金/钯哑铃状纳米晶的制备及其催化对硝基苯酚还原研究

采用晶种-溶液生长法制备了单分散性良好、长径比均一的Au纳米棒, 利用H₂PdCl₄作为前驱体, CTAC作为软模版, 抗坏血酸作为还原剂对Au纳米棒进行改性合成了金/钯哑铃状结构纳米晶(Au/Pd NDs)。采用透射电子显微镜(TEM)、X射线能谱仪(EDS)和紫外-可见分光光度计(UV-Vis-NIR)对样品的结构和形貌进行表征, 探讨了铃铛状结构形成的机理, 并研究了其对硼氢化钠还原对硝基苯酚反应的催化性能。结果表明: 大量的多晶钯颗粒定向选择生长在金纳米棒(AuNRs)两端, 形成哑铃状结构; 通过调控还原剂与前驱体的比例, 铃铛尺寸连续可调。当钯的分散性好且总的催化活性位点多时, 金/钯哑铃状结构纳米晶催化对硝基苯酚还原的效率高。钯颗粒尺寸为20.7 nm的Au/Pd NDs(0.04 mg/mL)催化对硝基苯酚还原的反应速率常数可达0.44 min^-1, 证明其是一种非常有效的催化剂。     

MOFs基复合催化材料的构筑及催化还原对硝基苯酚的研究进展

催化还原法可将高毒性、难生物降解的对硝基苯酚(p-NP)进行还原性降解和化学资源转化，而研发高效稳定的催化剂对促进该方法的实际应用至关重要。金属有机框架(MOFs)基复合材料是通过MOFs材料与其他功能材料复合而形成，其结构和功能属性可调控，能较好地发挥复合组分的良好特性，且产生协同催化效应，在p-NP还原反应中展现更为优异的催化性能。介绍了MOFs基复合材料的构筑方法及在p-NP催化还原反应的研究进展，对该领域未来研究方向提出了展望。     

氮化硼纳米片剥离法制备及表面改性研究进展

综述以六方氮化硼(hexagonal boron nitride, h-BN)粉体为原料制备氮化硼纳米片(boron nitride nanosheet, BNNS)的方法，归纳原料粒径、溶剂、超声波功率、磨球用量、助剂及预处理工艺等因素对BNNS制备的影响机理；概述h-BN和BNNS表面修改性的途径和方法，总结共价改性法和非共价改性法的机理和优缺点。同时提出：与化学剥离法、液相剥离法、机械剥离法和超临界剥离法相比，由于h-BN层间的π-π共轭和lip-lip作用，介质增强液相剥离法更加简便、高效，适合工业化批量生产，但是需选择恰当的剥离助剂并进一步揭示剥离过程的机理；由于h-BN结构中B、 N原子的化学惰性和局部共轭作用，纯h-BN和BNNS很难被基于化学反应的共价改性法进行直接修饰；h-BN及BNNS的非共价改性法操作简便，但以物理作用为基础的非共价改性结合力较弱，容易在高温、强酸碱等苛刻条件下失效。     

一体式陶瓷膜反应器在对硝基苯酚催化加氢中的应用

设计了液固一体式陶瓷膜反应器,开展对硝基苯酚加氢过程的研究,着重考察了不同膜组件对加氢反应和膜过滤的影响,并对一体式反应器的反应分离性能进行了研究.结果表明,膜组件的引入都会增加纳米镍催化剂的吸附,使加氢速率降低,其中水平膜组件使加氢速率下降了36.4%,影响最大.L型膜组件的渗透性能最高,且对加氢速率的影响较小.一体式陶瓷膜反应器中催化加氢速率的衰减程度小于分置式膜反应器,随着催化剂套用次数的增加,膜处理能力先明显下降后趋于平缓.     

纳米TiO2-Cu2O可见光下光催化降解活性艳红及其机理研究

采用钛酸丁酯水解和肼还原醋酸铜的方法制备出TiO2-Cu2O复合氧化物,研究了TiO2-Cu2O复合光催化剂在可见光照射下光催化降解活性艳红X-3B的性能,考察了催化剂组成、催化剂投加量、溶解氧、H2O2等对光催化反应的影响,探讨了Cu2O及TiO2-Cu2O光催化降解有机污染物的机理。结果表明,由于TiO2和Cu2O之间存在协同作用,使得复合氧化物的活性比单一的Cu2O高。Cu2O光催化的氧化物种为·OH和光生空穴。光生电子(e-)还原吸附在Cu2O表面上的氧,产生超氧阴离子,然后再进一步生成·OH,光生空穴(h+)无法直接将吸附在Cu2O表面的OH-氧化成·OH。     

硅钛杂化介孔球负载金纳米粒子及其催化性能调控

以能源开发(如光解水制氢)及环境保护(如有机物降解)应用为目标, 负载型贵金属催化剂在设计、制备及理论研究方面已取得了长足的发展。本工作以具有特异形貌及结构的树枝状二氧化硅纳米球载体为基础, 通过溶胶-凝胶法在其孔道引入二氧化钛纳米颗粒形成硅钛杂化结构。通过有机改性技术, 在树枝状硅钛杂化纳米球表面接枝氨基官能团。然后, 通过浸渍法和硼氢化钠还原手段, 在杂化纳米球孔道负载超细金纳米粒子。不同手段表征结果显示实验成功制备了树枝状硅钛杂化纳米球负载金纳米颗粒复合材料。在模拟太阳光下, 所得催化剂光解水产氢量及速率为69.08 μmol·g^-1和13.82 μmol·g^-1·h^-1, 约为对比样催化剂(树枝状二氧化硅纳米球负载金纳米粒子)的7倍。在无光条件下, 其降解对硝基苯酚的表观动力学常数为6.540×10^-3 s^-1, 约为对比样的17倍(0.372×10^-3 s^-1)。由此可见, 设计合成的新型催化剂展现出优越的多功能催化活性。     

纳米金@石墨烯复合多孔材料还原4-硝基苯酚

以负载纳米金颗粒的还原石墨烯(APR)为二维模板，采用溶剂编织法在石墨烯表面成功构建具有多孔结构的超交联聚合物(hyper-crosslinked polymer, HCP)并命名为APfR-HCP,探讨复合材料比表面积的变化及还原4-硝基苯酚(4-NP)的性能。结果表明：该新型复合材料具有较大的比表面积(568 m²/g)和丰富的孔道结构；多孔层结构的存在可以快速吸附水体中的小分子有机污染物并富集到金纳米颗粒表面，大大提升复合材料对常见有机污染物4-NP的催化性能；同时还可以有效阻止金纳米颗粒的团聚。APfR-HCP复合多孔材料可以在4 min内迅速将4-NP还原为4-氨基苯酚(4-AP),反应速率常数K可达1.10 min^-1。APfR-HCP复合多孔材料的催化效率远大于模板APR(K=0.068 min^-1),并且具有良好的循环利用性，循环使用5次后仍具有良好的催化性能。     

油酸对纳米Cu_2O的表面修饰

采用油酸作为改性剂对纳米Cu_2O(nano-Cu_2O)进行表面修饰,通过红外光谱分析仪(FTIR)、透射电镜(TEM)、综合热分析仪(TG-DTA)、接触角测试仪、分光光度计等测试设备对修饰的纳米Cu_2O进行表征和性能测试,结果表明,油酸可接枝到Cu_2O纳米粒子表面,并有效抑制纳米粒子的团聚;随着油酸用量的增加,纳米Cu_2O与水的接触角逐渐增大;改性后产物的分散性得到了显著的改善,较之未改性样品,其吸光度均有不同程度的增加。     

氮化硼纳米片的制备及其增强环氧树脂复合材料导热性能的研究进展

随着对新型高导热、高绝缘热界面材料需求的显著增加,具有多种优异性能的环氧树脂(EP)已被广泛用作导热复合材料的基体,然而其固有的低热导率限制了其实际应用.通过向EP中引入具有高导热系数及高绝缘性的氮化硼纳米片(BNNS)可有效弥补EP的缺陷,从而显著提高复合材料的综合性能.基于国内外研究,介绍了BNNS的不同制备方法,...     

Boron Nitride Nanosheets for Metal Protection

Although the high impermeability of graphene makes it an excellent barrier to inhibit metal oxidation and corrosion, graphene can form a galvanic cell with the underlying metal that promotes corrosion of the metal in the long term. Boron nitride (BN) nanosheets which have a similar impermeability could be a better choice as protective barrier, because they are more thermally and chemically stable than graphene and, more importantly, do not cause galvanic corrosion due to their electrical insulation. In this study, the performance of commercially available BN nanosheets grown by chemical vapor deposition as a protective coating on metal has been investigated. The heating of the copper foil covered with the BN nanosheet at 250 °C in air over 100 h results in dramatically less oxidation than the bare copper foil heated for 2 h under the same conditions. The electrochemical analyses reveal that the BN nanosheet coating can increase open circuit potential and possibly reduce oxidation of the underlying copper foil in sodium chloride solution. These results indicate that BN nanosheets are a good candidate for oxidation and corrosion protection, although conductive atomic force microscopy analyses show that the effectiveness of the protection relies on the quality of BN nanosheets.     

Tuning of the Optical,Electronic, and Magnetic Properties of Boron Nitride Nanosheets with Oxygen Doping and Functionalization

Engineering of the optical, electronic, and magnetic properties of hexagonal boron nitride (h‐BN) nanomaterials via oxygen doping and functionalization has been envisaged in theory. However, it is still unclear as to what extent these properties can be altered using such methodology because of the lack of significant experimental progress and systematic theoretical investigations. Therefore, here, comprehensive theoretical predictions verified by solid experimental confirmations are provided, which unambiguously answer this long‐standing question. Narrowing of the optical bandgap in h‐BN nanosheets (from ≈5.5 eV down to 2.1 eV) and the appearance of paramagnetism and photoluminescence (of both Stokes and anti‐Stokes types) in them after oxygen doping and functionalization are discussed. These results are highly valuable for further advances in semiconducting nanoscale electronics, optoelectronics, and spintronics.     

高结晶度氮化硼纳米片的制备及其与聚乙烯醇复合薄膜的性能

以具有特殊花瓣状形貌的硼酸镁纳米片为模板、前驱体和硼源, 以氨气为氮源合成了氮化硼纳米片(BNNSs), 通过 SEM、TEM、XRD、Raman和FT-IR等对其形貌和结构等进行了分析。结果表明: 合成的BNNSs为厚度仅约5 nm、横向尺寸150~300 nm、结晶度极高的单晶片层状h-BN, 多个BNNSs聚集形成了形貌与硼酸镁纳米片类似的形状。以所合成的BNNSs为填料, 制备了不同BNNSs添加量的BNNSs/聚乙烯醇(PVA)复合材料薄膜, 结果表明添加30% BNNSs的复合薄膜的弹性模量较纯PVA薄膜提高了约39.8%, 面内热扩散系数和热导率则分别最大提高了约7和8倍, 说明以此BNNSs做为填料能明显改善BNNSs/PVA复合薄膜的热学性能。     

Highly Thermoconductive,Thermostable, and Super-Flexible Film by Engineering 1D Rigid Rod-Like Aramid Nanofiber/2D Boron Nitride Nanosheets

Polymer-based thermal management materials have many irreplaceable advantages not found in metals or ceramics, such as easy processing, low density, and excellent flexibility. However, their limited thermal conductivity and unsatisfactory resistance to elevated temperatures (<200 °C) still prevent effective heat dissipation during applications with high-temperature conditions or powerful operation. Therefore, herein highly thermoconductive and thermostable polymer nanocomposite films prepared by engineering 1D aramid nanofiber (ANF) with worm-like microscopic morphologies into rigid rod-like structures with 2D boron nitride nanosheets (BNNS) are reported. With no coils or entanglements, the rigid polymer chain enables a well-packed crystalline structure resulting in a 20-fold (or greater) increase in axial thermal conductivity. Additionally, strong interfacial interactions between the weaved ANF rod and the stacked BNNS facilitate efficient heat flux through the 1D/2D configuration. Hence, unprecedented in-plane thermal conductivities as high as 46.7 W m⁻¹ K⁻¹ can be achieved at only 30 wt% BNNS loading, a value of 137% greater than that of a worm-like ANF/BNNS counterpart. Moreover, the thermally stable nanocomposite films with light weight (28.9 W m⁻¹ K⁻¹/10³ (kg m⁻³)) and high strength (>100 MPa, 450 °C) enable effective thermal management for microelectrodes operating at temperatures beyond 200 °C.     

Graphene‐Analogues Boron Nitride Nanosheets Confining Ionic Liquids: A High‐Performance Quasi‐Liquid Solid Electrolyte

Solid electrolytes are one of the most promising electrolyte systems for safe lithium batteries, but the low ionic conductivity of these electrolytes seriously hinders the development of efficient lithium batteries. Here, a novel class of graphene‐analogues boron nitride (g‐BN) nanosheets confining an ultrahigh concentration of ionic liquids (ILs) in an interlayer and out‐of‐layer chamber to give rise to a quasi‐liquid solid electrolyte (QLSE) is reported. The electron‐insulated g‐BN nanosheet host with a large specific surface area can confine ILs as much as 10 times of the host's weight to afford high ionic conductivity (3.85 × 10^?3 S cm^?1 at 25 °C, even 2.32 × 10^?4 S cm^?1 at ?20 °C), which is close to that of the corresponding bulk IL electrolytes. The high ionic conductivity of QLSE is attributed to the enormous absorption for ILs and the confining effect of g‐BN to form the ordered lithium ion transport channels in an interlayer and out‐of‐layer of g‐BN. Furthermore, the electrolyte displays outstanding electrochemical properties and battery performance. In principle, this work enables a wider tunability, further opening up a new field for the fabrication of the next‐generation QLSE based on layered nanomaterials in energy conversion devices.     

Synthesis of Composite Nanosheets of Graphene and Boron Nitride and Their Lubrication Application in Oil

Composite nanosheets of graphene and boron nitride have been produced in large quantities for the first time using high‐energy ball milling in ammonia gas as an exfoliation agent. The anti‐wear properties of the composite nanosheets as a lubricant additive are investigated via a four‐ball method. The results show that the composite nanosheets are exfoliated from the commercial graphite and h‐BN powders and combined into graphene/BN composite nanosheets during the ball milling process. The composite nanosheets formed have diameters larger than 200 nm and consist of heterostructures of approximately 10 monolayers of graphene and BN. The composite nanosheets exhibit better wear resistance and friction reduction properties than the homogeneous nanosheets because of the stronger interaction between graphene and BN nanosheets, which can effectively improve the anti‐wear properties of mineral base oil as a lubricant additive.

     

In Situ Growth of Pd Nanosheets on g‐C3N4 Nanosheets with Well‐Contacted Interface and Enhanced Catalytic Performance for 4‐Nitrophenol Reduction

Loading novel metal nanosheets onto nanosheet support can improve their catalytic performance, but the morphological incompatibility makes it difficult to construct a well‐contacted interface, which is of particular interest in supported catalysts. Herein, Pd nanosheets (Pd NSs) are supported onto graphitic carbon nitride nanosheets (CNNSs) with intimate face‐to‐face contact through an in situ growth method. This method overcomes the limitations of the morphological incompatibility and ensures the intimate interfacial contact between Pd NSs and CNNSs. The nitrogen‐rich nature of CNNSs endows Pd NSs with abundant anchoring sites, which optimizes the electronic structure and improves the chemical and morphological stability of Pd NSs. The supported Pd NSs demonstrate high dispersion and exhibit largely enhanced activity toward the reduction of 4‐nitrophenol. The concentration‐normalized rate constant is up to 3052 min^?1 g^?1 L, which is 5.4 times higher than that obtained by unsupported Pd NSs. No obvious deactivation is observed after six runs of the recycling experiments. It is believed that the supported novel metal nanosheets with the intimately contacted interface may show promising applications in catalysis.     

2D Boron Imidazolate Framework Nanosheets with Electrocatalytic Applications for Oxygen Evolution and Carbon Dioxide Reduction Reaction

Ultrathin 2D materials possess unique properties that translate to enhanced efficiency as electrocatalysts, stimulating research toward methodologies that support their preparation. Herein, a two‐step strategy is reported that involves the preparation of the new boron imidazolate framework ( BIF‐73 ) which is subsequently utilized as a precursor to yield the crystalline 2D nanosheet material ( Fe@BIF‐73‐NS ) via post‐synthetic modification. This new electrocatalytic material stabilizes ultra‐small (Fe₂O₃) fragments resulting in an excellent electrocatalytic performance for the oxygen evolution reaction (OER: lower overpotential with 291 mV at the current density of 10 mA cm^?2) and carbon dioxide reduction reaction (faradaic efficiency of CO reaching 88.6% at ?1.8 V vs Ag/AgCl) without the need for noble metals. Additionally, theoretical calculations and microscopy reveal that the superior OER performance can be attributed to the increased exposure of binding sites within the material to which the catalytically active Fe³⁺ centers are bound through a post‐synthetic modification procedure. A red‐shift of the Fermi level around the valence band is observed and is proposed to be a result of the aforementioned interactions. This work opens an avenue toward the development of 2D functional metal organic framework nanosheets for energy conversion applications.