Texture and Geochemistry of Multi-stage Hydrothermal Scheelite in the Mamupu Cu-Au-Mo(-W)Deposit,Eastern Tibet:Implications for Tungsten Mineralization in the Yulong Belt

Multistage tungsten mineralization was recently discovered in the Mamupu copper-polymetallic deposit in the southern Yulong porphyry copper belt(YPCB),Tibet.This study reports the results of cathodoluminescence,trace element and Sr isotope analyses of Mamupu scheelite samples,undertaken in order to better constrain the mechanism of W mineralization and the sources of the ore-forming fluids.Three different types of scheelite are identified in the Mamupu deposit:scheelite A(Sch A)mainly occurs in breccias during the prograde stage,scheelite B(Sch B)forms in the chlorite-epidote alteration zone in the retrograde stage,while scheelite C(Sch C)occurs in distal quartz sulfide veins.The extremely high Mo content and negative Eu anomaly in Sch A represent high oxygen fugacity in the prograde stage.Compared with ore-related porphyries,Sch A has a similar REE pattern,but with higher ΣREE,more depleted HREE and slightly lower(^(87)Sr/^(86)Sr)i ratios.These features suggest that Sch A is genetically related to ore-related porphyries,but extensive interaction with carbonate surrounding rocks affects the final REE and Sr isotopic composition.Sch B shows dark(Sch B-I)and light(Sch B-II)domains under CL imaging.From Sch B-I to Sch B-II,LREEs are gradually depleted,with MREEs being gradually enriched.Sch C has the highest LREE/HREE ratio,which indicates that it inherited the geochemical characteristics of fluids after the precipitation of HREE-rich minerals,such as diopside and garnet,in the early prograde stage.The Mo content in Sch B and Sch C gradually decreased,indicating that the oxygen fugacity of the fluids changed from oxidative in the early stages to reductive in the later,the turbulent Eu anomaly in Sch B and Sch C indicating that the Eu anomaly in the Mamupu scheelite is not solely controlled by oxygen fugacity.The extensive interaction of magmatic-hydrothermal fluids and carbonate provides the necessary Ca^(2+)for the precipitation of scheelite in the Mamupu deposit.

Trace element compositions of pyrite and stibnite:implications for the genesis of antimony mineralization in the Yangla Cu skarn deposit,Northwestern Yunnan,China

The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.

Magmatic-hydrothermal Evolution and Mineralization Mechanisms of the Wangjiazhuang Cu(-Mo)Deposit in the Zouping Volcanic Basin,Shandong Province,China:Constraints from Fluid Inclusions

The Wangjiazhuang Cu(-Mo)deposit,located within the Zouping volcanic basin in western Shandong Province,China,is unique in this area for having an economic value.In order to expound the metallogenetic characteristics of this porphyry-like hydrothermal deposit,a detailed fluid inclusion study has been conducted,employing the techniques of representative sampling,fluid inclusion petrography,microthermometry,Raman spectroscopy,LA-ICP-MS analysis of single fluid inclusions,as well as cathode fluorescence spectrometer analysis of host mineral quartz.The deposit contains mainly two types of orebodies,i.e.veinlet-dissemination-stockwork orebodies in the K-Si alteration zone and pegmatiticquartz sulfide veins above them.In addition,minor breccia ore occurs locally.Four types of fluid inclusions in the deposit and altered quartz monzonite are identified:L-type one-or two-phase aqueous inclusions,V-type vapor-rich inclusions with V/L ratios greater than 50%-90%,D-type multiphase fluid inclusions containing daughter minerals or solids and S-type silicate-bearing fluid inclusions containing mainly muscovite and biotite.Ore petrography and fluid inclusion study has revealed a three-stage mineralization process,driven by magmatic-hydrothermal fluid activity,as follows.Initially,a hydrothermal fluid,separated from the parent magma,infiltrated into the quartz monzonite,resulting in its extensive K-Si alteration,as indicated by silicate-bearing fluid inclusions trapped in altered quartz monzonite.This is followed by the early mineralization,the formation of quartz veinlets and dissemination-stockwork ores.During the main mineralization stage,due to the participation and mixing of meteoric groundwater with magmatic-sourced hydrothermal fluid,the cooling and phase separation caused deposition of metals from the hydrothermal fluids.As a result,the pegmatitic-quartz sulfide-vein ores formed.In the late mineralization stage,decreasing fluid salinity led to the formation of L-type aqueous inclusions and chalcopyrite-sulfosalt ore.Coexistence of V-type and D-type inclusions and their similar homogenization temperatures with different homogenization modes suggest that phase separation or boiling of the ore-forming fluids took place during the early and the main mineralization stages.The formation P-T conditions of S-type inclusions and the early and the main mineralization stages were estimated as ca.156-182 MPa and 450-650℃,350-450℃,18-35 MPa and 280-380℃,8-15 MPa,respectively,based on the microthermometric data of the fluid inclusions formed at the individual stages.

Fabrication of Graphene/Cu Composite by Chemical Vapor Deposition and Effects of Graphene Layers on Resultant Electrical Conductivity

Graphene(Gr)has unique properties including high electrical conductivity;Thus,graphene/copper(Gr/Cu)composites have attracted increasing attention to replace traditional Cu for electrical applications. However,the problem of how to control graphene to form desired Gr/Cu composite is not well solved. This paper aims at exploring the best parameters for preparing graphene with different layers on Cu foil by chemical vapor deposition(CVD)method and studying the effects of different layers graphene on Gr/Cu composite’s electrical conductivity. Graphene grown on single-sided and double-sided copper was prepared for Gr/Cu and Gr/Cu/Gr composites. The resultant electrical conductivity of Gr/Cu composites increased with decreasing graphene layers and increasing graphene volume fraction. The Gr/Cu/Gr composite with monolayer graphene owns volume fraction of less than 0.002%,producing the best electrical conductivity up to59.8 ×10^(6)S/m,equivalent to 104.5% IACS and 105.3% pure Cu foil.

New insights into the deposition of natural gas hydrate on pipeline surfaces:A molecular dynamics simulation study

Natural gas hydrate(NGH)can cause pipeline blockages during the transportation of oil and gas under high pressures and low temperatures.Reducing hydrate adhesion on pipelines is viewed as an efficient way to prevent NGH blockages.Previous studies suggested the water film can greatly increase hydrate adhesion in gas-dominant system.Herein,by performing the molecular dynamics simulations,we find in water-dominant system,the water film plays different roles in hydrate deposition on Fe and its corrosion surfaces.Specifically,due to the strong affinity of water on Fe surface,the deposited hydrate cannot convert the adsorbed water into hydrate,thus,a water film exists.As water affinities decrease(Fe>Fe_(2)O_(3)>FeO>Fe_(3)O_(4)),adsorbed water would convert to amorphous hydrate on Fe_(2)O_(3)and form the ordered hydrate on FeO and Fe_(3)O_(4)after hydrate deposition.While absorbed water film converts to amorphous or to hydrate,the adhesion strength of hydrate continuously increases(Fe<Fe_(2)O_(3)<FeO<Fe_(3)O_(4)).This is because the detachment of deposited hydrate prefers to occur at soft region of liquid layer,the process of which becomes harder as liquid layer vanishes.As a result,contrary to gas-dominant system,the water film plays the weakening roles on hydrate adhesion in water-dominant system.Overall,our results can help to better understand the hydrate deposition mechanisms on Fe and its corrosion surfaces and suggest hydrate deposition can be adjusted by changing water affinities on pipeline surfaces.

Surface Metallization of Glass Fiber(GF)/Polyetheretherketone(PEEK) Composite with Cu Coatings Deposited by Magnetron Sputtering and Electroplating

Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.

Acupotomy ameliorates knee osteoarthritis-related collagen deposition and fibrosis in rabbit skeletal muscle through the TGF-β/Smad pathway

Objective To investigate the effects of acupotomy on skeletal muscle fibrosis and collagen deposition in a rabbit knee osteoarthritis(KOA)model.Methods Rabbits(n=18)were randomly divided into control,KOA,and KOA+acupotomy(Apo)groups(n=6).The rabbits in the KOA and Apo groups were modeled using the modified Videman's method for 6 weeks.After modeling,the Apo group was subjected to acupotomy once a week for 3 weeks on the vastus medialis,vastus lateralis,rectus femoris,biceps femoris,and anserine bursa tendons around the knee.The behavior of all animals was recorded,rectus femoris tissue was obtained,and histomorphological changes were observed using Masson staining and transmission electron microscopy.The expression of transforming growth factor-β1(TGF-β1),Smad 3,Smad 7,fibrillar collagen types I(Col-I)and III(Col-III)was detected using Western blot and real-time polymerase chain reaction(RT-PCR).Results Histological analysis revealed that acupotomy improved the microstructure and reduced the collagen volume fraction of rectus femoris,compared with the KOA group(P=.034).Acupotomy inhibited abnormal collagen deposition by modulating the expression of fibrosis-related proteins and mRNA,thus preventing skeletal muscle fibrosis.Western blot and RT-PCR analysis revealed that in the Apo group,Col-I,and Col-III protein levels were significantly lower than those in the KOA group(both P<.01),same as Col-I and Col-III mRNA levels(P=.0031;P=.0046).Compared with the KOA group,the protein levels of TGF-β1 and Smad 3 were significantly reduced(both P<.01),as were the mRNA levels of TGF-β1 and Smad 3(P=.0007;P=.0011).Conversely,the levels of protein and mRNA of Smad 7 were significantly higher than that in the KOA group(P<.01;P=.0271).Conclusion Acupotomy could alleviate skeletal muscle fibrosis and delay KOA progress by inhibiting collagen deposition through the TGF-β/Smad pathway in the skeletal muscle of KOA rabbits.

Reduced magma generation and its implications for the Pulang giant porphyry Cu-polymetallic deposit in Northwest Yunnan,China

The Pulang giant porphyry Cu-Mo polymetallic deposit is located in the Zhongdian area in the center of the Sanjiang Tethys tectonic domain,which was formed by the westward subduction of the Garze-Litang oceanic slab beneath the Zhongza massif.Chalcopyrite-pyrrhotite-pyritemolybdenite occurs as disseminations,veins,veinlets,and stockworks distributed in the K-silicate alteration zone in the monzonite porphyry,which is superimposed by propylitization.The chemical compositions of biotite and amphibole analyzed by electron probe microanalysis(EPMA)indicate that the ore-forming magma and exsolved fluids experienced a continuous decrease in the oxygen fugacity(fO_(2)).Primary amphibolite and biotite(type I)crystallized at relatively high temperatures(744-827°C)and low fO_(2)(log fO_(2)=−12.26 to−11.91)during the magmatic stage.Hydrothermal fluids exsolved from the magma have a relatively lower temperature(621-711°C)and fO_(2)(log fO_(2)=−14.36 to−13.32)than the original magma.In addition,the presence of a high abundance of pyrrhotite and an insufficiency of primary magnetite and sulfate in the ore(i.e.,anhydrite and gypsum)indicate that the deposit may be a reduced porphyry deposit.Magma and fluid fO_(2)results,combined with previous research on magmatic fO_(2)at the Pulang deposit,indicate that the magma associated with the reduced Pulang ore assemblages was initially generated as a highly oxidized magma that was subsequently reduced by sedimentary rocks of the Tumugou Formation.

Geochemistry, mineral paragenesis and geothermal conditions of oreforming fluids from the Ain El Bey Cu–Fe deposit: potential occurrence of native gold and precious metal traces (North African orogenic belt, Northern Tunisia)

The Ain El Bey abandoned mine, in North-West Tunisia, fits into the geodynamic context of the European and African plate boundary. Ore deposit corresponds to veins and breccia of multiphase Cu–Fe-rich mineralization related to various hydrothermal fluid circulations. Petromineralogical studies indicate a rich mineral paragenesis with a minimum of seven mineralization phases and, at least, six pyrite generations. As is also the case for galena and native silver, native gold is observed for the first time as inclusion in quartz which opens up, thus, new perspectives for prospecting and evaluating the potential for noble metals associated with the mineralization. Scanning Electron Microscope--Energy Dispersive Spectroscopy and Transmission electron microscopy analyses show, in addition, a large incorporation of trace elements, including Ag and Au, in mineral structures such as fahlores(tetrahedrite-tennantite) and chalcopyrite ones. The mineral/mineral associations, used as geothermometers, gave estimated temperatures for the mineralizing fluids varying from 254 to 330 ℃ for phase Ⅲ, from 254 to 350 ℃ for phase Ⅳ, and from 200 to 300 ℃ for phases Ⅴ and Ⅵ. The seventh and last identified mineralization phase, marked by a deposit of native gold, reflects a drop in the mineralizing fluid’s temperature(< 200 ℃) compatible with boiling conditions. Such results open up perspectives for the development of precious metal research and the revaluation of the Cu–Fe ore deposit at the Ain El Bey abandoned mine, as well as at the surrounding areas fitting in the geodynamic framework of the Africa-Europe plate boundary.

Electroacupuncture improves myocardial fibrosis in heart failure rats by attenuating ECM collagen deposition through modulation of TGF-β1/Smads signaling pathway

Background: To explore the effects of electroacupuncture on cardiac function and myocardial fibrosis in rat models of heart failure, and to elucidate the underlying mechanism of electroacupuncture in heart failure treatment. Methods: Healthy male Sprague-Dawley rats were allocated into three groups: Sham group, Model group, and electroacupuncture (Model + EA) group, with each group comprising 8 rats. The model underwent a procedure involving the ligation of the left anterior descending coronary artery to induce a model of heart failure. The Model + EA group was used for 7 consecutive days for electroacupuncture of bilateral Shenmen (HT7) and Tongli (HT5), once a day for 30 min each time. Left ventricular parameters in rats were assessed using a small-animal ultrasound machine to analyze changes in left ventricular end-diastolic volume, left ventricular end-systolic volume, left ventricular ejection fraction, and left ventricular fractional shortening. Serum interleukin-1β (IL-1β), cardiac troponin (cTn), and N-terminal brain natriuretic peptide precursor levels were measured using ELISA. Histopathological changes in rat myocardium were observed through HE staining, while collagen deposition in rat myocardial tissue was assessed using the Masson staining method. Picro sirius red staining, immunohistochemical staining, and RT-qPCR were utilized to distinguish between the various types of collagen deposition. The expression level of TGF-β1 and SMAD2/3/4/7 mRNA in rat myocardial tissues was determined using RT-qPCR. Additionally, western blot analysis was conducted to assess the protein expression levels of TGF-β1, SMAD3/7, and p-SMAD3 in rat myocardial tissues. Results: Compared with the Sham group, the left ventricular ejection fraction and left ventricular fractional shortening values of the Model group were significantly decreased (P < 0.01);the left ventricular end-diastolic volume and left ventricular end-systolic volume values were remarkably increased (P < 0.01);serum N-terminal brain natriuretic peptide precursor content was increased (P < 0.01);serum IL-1β and cTn levels were increased (P < 0.01);myocardial collagen volume fraction were increased (P < 0.01);and those of the expression of TGF-β1 and SMAD2/3/4 mRNA was increased (P < 0.01);the expression of SMAD7 mRNA was decreased (P < 0.01);the protein expression levels of TGF-β1, SMAD3, and p-Smad3 were increased (P < 0.01);the protein expression level of SMAD7 was decreased (P < 0.01) in the Model group. Compared to the Model group, the expression levels of the proteins TGF-β1, SMAD3, and p-Smad3 in myocardial tissue were found to be decreased (P < 0.01), and the expression level of the protein SMAD7 was found to be increased (P < 0.01) in the Model + EA group;the collagen volume fraction and deposition of type Ⅰ /Ⅲ collagen were decreased (P < 0.01) in the Model + EA group. Conclusion: Electroacupuncture alleviates myocardial fibrosis in rats with heart failure, and this effect is likely due to attributed to the modulation of the TGF-β1/Smads signaling pathway, which helps reduce collagen deposition in the extracellular matrix.

Cu/Ce负载对赤泥脱除中低温烟气中NO的促进作用

本研究对酸洗赤泥催化剂进行Cu、Ce、Cu/Ce浸渍负载,并研究了金属改性赤泥对烟气中NOx的催化转化性能。研究结果表明,Cu负载催化剂中的Cu+与Cu^(2+),有效促进了赤泥对低温烟气(200–300℃)中的NO转化率,Cu的负载量达到6%时,赤泥的最高NO转化率达到了90.7%;而Ce负载催化剂中的Ce^(3+)与Ce^(4+),有效促进了赤泥对中温烟气(200–400℃)中的NO转化率,Ce的负载量达到8%时,赤泥的最高NO转化率达到了94.0%;Cu/Ce负载催化剂表现出比单金属负载催化剂更好的低温NO转化率,最佳的负载Cu:Ce比例为1∶1,双金属负载催化剂表现出比Cu负载催化剂更好的中温(300–400℃)中的NO转化率,最高达到了95.5%。其原因是,在Cu/Ce协同作用下,Cu+以及Cu^(2+)的还原过程分别从229、302℃降至201以及247℃,同时使发生Fe2O3→FeO的还原过程的温度降低,促使ACRM-Cu1Ce1具有更强的低温氧化还原能力,同时,双金属负载使催化剂具有更高的弱酸性峰,也使催化剂的强、弱酸性峰都向低温偏移,并使负载后的赤泥具有了较高的Fe离子平均氧化态以及较高的Cu+含量,促进了赤泥催化剂对低温NO的转化率。

Cu、Sn、Ag同位素在古金属制品溯源研究中的应用

近年来,随着同位素分析方法的不断突破和新一代多接收电感耦合等离子体质谱(MC-ICP-MS)测试技术的广泛应用,Cu、Sn、Ag等非传统同位素在古代金属制品溯源研究中显示出较好的应用前景。本文综述了近20年来Cu、Sn、Ag同位素在古代金属制品应用研究的相关进展,并展望了其应用前景:①由于不同矿床之间Cu、Sn、Ag同位素存较大重叠,这些同位素均难以作为独立的证据追溯金属制品的地质来源;②Cu同位素在原生矿石与表生矿石之间存在较大的分馏,是示踪铜矿石类型的可靠方法,Ag同位素也具推断银矿石类型的潜力;③将Cu、Sn、Ag同位素与Pb同位素、微量元素相结合,并采用合理的统计方法,开展综合溯源研究将是今后应用非传统同位素进行古代金属制品溯源研究的发展方向。

Cu含量以及Cu/Mg比对Al-Si-Cu-Mg合金组织和力学性能的影响

研究了Cu含量和Cu/Mg比对Al-Si-Cu-Mg合金组织和力学性能的影响。结果表明Al-Si-Cu-Mg合金凝固组织是否形成Mg_(2)Si、Q-Al_(5)Cu_(2)Mg_(8)Si_(6)以及θ-Al_(2)Cu取决于Cu含量以及Cu/Mg比。当Cu/Mg比相对低时形成Mg_(2)Si中间相,而Cu/Mg比高时则倾向于生成Q-Al_(5)Cu_(2)Mg_(8)Si_(6)和θ-Al_(2)Cu相。当Cu/Mg比相同时,高Cu含量和高Mg含量都会促进Q相θ相的形成。通过观察T6热处理后的组织发现Cu含量以及Cu/Mg比控制了初生相的溶解以及析出相的形成,从而影响合金的强度与韧性。通过控制Cu含量及Cu/Mg比使Al-9Si-2Cu-0.5Mg合金中析出较少数量的初生相,再通过热处理析出大量的Q′强化相,使合金具有较高的强度和相对适中的伸长率。

Cu(Ⅱ)催化NaOCl氧化碘帕醇的效果和过程解析

本文研究Cu(Ⅱ)催化NaOCl氧化非离子型碘代X射线造影剂—碘帕醇(IPM),对IPM降解过程中Cu的回收和形态进行解析,考察Cu(Ⅱ)、NaOCl浓度和卤素离子对IPM降解效果及碘代消毒副产物-碘仿的生成影响;采用XRD、XPS分析Cu(Ⅱ)反应后的产物晶型和形态变化,结合循环伏安曲线和计时电流表征Cu(Ⅲ)的生成,推测Cu(Ⅱ)催化NaOCl氧化IPM的机理.利用HPLC/MS/MS分析中间产物,推测IPM的降解路径.结果表明,与Co(Ⅱ)、Fe(Ⅱ)、Mn(Ⅱ)相比,Cu(Ⅱ)显著提高了NaOCl的分解率和IPM的氧化效果,25℃、pH=6.71,500r/min,NaOCl和Cu(Ⅱ)浓度分别为0.5和0.05mmol/L,60min,8.0mg/L IPM的降解率达到77.51%;HO·、活性氯自由基和Cu(Ⅲ)都有助于Cu(Ⅱ)/NaOCl氧化IPM,且Cu(Ⅲ)的贡献随pH值升高而增大.NaOCl浓度在0.1~2.5mmol/L范围增加,IPM降解率增加;Cu(Ⅱ)浓度在0.005~0.5mmol/L存在适宜值.HPLC/MS/MS共检测出13种产物,IPM的降解途径主要包括:侧链酰胺键水解和氧化,碘取代、羟基加成.Cl^(−)、Br^(−)和I^(−)(1~5mmol/L)在影响IPM氧化效果的同时,Br^(-)显著促进了CHI_(3)的生成,生成量达到48.28μg/L.

CTAB改性Cu-BTC材料的合成及其吸附分离二甲苯异构体的性能

通过水热法合成Cu-BTC晶体的过程中添加十六烷基三甲基溴化铵(CTAB),通过调节CTAB的添加量对吸附材料的形貌和孔结构进行改性,改性后的Cu-BTC材料与原Cu-BTC相比,其对对二甲苯(PX)的静态吸附量明显提高,且高于间二甲苯(MX)和邻二甲苯(OX),从而提高了异构体的吸附选择性。研究了二甲苯异构体在Cu-BTC-CTAB材料上的静态吸附性能和吸附动力学性能。在298K、318K和338K温度下进行了一系列二甲苯有机蒸气吸附平衡实验,得到了静态吸附速率曲线和吸附等温线。改性材料中CTAB添加量为0.08%的Cu-BTC-CTAB样品对PX的吸附量和选择性最优。动力学研究表明,二甲苯异构体在Cu-BTC-CTAB上的吸附过程可以用一级动力学模型来描述。

g-C_(3)N_(4)锚定Cu(Ⅰ)高选择性催化CCl_(4)合成2,4,4,4-四氯丁腈

以尿素和Cu(NO_(3))_(2)·3H_(2)O为前体,采用热缩合法制备了不同Cu负载量的氮化碳(g-C_(3)N_(4))基催化剂Cu/CNn(n=1、2、3),采用X射线衍射仪、傅里叶变换红外光谱、X射线光电子能谱、比表面积测试、扫描电子显微镜及透射电子显微镜对其结构和形貌进行了表征,比较了不同Cu负载量的Cu/CNn催化CCl_(4)与丙烯腈(AN)的原子转移自由基加成(ATRA)反应合成2,4,4,4-四氯丁腈(TBN)的催化性能。结果表明,Cu/CN1呈现优异的催化性能,以乙腈(MeCN)为溶剂,n(Cu/CN1)∶n(AN)=1∶1000,120℃反应12h,TBN的选择性可达96.5%,产率可达83.3%,Cu/CN作为多相催化剂,经过滤处理便可重复利用,使用7次其催化活性仍能稳定保持。基于相关的实验结果,提出了Cu/CN催化CCl_(4)和AN的ATRA反应的氧化-还原循环机理。实验结果揭示了Cu与g-C_(3)N_(4)载体的协同作用机制,为CCl_(4)深加工开发高效的催化体系提供了新的思路。

络合剂对固相法Cu/ZnO/In_(2)O_(3)催化剂的CO_(2)加氢制甲醇反应性能的影响

为了促进催化剂中Cu物种的分散,在金属硝酸盐中分别加入草酸、甲酸和柠檬酸,采用固态研磨合成Cu/ZnO/In_(2)O_(3)催化剂.结果表明:草酸的加入对Cu的分散效果最好,在280℃,2 MPa,3.6 L·gcat^(-1)·h^(-1),V(H2)∶V(CO_(2))=3∶1时,甲醇收率最高,达到2.1 mmol·gcat^(-1)·h^(-1).但甲酸在高温下会分解为CO_(2)和H_(2),导致制备的CuO/ZnO/In_(2)O_(3)催化剂部分还原,随后此催化剂在H_(2)预处理后被过度还原,形成Cu_(3)In_(7)合金相,导致甲醇产率降低.

PEI/SA/Cu三元体系改性荷正电纳滤膜及其脱盐性能

通过将海藻酸钠(SA)与聚乙烯亚胺(PEI)共混作为二次界面聚合反应的水相溶液,SA与PEI强相互作用使SA嵌入到聚酰胺层中,从而提高膜的致密性.随后通过Cu^(2+)与SA结合提高膜表面荷正电性,提高膜对多价阳离子的截留性能.对比研究了SA和Cu^(2+)浓度对复合膜物化性质、表面形貌及分离性能的影响.结果表明,荷正电纳滤膜的最佳制备条件为:SA质量分数为0.01%,Cu^(2+)浓度为25 mmol/L,所对应的PS/Cu-3复合膜亲水性提高.与Control-PEI膜相比,其通量提高了257%,为(40.0±0.8)L/(m^(2)·h),对MgCl2的截留率从92.0%提升至97.1%,且具有良好的耐压性和稳定性.

晶粒尺寸对界面含Cr-O-C防黏层Cu/Ni复合体拉伸性能的影响

通过分子动力学方法研究含Cr-O-C防黏层的具有不同晶粒尺寸的Cu/Ni复合体的拉伸变形。结果表明:当Cu/Ni复合体的晶粒尺寸大于12 nm时,不论界面不含Cr、O和C原子或含有定量Cr、O和C原子,复合体的屈服强度随着晶粒尺寸的减小呈现增大趋势,符合细晶强化规律,晶粒塑性变形主要受晶体内部的位错滑移控制,最大应力增加9.52%;当晶粒尺寸小于12 nm时,由于晶界所占比例的增加,拉伸过程的塑性变形更多受晶界变形控制,屈服强度下降。Cr-O-C界面弱化了Cu/Ni复合体的强度,随着界面上Cr、O和C原子数量的增加,Cu/Ni复合体的抗拉强度随之降低,最大应力下降56.40%,Cu/Ni复合体内部的位错数量也随之降低,转移到Ni表面的Cu原子数量随之减少。

基于层状锌铝复合氢氧化物前驱体优化制备Cu/ZnO/Al_(2)O_(3)气相醛加氢催化剂

以偏铝酸钠作为铝源通过一步法、两步法和混合法引入Cu制备基于ZnAl-LDH前驱体的3种不同的Cu/ZnO/Al_(2)O_(3)催化剂,对催化剂及其前驱体结构性质进行表征,结合辛烯醛(2-乙基-2-己烯醛,EPA)加氢反应评价结果,探究不同制备方法、不同铝的引入方式对ZnAl_(2)O_(4)尖晶石形成的影响,考察不同条件下所得催化剂的结构与反应性能之间的构效关系。结果表明:与工业催化剂相比,在辛烯醛气相加氢反应中混合法制得的催化剂与工业催化剂活性相当,产物选择性在空速1.5 h^(-1)时高于工业剂1.9%,在空速4.0 h^(-1)时高于工业剂2.5%;以偏铝酸钠作为铝源制备的ZnAl-LDH前驱物大大提高锌铝结合效率,减少非结合Al_(2)O_(3)的产生,提高产物选择性,同时实现380℃低温焙烧条件下ZnAl-LDH向ZnAl_(2)O_(4)尖晶石的转变,避免传统的高温焙烧过程中CuO的烧结。