶10时,SiO_(2)气凝胶表面的接触角达到最大值139.6°,疏水性能最佳,热稳定性也得到改善。

3D打印柔性SiO_(2)气凝胶复合材料的研究

SiO_(2)气凝胶因特殊网络结构而存在优异的性质,如高比表面积、高孔隙率、低热导率和低密度,是优异的保温绝热材料。但SiO2气凝胶机械性能脆弱,导致传统制造方法难以制备复杂和微小型构件,极大地阻碍了SiO_(2)气凝胶在隔热领域的发展和应用。本文通过3D打印直写技术制备了柔性SiO_(2)气凝胶复合材料,通过研究不同聚乙烯醇(PVA)溶液和十八酸钠(C_(17)H_(35)COONa)的含量,找到最佳浆料配比,打印的柔性SiO_(2)气凝胶复合材料在100℃下的热导率低至0.026 W/(m·K),同时具有较好的压缩性能、弯曲性能和疏水性。这项研究为SiO_(2)气凝胶的规模化应用提供一种可能。

Research on a New Process of Preparation for Nano-SiO_2 with High Activity and Mesopores

Nano-SiO_2 with high activity and mesopores was prepared through sol-gel synthesis followed by low-temperatureheat treatment and ball milling firstly in our experiments. TEM was performed to measure particle sizes. Nitrogenadsorption experiments were carried out to estimate specific surface area, porous distribution and porous ratio by BETand BJH methods. The content of Si-OH in SiO_2 surface was calculated by analysis of the results of hydrogen-oxygencontent mensuration (HOCM). As a result, appropriate heat treatment system and ball milling time are important topreparation for nano-SiO_2 with high activity and mesopores, which are 5～50 nm particles, 5～6 nm average aperture,85%～93% porous ratio, and 51%～55% Si-OH content in surface. Nano-SiO_2 with that structure has high surfaceenergy and activity. This process, which has simple facilities and operation rules, is a new way of preparation fornano-SiO_2 with high activity and mesopores.

Hydrophobic modification of SAPO-34 membranes for improvement of stability under wet condition

SAPO-34 zeolite membranes show high efficiency for CO2/CH4 separation but suffer from the reduction of separation performance when exposed to humid atmosphere.In this work,n-dodecyltrimethoxysilane(DTMS)was used to modify the hollow fibers supported SAPO-34 membranes to increase the external surface hydrophobicity and thus sustain their performance under moisture environment.The modified membranes were fully characterized.Their separation performance was extensively investigated in both dry and wet gaseous systems and compared with the un-modified ones.The un-modified SAPO-34 membrane exhibited a high separation selectivity of 160 and CO2 permeance of 1.18×10-6 mol·m-2·s-1·Pa-1 for separation of dry CO2/CH4 at 298 K.However,its separation selectivity declined to 0.9 and the CO2 permeance was only about 1.7×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 at same temperature.High temperature(e.g.353 K)could reduce the effect of moisture to improve SAPO-34 separation selectivity,but further increasing temperature(e.g.373 K)led to decrease in CO2/CH4 separation selectivity.A significant decrease of selectivity was observed at higher pressure drop.The modified SAPO-34 membrane showed decreased CO2 permeance but increased separation selectivity for dry CO2/CH4 gas mixture,and super performance for wet CO2/CH4 gas mixture due to the improved hydrophobicity of membrane surface.A separation selectivity of 65 and CO2 permeance of 4.73×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 mixture can be observed at 353 K with a pressure drop of 0.4 MPa.Furthermore,the modified membrane exhibited stable separation performance during the 120-hour test for wet CO2/CH4 mixture at 353 K.The hydrophobic modification paves a way for SAPO-34 membranes in real applications.

Hydrophobic intensification flotation:Comparison of collector containing two minerophilic groups with conventional collectors

The surface hydrophobization and flotation of a xanthate−hydroxamate collector toward copper oxide mineral were compared with the combined collectors of xanthate and hydroxamate through water contact angle(WCA)and micro-flotation experiments.The results showed that S-[(2-hydroxyamino)-2-oxoethyl]-O-octyl-dithiocarbonate ester(HAOODE)exhibited stronger hydrophobization and better flotation performance to malachite(Cu2(OH)2CO3)than octyl-hydroxamic acid(OHA)and its combination with S-allyl-O-ethyl xanthate ester(AEXE).To understand the hydrophobic intensification mechanism of HAOODE to malachite,zeta potential,atomic force microscopy(AFM)and XPS measurements were carried out.The results recommended that malachite chemisorbed HAOODE to form Cu—HAOODE complexes in which the hydroxamate—(O,O)—Cu and—O—C(—S—Cu)—S—configurations co-existed.The co-adsorption of HAOODE’s hetero-difunctional groups was more stable than the single-functionalgroup adsorption of OHA and AEXE,which produced the“loop”structure and intensified the self-assembly alignment of HAOODE on malachite surfaces.In addition,the“h”shape steric orientation of the double hydrophobic groups in HAOODE facilitated stronger hydrophobization toward malachite than the“line”or“V”hydrophobic carbon chains of OHA or AEXE.Thus,HAOODE achieved the preferable flotation recovery of malachite particles in comparison with OHA and AEXE.

SYNTHESIS AND CHARACTERIZATION OF A NOVEL FLUORINE-CONTAINING HYDROPHOBICALLY ASSOCIATING POLYMER

In this article, the synthesis and characterization of a novel fluoromonomer and its copolymer with acrylamide is reported. 2-perfluoroamyl-4-hydroxylquinoline 2 was synthesized from ethyl 2, 2-dihydroperfluoroheptanoate in high yields. The monomer 4 was then synthesized from 2 in two steps readily in high yields. Synthesis and characterization of copolymers of acrylamide (AM) and the fluoromonomer were investigated. The composition and intrinsic viscosity of these copolymers were studied. It was found that the rheological properties of aqueous solutions of polyacrylamide were modified significantly when a small proportion of the fluoromonomer 4 was incorporated on investigating the viscosity-concentration profiles, pseudoplasticity of these solutions and the effect of the presence of surfactant. These results could be explained by the hydrophobic association of the fluorocarbon segments in the aqueous solutions of these copolymers.

Nano-SiO_(2)和镍渣掺量对碱矿渣砂浆强度和自收缩的影响

为改善碱矿渣砂浆自收缩大的缺陷,将Nano-SiO_(2)和镍渣掺入其中,研究两者掺量对抗折强度、抗压强度和自收缩的影响。研究结果表明:在镍渣掺量一定时,随着Nano-SiO_(2)掺量的增加强度值先提高后降低,掺量为1%时强度值最高,对强度的提高幅度也最大;当Nano-SiO_(2)掺量一定时,随着镍渣掺量的增加强度值逐渐降低,掺量为30%时强度降低幅度最小;当镍渣掺量为30%,随着Nano-SiO_(2)掺量的增加,自收缩值先降低后提高,掺量为1%时,自收缩值最小,对自收缩的降低幅度也最大;当Nano-SiO_(2)掺量为1%时,随着镍渣掺量的增加自收缩值逐渐降低,掺量为30%时降低幅度最大。

Ultraviolet shielding property of crylic acid resin filled with nano-SiO_2

The present status and development trends of nano-composite coatings were briefly introduced. The nano-SiO2 was dispersed into crylic acid resin by ultrasonic wave and high-energy ball milling, the influence of nano-SiO2 on shielding property of coatings was investigated. Relation between particle size distribution of original nano-SiO2 and its dispersal in water and alcohol after treatment were analyzed, respectively. The ultraviolet permeation rate of coatings filled with nano-SiO2 was detected by ultraviolet spectral photometer. And the particle size distribution of coatings was examined by TEM. The results show that particle size distribution is comparative convergence and smaller one order of magnitude after dispersal treatment. The size of most nano-SiO2 in coatings is smaller than 100nm, which indicates that the amount of nano-SiO2 in the resin is 20% （solid content of resin）, the permeation rate of ultraviolet of composite coatings decreases to 20%. The research of its excellent ultraviolet shielding property mechanism indicates minor size and high surface energy of nano-SiO2 can produce different absorption, reflection and scatter actions to different wavelengths.

Mechanical Properties and Fire Retardancy of Wood Flour/High-Density Polyethylene Composites Reinforced with Continuous Honeycomb-Like Nano-SiO_(2)Network and Fire Retardant

The mechanical properties of wood flour/high-density polyethylene composites(WPC)were improved by adding a small amount of nano-SiO_(2)to obtain a network-structured WPC with a continuous honeycomb-like nano-SiO_(2)network.The wood flour was modified with a fire retardant(a mixture of sodium octabonate and amidine urea phosphate)to improve its fire retardancy.The flexural properties,creep resistance,thermal expansion,and fire retardancy of the WPC were compared to a control(WPCCTRL)without nano-SiO_(2)or fire retardant.The flexural strength and modulus of the WPC containing only 0.55 wt.%nano-SiO_(2)were 6.6%and 9.1%higher than the control,respectively,while the creep strain and thermal expansion rate at 90°C were 33.8%and 13.6%lower,respectively.The cone calorimetry tests revealed that the nano-SiO_(2)network physically shielded the WPC,giving it lower heat release and smoke production rates.The thermal expansion was further decreased by incorporating fire retardants into the WPC,which showed the lowest total heat release and total smoke production and the highest mass retention.This study demonstrates a facile procedure for producing WPC with desired performances by forming a continuous honeycomb-like network by adding a small amount of nanoparticles.

Synthesis and Characterization of Modified Epoxy Resins by Silicic Acid Tetraethyl Ester and Nano-SiO_2

A kind of modified epoxy resins was obtained by condensation of epoxy resin with silicic acid tetraethyl ester（TEOS） and nano-SiO2. The reactions were performed with hydrochloric acid as a catalyst at 63 ℃. The structure, thermal stability and morphological characteristics of the modified epoxy resins were studied through infrared spectra（FT-IR） analysis, thermogravimetric（TG） analysis and scanning electron microscopy respectively. It has been found from the IR and TG study that modified epoxy resins have greater thermal stability than epoxy resins, and its thermal stability has been improved by the formation of inter-crosslinked network structure. The modified epoxy resins exhibit heterogeneous morphology and heterogeneity increases with more TEOS feeding, which in turn confirms the formation of inter-crosslinked network structure in modified epoxy resins.

硅烷偶联剂改性对气相SiO_(2)电缆绝缘复合材料性能的影响

气相SiO_(2)是一种多孔的纳米材料,具有低介电常数、耐高温和耐辐射等优点,作为SiO_(2)电缆的绝缘材料在航空航天等领域得到广泛应用,但气相SiO_(2)复合材料表面存在大量硅羟基使之容易吸潮,因此研究改性剂对气相SiO_(2)复合材料介电性能的影响具有重要意义。选用3种不同的硅烷偶联剂(KH550、KH560、KH570)对气相SiO_(2)电缆绝缘复合材料进行改性,采用显微结构分析、红外光谱分析、宽频介电阻抗谱仪分析等方法研究了不同硅烷偶联剂对气相SiO_(2)电缆绝缘复合材料疏水性能以及介电性能的影响。结果表明硅烷偶联剂KH570对气相SiO_(2)电缆绝缘复合材料的改性效果最好,改性后复合材料吸潮率降低了89.95%,10MHz频率下介电常数和介电损耗角正切分别减小8.63%和31.85%,大幅度提高了气相SiO_(2)电缆绝缘复合材料的疏水性能和介电性能。

Dispersion hydrophobic electrolyte enables lithium-oxygen battery enduring saturated water vapor

Li-O_(2) batteries gain widespread attention as a can didate for next-generati on energy storage devices due to their extraordinary theoretic specific energy.The semi-open structure of Li-O_(2) batteries causes many parasitic reactions,especially related to water.Water is a double-edged sword,which destroys Li anode and simultaneously triggers a solution-based pathway of the discharge product.In this work,hexamethyldisilazane(HMDS)is introduced into the electrolyte of an aprotic Li-O_(2) battery.HMDS has a strong ability to combine with a trace of water to gen erate a hydrophobic hexamethyldisiloxa ne(MM),which eliminates water from the electrolyte decomposition and then prevents the Li anode from producing the insulating LiOH with water.In this case,the hydrophobic MM disperses in the ether-based electrolyte,forming a dispersion hydrophobic electrolyte.This electrolyte can anchor water from the environment on the cathode side,which triggers a solution-based pathway and regulates the growth morphology of the discharge product and consequently increases the discharge capacity.Compared with the Li-O_(2) battery without the HMDS,the HMDS-containing Li-O_(2) battery contributes an about 13-fold increase of cyclability(400 cycles,1800 h)in the extreme environment of saturated water vapor.This work opens a new approach for directly operating aprotic Li-O_(2) batteries in ambient air.

pH值对双(2-甲基-3-呋喃基)二硫醚与α-淀粉酶结合的影响及相互作用机制研究

双(2-甲基-3-呋喃基)二硫醚[bis(2-methyl-3-furyl)disulfide,BMFDS]是肉类的一种关键香气化合物,它与口腔中的α-淀粉酶相互作用,影响人体对香气的感知。该研究采用气相色谱-质谱、紫外吸收光谱、荧光光谱、zeta-电位检测、蛋白质表面疏水性、分子对接分析等方法研究BMFDS与α-淀粉酶之间的相互作用机制以及pH值对其相互作用的影响。结果表明,BMFDS与α-淀粉酶之间自发的相互作用形成了基态复合物,对α-淀粉酶的荧光产生了静态猝灭。不同pH条件下其相互作用强度顺序为pH 7.0>pH 8.5>pH 5.0,但都以疏水相互作用为主。pH会影响BMFDS与α-淀粉酶之间的相互作用强度,但并不会改变二者间的相互作用力和反应类型。总之,BMFDS和α-淀粉酶之间存在非共价相互作用,使α-淀粉酶结构松散,且在3种pH条件下的作用强度有差异。该研究可为后续肉类风味调控提供理论依据。