新工科创新型工程人才培养探索——以“纳米材料合成制备实验”课程改革为例

“纳米合成制备实验”课程是纳米材料与技术专业的必修环节实验课程。针对目前传统工科实验教学中存在的一些亟须解决的问题,基于新工科建设的发展趋势,以创新型工程人才培养为目标,对“纳米材料合成制备实验”课程教学模式进行改革探索。主要措施包括:以科教融合设计综合设计性实验项目;以线上线下混合式教学提升教学效率;以多元化考核完善实验教学考核评价体系,改进教学并提高质量。通过以上改革探索,学生的综合素质得到较大提升。第一届纳米材料与技术专业毕业班深造率为61.1%,就业率达97.2%,表明北京工业大学“纳米材料合成制备实验”课程改革取得了良好的成效,为新工科背景下纳米材料与技术专业其他课程改革提供了思路和参考依据。

探究式教学法在“纳米材料合成与制备”实验课程中的实践

为了改善“纳米材料合成与制备”实验课程教学效果,提升学生思考问题、分析问题、解决问题的能力,比较了传统讲义式教学方法与探究式教学方法的不同,并结合实验课程教学目标,阐述了探究式教学法应用于“纳米材料合成与制备”实验课程教学中的积极意义,并提出了实践策略。应用结果表明,该教学方法有助于学生理解实际原理、了解实验过程、提升分析关键影响因素的能力,改善了教学效果。

基础化学原理与前沿研究领域的契合——以功能纳米材料的合成为例

列举几种重要的基础化学原理在功能纳米材料制备过程中的典型应用实例,深入分析化学基础知识点与纳米材料形成过程中结构及形貌控制之间的内在联系。这些事例将有助于加深学生对于基础学科与前沿研究课题之间密切联系的体会,提高学生的学习兴趣,培养学生的基础知识应用能力。

合成纳米材料对神经系统的影响

合成纳米材料具有独特的物理化学特性,在能源、电子、食品、农业、环境科学、化妆品和医药等领域都得到广泛应用,与此同时其安全性也受到了广泛关注。体内和体外模型研究已报道合成纳米材料能够穿过或绕过血脑屏障,进入中枢神经系统,造成神经损伤。本文总结了合成纳米材料产生毒性的影响因素,进入中枢神经系统的途径以及诱导神经毒性的分子机制,包括氧化应激、DNA损伤、炎症、自噬和凋亡的诱导以及DNA甲基化等。通过系统地综述合成纳米材料神经毒性研究进展,并对该研究方向进行展望,为进一步深入研究合成纳米材料神经毒性提供参考。

卟啉微纳米材料的制备及应用研究进展

综述了卟啉微纳米材料合成的制备方法,以及将其作为传感、光电器件等应用的研究进展。卟啉类化合物是广泛存在于自然界重要的生物分子,其独特的平面骨架和共轭大π结构,使之成为分子组装体系中优良的构筑基元。制备的卟啉微纳米材料因其良好的光、热稳定性,已被广泛用于分析化学、仿生、催化及材料科学等领域。

Ag掺杂氧化锌纳米材料的制备及高压相变拉曼光谱研究

宽禁带直接带隙半导体材料氧化锌(ZnO),具有优异的光电性能、机械性能和化学特性。ZnO材料的结构对其性能影响较大,元素掺杂可改变ZnO晶体结构和带隙宽度,是提升ZnO材料性能的有效手段,当前常用Ag掺杂ZnO即为提高光催化反应效率。高压独立于温度、成分,是调控材料结构组织性能的重要手段,是产生新材料、发现新调控原理的重要因素。该研究通过对比纯ZnO晶体和Ag掺杂ZnO晶体的高压相变行为,揭示了元素掺杂对ZnO纳米晶体材料结构性能的影响。研究首先采用水热法辅助制备纯ZnO纳米微球和Ag掺杂ZnO纳米微球(1∶150Ag/ZnO),表征结果显示水热法合成的纯ZnO和1∶150Ag/ZnO均为六角纤锌矿晶体结构,形貌均为几十纳米尺寸小颗粒堆积形成的微球,ZnO晶格常数随着Ag离子掺杂而变大,Ag掺杂导致ZnO晶格膨胀。随后应用金刚石压腔结合原位拉曼光谱技术测定了纯ZnO和Ag掺杂ZnO的高压结构相变行为。相比于纯ZnO拉曼峰,Ag掺杂ZnO的E2(high)振动模式439 cm^-1拉曼峰峰宽变窄,并呈现向低频方向移动的趋势,与无定形ZnO谱峰相近,表明Ag+取代Zn^2+影响了Zn—O键,同时也影响了ZnO晶格结构的长程有序性。随体系压力增大,表征六角纤锌矿结构ZnO的拉曼特征峰439 cm^-1出现瞬间弱化和宽化。压力增大至9.0 GPa时,纤锌矿结构ZnO拉曼特征峰439 cm^-1消失,585 cm-1处出现新峰,ZnO晶体发生由六角纤锌矿向岩盐矿的结构转变。压力继续增大至11.5 GPa,新的拉曼峰显著增强,峰形变窄,同时向高波数方向移动,相变完成,岩盐矿结构ZnO性能稳定。1∶150 Ag/ZnO从六角纤锌矿结构到立方岩盐结构的相变压力为7.2 GPa,低于纯ZnO。相变压力降低表明晶体结构稳定性下降,可能的原因在于掺杂Ag导致ZnO晶格膨胀,晶体结构松弛,两相相对体积变化增加,从而导致相变势垒降低,使样品在较低压力下发生相变。纳米材料的高压研究揭示了元素掺杂对材料结构稳定性的影响,是纳米材料调控原理的潜在研究手段。

纳米材料与环境抗生素耐药性:抗性基因流在土壤-植物系统中的迁移与阻断

抗生素抗性基因(antibiotic resistance genes,ARGs)作为一种新兴污染物正威胁着全球卫生健康,应对抗生素耐药性(antimicrobial resistance,AMR)已成为一项全球性挑战.粪源性ARGs是农业土壤AMR的主要来源,可通过水平基因转移(horizontal gene transfer,HGT)在土壤-植物系统中迅速传播最终进入食物链,威胁人类健康.人工合成纳米材料(engineered nanomaterials,ENMs)和微纳塑料的大规模生产与应用使得环境中ENMs和微纳塑料的浓度持续增加,最终进入环境对土壤-植物系统中ARGs的迁移与传播产生不可忽视的影响.ENMs(如AgENMs、CuO ENMs和TiO2/Ag/GO ENMs等)可通过积累胞内活性氧(reactive oxygen species,ROS)、增加细胞膜透性和上调接合相关基因表达促进ARGs的传播.此外,土壤中的ENMs与微纳塑料可影响土壤微生物抗性组和植物根部形态、结构及根系分泌物等,进而影响抗生素抗性细菌(antibiotic resistance bacteria,ARB)和ARGs从根际向植物的迁移.另有报道显示,CeO2ENMs、Fe2O3@MoS2ENMs和微塑料(microplastics,MPs)具有清除胞内ROS或抑制根系生长控制ARGs传播的潜力.本文将系统阐明ENMs和微纳塑料影响ARGs传播的潜在分子机制,聚焦ARGs在土壤-植物系统中迁移并影响微生物抗性组的微界面过程,探讨阻断抗性基因流迁移的新兴纳米技术,对遏制AMR传播、保障粮食安全与人体健康具有重要意义.

等离子体法制备超细粉体氮化铝的研究

以微米级铝粉为原料 ,用N2 热等离子体法制备了超细氮化铝粉体。在等离子体功率12kW ,运行N2 流量 2m3/h ,急冷NH3流量 0 6m3/h ,送粉N2 流量 0 8m3/h条件下 ,铝粉全部转化为纳米氮化铝。采用SEM技术和粒度分析仪对产品进行了分析 ,制得的氮化铝粉末平均粒径为10 0nm ,粒度分布为 4 0～ 14

Synthesis and characterization of ε-VOPO_4 nanosheets for secondary lithium-ion battery cathode

Vanadium （III） phosphate monoclinic VPO4·H2O was synthesized hydrothermally. The ε-VOPO4 nanosheets, formed by the oxidative de-intercalation of protons from monoclinic VPO4·H2O, can reversibly react with more than 1 mol lithium atoms in two steps. Crystal XRD analysis revealed that the structure of the ε-VOPO4 nanosheets is monoclinic with lattice parameters of α=7.2588（4） A, b=6.8633（2） A and c=7.2667（4） A. The results show that the ε-VOPO4 nanosheets have a thickness of 200 nm and uniform crystallinity. Electrochemical characterization of the ε-VOPO4 monoclinic nanosheets reveals that they have good electrochemical properties at high current density, and deliver high initial capacity of 230.3 mA· h/g at a current density of 0.09 mA/cm2. Following the first charge cycle, reversible electrochemical lithium extraction/insertion at current density of 0.6 mA/cm2 affords a capacity retention rate of 73.6% （2.0？4.3 V window） that is stable for at least 1000 cycles.

Amorphous nanomaterials in electrocatalytic water splitting

Electrochemical water splitting,as a promising method for hydrogen production,has attracted significant attention.However,the lack of an electrocatalyst with a small energy loss and fast reaction kinetics has hindered the development of this technology.Amorphous nanomaterials with short-range order and long-range disorder features have recently shown superior activity compared to their crystalline counterparts in water electrolysis.The enhanced activity arising from their intrinsic disordered structure results in more active sites and a higher intrinsic activity of such sites.In this regard,this review is aimed at summarizing the progress in amorphous electrocatalysts for water splitting.First,the synthesis strategies for amorphous electrocatalysts are discussed.Characterization tools for amorphous nanomaterials are then summarized.Moreover,the origin of the enhanced activity and stability of amorphous nanomaterials is analyzed.Finally,the current challenges and promising opportunities in this research area are discussed.This review aims to provide a guide for designing and developing amorphous nanomaterials with a fascinating electrocatalytic water splitting performance.

Production of Ag-ZnO powders by hot mechanochemical processing

Ag–CdO composites are still one of the most commonly used electrical contact materials in low-voltage applications owing to their excellent electrical and mechanical properties.Nevertheless,considering the restriction on using Cd due to its toxicity,it is necessary to find alternative materials that can replace these composites.In this study,the synthesis of Ag-ZnO alloys from Ag-Zn solid solutions was investigated by hot mechanochemical processing.The hot mechanochemical processing was conducted in a modified attritor mill at 138℃under flowing O2 at 1200 cm3/min for 3.0 h.The microstructure and phase evolution were investigated using X-ray diffractometry,field emission gun scanning electron microscopy and transmission electron microscopy.The results suggest that it is possible to complete the oxidation of Ag-Zn solid solution by hot mechanochemical processing at a low temperature and short time.This novel synthesis route can produce Ag-ZnO composites with a homogeneous distribution of nanoscale ZnO precipitates,which is impossible to achieve using the conventional material processing methods.Considering the fact that the fundamental approach to improving electric contact material performance resides in obtaining uniform dispersion of the second-phase in the Ag matrix,this new processing route could open the possibility for Ag-ZnO composites to replace non-environmentally friendly Ag-CdO.

Synthesis of γ-Al_2O_3 nanoparticles by chemical precipitation method

Highly pure active γ-Al2O3 nanoparticles were synthesized from aluminum nitrate and ammonium carbonate with a little surfactant by chemical precipitation method. The factors affecting the synthesis process were studied. The properties of γ-Al2O3 nanoparticles were characterized by DTA, XRD, BET, TEM, laser granularity analysis and impurity content analysis. The results show that the amorphous precursor AI（OH）3 sols are produced by using 0.1 mol/L Al（NO3）3·9H2O and 0.16 mol/L （NH4）2CO3·H2O reaction solutions, according to the volume ratio 1.33, adding 0.024%（volume fraction） surfactant PEG600, and reacting at 40℃, 1000 r/min stirring rate for 15min. Then, after stabilizing for 24 h, the precursors were extracted and filtrated by vacuum, washed thoroughly with deionized water and dehydrated ethanol, dried in vacuum at 80℃ for 8h, final calcined at 800℃ for 1h in the air, and high purity active γ-Al2O3 nanoparticles can be prepared with cubic in crystal system, OH^7-FD3M in space group, about 9 nm in crystal grain size, about 20 nm in particle size and uniform size distribution, 131.35 m^2/g in BET specific surface area, 7 - 11 nm in pore diameter, and not lower than 99.93% in purity.

Solvothermal synthesis and characterization of nanocrystalline vanadium-chromium composite oxides and catalytic ammoxidation of 2,6-dichlorotoluene

Vanadium‐chromium oxides(VCrO)were usually prepared by high‐temperature solid‐state reactions;however,mixed phases were frequently produced and the morphology of the products was not well controlled.In this work,we prepared amorphous VCrO precursors by using V2O5 and CrO3 and alcohols or mixtures of alcohol and water via solvothermal reaction at 180°C.The precursors were then calcined under nitrogen at various temperatures.The products were characterized by powder X‐ray diffraction,transmission electron microscopy,and X‐ray photoelectron spectroscopy.It was revealed that pure‐phase nanocrystalline orthorhombic CrVO4 was obtained when methanol or methanol/water was used as the solvothermal medium and the precursor was calcined at 700°C.The size of the CrVO4 crystals was around 500 nm when methanol was used,whereas it reduced significantly to less than 50 nm when a mixture of methanol and water was used.The sizes could be effectively tuned from 10 to 50 nm by varying the methanol/water volume ratio.To the best of our knowledge,this is the first report on the synthesis of pure‐phase CrVO4 nanocrystals.The nano‐CrVO4 showed almost the highest catalytic activity for the ammoxidation of 2,6‐dichlorotoluene to 2,6‐dichlorobenzonitrile among the reported bi‐component composite oxides,owing to its smaller particle size,larger specific surface area,and more exposed active centers.

A Facile Route for Synthesis of LiFePO_4/C Cathode Material with Nano-sized Primary Particles

A facile and practical route was introduced to prepare LiFePO4/C cathode material with nano-sized primary particles and excellent electrochemical performance. LiH2PO4 was synthesized by using H3PO4 and LiOH as raw materials. Then, as-prepared LiH2PO4, reduced iron powder andα-D-glucose were ball-milled, dried and sin-tered to prepare LiFePO4/C. X-ray diffractometry was used to characterize LiH2PO4, ball-milled product and LiFePO4/C. Differential scanning calorimeter-thermo gravimetric analysis was applied to investigate possible reac-tions in sintering and find suitable temperature for LiFePO4 formation. Scanning electron microscopy was em-ployed for the morphology of LiFePO4/C. As-prepared LiH2PO4 is characterized to be in P21cn（33） space group, which reacts with reduced iron powder to form Li3PO4, Fe3（PO4）2 and H2 in ball-milling and sintering. The appro-priate temperature for LiFePO4/C synthesis is 541.3-976.7 ℃. LiFePO4/C prepared at 700 ℃ presents nano-sized primary particles forming aggregates. Charge-discharge examination indicates that as-prepared LiFePO4/C displays appreciable discharge capacities of 145 and 131 mA·h·g^-1 at 0.1 and 1 C respectively and excellent discharge ca-pacity retention.

Facile synthesis of porous LiNiVO_4 powder as high-voltage cathode material for lithium-ion batteries

Porous LiNiVO4 powder was synthesized via solution combustion synthesis method using lithium nitrate, nickel nitrate,ammonium metavanadate and citric acid as raw materials. Thermogravimetry (TG) and differential scanning calorimetry (DSC),X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM) were used toevaluate the structures and morphologies of samples. The results show that the calcination temperature has significant effect on thecrystallinity and morphologies. Pure LiNiVO4 flaky nanoparticles with a mean particle size around 20 nm can be readily prepared bycalcining the precursor in air at 500 °C for 2 h. As a cathode material for lithium-ion batteries, the porous LiNiVO4 powder exhibits agood structural reversibility.

Nanocomposite sodalite/ceramic membrane for pre-combustion CO2 capture： synthesis and morphological characterization

Carbon capture and storage （CCS） is amongst the possible options to reduce CO2 emission. In the application of CCS, CO2 capture techniques such as adsorption and membrane system have been proposed due to less energy requirement and environmental benign than the absorption process. However, membrane system has drawbacks such as poor membrane reproducibility, scale-up difficulty and high cost of the membrane supports. In this study synthesis and characterization of nanocomposite sodalite （HS）/ceramic membrane via ＂pore-plugging＂ hydrothermal synthesis （PPH） protocol for pre- combustion CO2 capture is reported. The morphology and crystallinity of the as-prepared membranes were checked with scanning electron microscopy and X-ray diffraction. Surface chemistry of the membrane was examined with Fourier Transform Infrared spectroscopy. In nanocomposite architecture membranes, zeolite crystals are embedded within the pores of the supports instead of forming thin-film layers of the zeolite crystals on the surface of the supports. Compared to the conventional in situ direct hydrothermal synthesis, membranes obtained from PPH possess higher mechanical strength and thermal stability. In addition, defect control with nanocomposite architecture membranes is possible because the zeolite crystals are embedded within the pores of the support, thereby limiting the maximum defect size to the pore size of the support. Furthermore, the nanocomposite architecture nature of the membranes safeguards the membrane from shocks or abrasion that could promote formation of defects. The aforementioned advantages of the nanocomposite architecture membranes could be beneficial in developing high performance and cost-effective membrane materials for pre-combustion CO2 capture.

Hydrogen Adsorption Study upon Ni/AI203 Nano-composite Synthesized by MOCVD Technique

The hydrogen adsorption （storage） studies upon Ni/A1203 nano-composite prepared by metal organic chemical vapor deposition technique （MOCVD） exploiting single source molec ular precursor （SSP） approach were carried out. The Ni/A1203 nano-composite is prepared in cold walled MOCVD reactor by the decomposition of SSP, [H2AI（OtBu）]2, on a substrate holding Ni（acac）2 powder. The SSP is a reducing agent which reduces Ni＋2 to Ni0 and works as source for Al203 matrix in which the Ni0 is dispersed. The resulting Ni/A1203 nano-composite is characterized by XRD, SEM, TEM, and EDX. The hydrogen adsorption （storage） studies are performed using home-made Sievert＇s type apparatus. The hydrogen storage studies reveal that approximately 2.9% （mass ratio） hydrogen can be stored in the Ni/A1203 nano-composite. The results show that Ni/A1203 nano-composite can be a po- tential candidate for hydrogen storage which can be used for onboard fuel purposes.

Exchange Interactions at the Interface FMIAFM Nanocomposite Obtained by Mechanochemical Synthesis

This paper presents a study of the relationship between the magnetic properties and microstructure of nanocomposite Ni/MnO, Ni/CoO, Co/MnO, Co/CoO. The objective is to understand how the coupling interface FM/AFM （ferromagnetic/anti-ferromagnetic） manifests itself in magnetic response of these materials to an applied field. Sample preparation was performed using mechanochemical synthesis by means of a ball mill planetary type high power at normal atmosphere. The characterization was done by XRD （X-ray diffraction）, SEM （scanning electron microscopy） and VSM （vibrating sample magnetometry）. Analyzing the XRD peaks of the samples studied, there was a decrease in the average particle diameter with increasing milling time, which is important in the magnetic interactions of the atoms of the surface. In addition, the diffraction pattern showed formation of new phases by oxidation interfering with the magnetic measurements. Analyses by SEM show chipboard multiform nano- and micrometer-sized grains on the surface of the clusters being responsible for the interaction. The magnetic measurements show a strong coupling between the phases present in nanocomposites showing once again that the MS （mechanosynthesis） is a powerful technique for this kind of purpose. The effect of the decrease in crystallite size leads to large variations of magnetic properties of the material which have been specifically observed changes in HC （coercive field） in the RM （remanent magnetization） and SM （saturation magnetization）. The decrease in crystallite size in the course of grinding intensifies the effects that depend on the surface-to-volume ratio of the material. M vs. T measures were taken for different values of applied field and found a jump in the moment of the sample near the N6el temperature of the antiferromagnetic.

Characterization of nano-Ag/PVP composites synthesized via ultra-violet irradiation

Nano-silver/polyvinylpyrrolidone(PVP)composite materials were successfully synthesized bi-insitu from silver nitrate solution with N-vinyl pyrrolidone (NVP) monomer,containing neither initiator nor reductant, in ultraviolet irradiation conditions.The resultant Ag/PVP nanocomposites were characterized by infrared spectroscopy (FT-IR), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD).TEM show that nano silver particles are homogeneously dispersed in PVP polymer matrix, and the mean size of spherical silver particles is about 5 nm.The spectroscopy of XPS and FTIR showed that there is an interaction between nano silver not only with carbonyl oxygen but also with the nitrogen group within the NVP molecule through the p-π conjugation effect in the nano-silver/PVP composites system.