过渡金属氧化物和金属负载型沸石催化剂上合成 纳米碳管及其表征

采用气相催化沉积法催化合成纳米碳管,比较了不同金属氧化物和金属负载型沸石催化剂以及不同分子筛载体对合成纳米碳管的影响,并用TEM,XRD表征其形貌和结晶度,用DTA-TG考察了纳米碳管的热和稳定性。实验结果表明纳米碳管的形成除了与金属种类有关外,还直接与催化剂的颗粒大小和分散状态有关。粒径在20nm左右的不规则形状的纳米粒子是形成纳米碳管的活性组分,非负载和负载型的催化剂均表明活性组分的粒径与纳米碳管的管径有一定的对应关系。化学提纯后能得到高纯度的纳米碳管;其管壁具有较好的石墨化结构,在空气中的热稳定性大于400℃,而在氮气中能维持到1200℃以上。     

Electrical Property of Tin Oxide Doped with Multi‐Walled Carbon Nanotubes

Tin oxide doped with multi‐walled carbon nanotubes (MWNTs) was prepared via a wet‐chemical process and characterized with x‐ray diffraction (XRD) and transmission electron microscope (TEM). Meanwhile, the conductivity of composites obtained was measured using Source Meter. The results show that carbon nanotubes have great effect on the electrical property of SnO₂ nanoparticles. Compared with undoped SnO₂ nanoparticles, the resistivity of SnO₂ nanoparticles doped with 0.3‰ wt MWNTs decreased by a factor of 37. This may be ascribed to the presence of π energy levers of MWNTs and their high aspect ratio. Moreover, the effect of annealing temperature on the electrical property of SnO₂ nanoparticles doped with MWNTs also was discussed.     

Synthesis of carbon nanotubes by catalytic pyrolysis method with Feitknecht compound as precursor of NiZnAl catalyst

Carbon nanotubes are synthesized by catalytic pyrolysis method with a kind of new type catalyst--nickel-zinc-alumina catalyst prepared from Feitknecht compound. Tubular carbon nanotubes, bamboo-shaped carbon naotubes, herringbone carbon nanotubues and branched carbon nanotubes are all found formed at moderate temperature. It is important for the formation of quasi-liquid state of the metal nanoparticles at the tip of carbon naotubes during the growth of carbon nanotubes to lead to different kinds of carbon nanotubes. It is likely that the addition of zinc make the activity of nickel catalyst after calcinations and reduction changed strangely.     

Ultrasonic approach for formation of erbium oxide nanoparticles with variable geometries

Ultrasound (20 kHz, 29 W·cm(-2)) is employed to form three types of erbium oxide nanoparticles in the presence of multiwalled carbon nanotubes as a template material in water. The nanoparticles are (i) erbium carboxioxide nanoparticles deposited on the external walls of multiwalled carbon nanotubes and Er(2)O(3) in the bulk with (ii) hexagonal and (iii) spherical geometries. Each type of ultrasonically formed nanoparticle reveals Er(3+) photoluminescence from crystal lattice. The main advantage of the erbium carboxioxide nanoparticles on the carbon nanotubes is the electromagnetic emission in the visible region, which is new and not examined up to the present date. On the other hand, the photoluminescence of hexagonal erbium oxide nanoparticles is long-lived (μs) and enables the higher energy transition ((4)S(3/2)-(4)I(15/2)), which is not observed for spherical nanoparticles. Our work is unique because it combines for the first time spectroscopy of Er(3+) electronic transitions in the host crystal lattices of nanoparticles with the geometry established by ultrasound in aqueous solution of carbon nanotubes employed as a template material. The work can be of great interest for "green" chemistry synthesis of photoluminescent nanoparticles in water.     

Nanostructure Engineering of Metal–Organic Derived Frameworks: Cobalt Phosphide Embedded in Carbon Nanotubes as an Efficient ORR Catalyst

Heteroatom doping is considered an efficient strategy when tuning the electronic and structural modulation of catalysts to achieve improved performance towards renewable energy applications. Herein, we synthesized a series of carbon-based hierarchical nanostructures through the controlled pyrolysis of Co-MOF (metal organic framework) precursors followed by in situ phosphidation. Two kinds of catalysts were prepared: metal nanoparticles embedded in carbon nanotubes, and metal nanoparticles dispersed on the carbon surface. The results proved that the metal nanoparticles embedded in carbon nanotubes exhibit enhanced ORR electrocatalytic performance, owed to the enriched catalytic sites and the mass transfer facilitating channels provided by the hierarchical porous structure of the carbon nanotubes. Furthermore, the phosphidation of the metal nanoparticles embedded in carbon nanotubes (P-Co-CNTs) increases the surface area and porosity, resulting in faster electron transfer, greater conductivity, and lower charge transfer resistance towards ORR pathways. The P-Co-CNT catalyst shows a half-wave potential of 0.887 V, a Tafel slope of 67 mV dec⁻¹, and robust stability, which are comparatively better than the precious metal catalyst (Pt/C). Conclusively, this study delivers a novel path for designing multiple crystal phases with improved catalytic performance for energy devices.     

La~2NiO~4催化制备纳米碳管

制备了四方结构复合氧化物La~2NiO~4,并以其为催化剂前体,甲烷和一氧化碳为碳,合成出大量高纯度的纳米碳管。XRD结果表明La~2NiO~4经还原后,在La~2O~3的隔离作用下Ni晶粒实现纳米级均匀分散。利用TEM,HRTEM,SEM,XRD,Raman等手段对所制备的纳米碳管进行了观察和表征。所制备的纳米碳管管径均匀、石墨化程度较高,该法制备纳米碳管工艺简单、产量较高,产品易于纯化。     

Three‐Dimensional Nitrogen‐Doped Reduced Graphene Oxide–Carbon Nanotubes Architecture Supporting Ultrafine Palladium Nanoparticles for Highly Efficient Methanol Electrooxidation

A three‐dimensional (3D) nitrogen‐doped reduced graphene oxide (rGO)–carbon nanotubes (CNTs) architecture supporting ultrafine Pd nanoparticles is prepared and used as a highly efficient electrocatalyst. Graphene oxide (GO) is first used as a surfactant to disperse pristine CNTs for electrochemical preparation of 3D rGO@CNTs, and subsequently one‐step electrodeposition of the stable colloidal GO–CNTs solution containing Na₂PdCl₄ affords rGO@CNTs‐supported Pd nanoparticles. Further thermal treatment of the Pd/rGO@CNTs hybrid with ammonia achieves not only in situ nitrogen‐doping of the rGO@CNTs support but also extraordinary size decrease of the Pd nanoparticles to below 2.0 nm. The resulting catalyst is characterized by scanning and transmission electron microscopy, X‐ray diffraction, Raman spectroscopy, and X‐ray photoelectron spectroscopy. Catalyst performance for the methanol oxidation reaction is tested through cyclic voltammetry and chronoamperometry techniques, which shows exceedingly high mass activity and superior durability.     

金属掺杂Ce-M(M=Fe、Ni和Cu)催化剂的CO低温氧化性能研究

采用水热合成法制备了一系列不同金属掺杂的Ce-M（M=Fe、Ni和Cu）复合氧化物,运用低温N₂吸附-脱附、XRD、H₂-TPR、拉曼光谱和XPS等表征技术对Ce-M复合氧化物的结构与其CO低温氧化反应性能之间的关系进行了关联。结果表明,将Fe、Ni和Cu掺入CeO₂明显提高了其氧空位的含量,提升了晶格氧的流动性,从而使Ce-M催化剂的还原能力和催化活性高于纯CeO₂。其中,CeCu催化剂氧空位最多、还原能力最好,催化活性最高,130 ℃下即可将CO完全氧化;其次是CeNi催化剂,180 ℃时实现CO完全氧化;与之相比,CeFe催化剂的活性最差,200 ℃时的CO转化率仅为92%。     

Catalytic Activation of a Solid Oxide in Electronic Contact With Gold Nanoparticles

Although inert in its bulk form, nanostructured gold supported on oxides has been found to be catalytically active. In many cases, the oxide promotes the activity of Au. It is now shown that in turn, nanoscale Au particles can chemically activate the solid oxide. Specifically, it was discovered that 4 nm Au nanoparticles deposited on zinc oxide catalyze the transformation of the oxide into the sulfide in the presence of an organosulfur species. Contact of the oxide with Au nanoparticles lowers the activation barrier for the solid‐state reaction by approximately 20 kJ mol^?1, allowing the reaction to be achieved closer to ambient temperatures. Electron transfer from oxygen vacancies to Au nanoparticles is proposed to generate acidic sites on the surface of the zinc oxide, resulting in the enhanced reactivity of the oxide. Knowledge of such electronic interactions between the noble metal and oxide can be exploited for engineering reactive heterostructures for low‐temperature pollutant sorption and hydrocarbon processing.     

Synthesis of Zn doped black TiO2 nanoparticles for degradation of 2, 4, 6 tri-chloro-phenol under visible light

A modified sol-gel method was used for synthesis of zinc doped black TiO₂ nanoparticles. The modified sol-gel synthesised catalyst was utilised for degradation of 2, 4, 6 tri-chloro-phenol under visible light irradiation. The catalyst was characterized using XRD, SEM, TEM, BET and DRS analysis. The nanoparticles were crystalline in nature and in anatase phase. The size of zinc doped black TiO₂ nanoparticles was 5 nm. The synthesised nanoparticles were mesoporous in nature and the specific surface area was found to be 34.15 m²/g. The band gap energy of zinc black TiO₂ nanoparticles was found to be 2.73 eV. The point of zero charge of zinc doped black TiO₂ nanoparticles was 6.7. The maximum degradation of 2, 4, 6 tri-chloro-phenol using 2 mol% zinc doped black TiO₂ was found to be 95%.     

Dopant-stimulated CuO Nanofibers for Electro-oxidation and Determination of Glucose

We described the preparation of copper oxide composite nanofibers doped with carbon nanotubes (CuO/C-NFs) or nickel oxide(CuO/NiO-NFs) by electrospinning for direct glucose determination. The interest in exploring practical CuO/C-NFs and CuO/NiO-NFs electrode materials for sensor application was fascinated by the possibility of promoting electron transfer for kinetically unfavorable glucose oxidation reactions at a lower overpotential and thus improving the selectivity of the electrode for glucose in electroanalysis. The morphologies of CuO/C-NFs and CuO/NiO-NFs were characterized by scanning electron microscopy(SEM) and X-ray powder diffraction(XRD). The electrocatalytic performances of glucose were evaluated in detail by cyclic voltammetry(CV) and chronoamperometry. Facile charge transport, enhanced current response(at a lower overpotential of +0.35 V), improved stability and selectivity, as well as excellent resistance towards electrode fouling were observed at CuO/ C-NFs electrode in direct glucose electroanalysis. These merits are attributed to the highly porous three-dimensional network film structure of CuO/C-NFs electrode materials and the potential synergic catalytic effect of CuO and carbon nanotubes in composite nanofibers. This study may provide a new insight into metal oxide-based composite nanofibers obtained via electrospinning for fabricating novel and high performance sensors and devices.     

Synthesis of Poly (methyl methacrylate)/Zinc Oxide Nanocomposite with Core-Shell Morphology by Atom Transfer Radical Polymerization

A method to prepare zinc oxide (ZnO) nanoparticles with a covalently bonded poly(methyl methacrylate) (PMMA) shell by surface initiated atom transfer radical polymerization (ATRP) was reported. First, the initiator for ATRP was covalently bonded onto the surface of zinc oxide nanoparticles through our novel method. Firstly, the surface of ZnO nanoparticle was treated with 3-aminopropyl triethoxysilane, a silane coupling agent, and then this functionalization nanoparticle was reacted with α-chloro phenyl acetyl chloride to prepare atom transfer radical polymerization macroinitiator. The metal-catalyzed radical polymerization of MMA with ZnOmacroinitiator was performed using a copper catalyst system to give the ZnO-based nanoparticles hybrids linking PMMA segments (poly (methyl methacrylate)/zinc oxide nanocomposite). These hybrid nanoparticles had an exceptionally good dispersability in organic solvents and were subjected to detailed characterization using FTIR, TEM and TGA and DSC analyzed.     

Highly active Co-doped LaMnO3 perovskite oxide and N-doped carbon nanotube hybrid bi-functional catalyst for rechargeable zinc–air batteries

Herein, non-precious cobalt doped lanthanum manganese perovskite oxide nanoparticles are used as a growth substrate for nitrogen-doped carbon nanotubes to form efficient and durable hybrid bi-functional catalyst (LMCO/NCNT). LMCO/NCNT demonstrates significantly enhanced onset and half-wave oxygen reduction reaction (ORR) potentials (− 0.11 and − 0.24 V vs. SCE, respectively), and oxygen evolution reaction (OER) current density (27 mA cm^− 2 at 0.9 V vs. SCE). Likewise, practical rechargeable zinc–air battery testing using atmospheric air reveals superior discharge voltages obtained with LMCO/NCNT, particularly at current densities higher than 30 mA cm^− 2, and significantly lower charge voltages at all current densities tested, compared to state-of-art commercial platinum on carbon catalyst. In addition, very stable charge and discharge voltages of 2.2 and 1.0 V, respectively, are obtained over 60 cycles. The excellent performance and durability of the hybrid catalyst are attributed to very uniformly distributed LMCO nanoparticles on the surface of NCNT resulting in enhanced surface area and material utilization.     

用于丁烷选择氧化制顺酐的铈锆复合钒磷氧催化剂的研究

 在钒磷氧（VPO）催化剂中添加适量铈锆复合氧化物，得到了一\r\n种新型的铈锆复合钒磷氧催化剂．该催化剂对丁烷选择性氧化制顺酐反\r\n应的催化性能比纯VPO催化剂有了显著提高．在丁烷／空气共进料反应\r\n条件下，其顺酐收率比纯VPO催化剂提高了一倍；在无氧反应条件下，\r\n其可参与选择性氧化制顺酐的晶格氧量为纯VPO催化剂的2．2倍．BET比\r\n表面积测试、X射线衍射、钒平均价态测定和程序升温实验等表征结果\r\n表明，混合在催化剂活性相中的少量铈锆复合氧化物参与了VPO体系的\r\n氧化还原过程，并起到了以下两方面的作用：（1）促进了（VO）2P2O\r\n7相的形成，稳定了钒的平均价态，有利于最终形成晶相结构良好和反\r\n应性能稳定的VPO催化剂；（2）显著提高了VPO催化剂的氧化还原性能\r\n，大大增加了催化剂的可逆储氧量．     

Parameters affecting carbofuran photocatalytic degradation in water using ZnO nanoparticles

Carbofuran photodegradation in water using zinc oxide nanoparticles as a catalyst was examined as well as some parameters influencing its percentage degradation rate such as zinc oxide load, initial concentration of carbofuran, the temperature of the reaction, the initial pH of the solution, and doping of zinc oxide nanoparticles with 5% (w:w) silver. Zinc oxide and Ag-doped zinc oxide nanoparticles were produced using solvothermal and photoreduction methods, respectively, and silver doping effects on the structural, optical, and photocatalytic properties of zinc oxide nanoparticles were investigated using XRD, UV-VIS spectrophotometer, TEM, SEM, SEM/EDX, and FTIR. The average diameter of the synthesized samples was 26.6, 30.55 nm for undoped zinc oxide and Ag-doped zinc oxide, respectively. Zinc oxide doping with silver did not change the shape of the zinc oxide crystal, but decreased the reflection in the visible region, as well as the energy of the bandgap, and increased the zinc oxide photocatalytic activity.     

Screening of MgO——and Ce02-Based Catalysts for Carbon Dioxide Oxidative Coupling of Methane to C2＋ Hydrocarbons

The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM)have been investigated over ternary and binary metal oxide catalysts.The catalysts are prepared by doping MgO-and CeO2-based solids with oxides from alkali(Li2O),alkaline earth (CaO),and transition metal groups (WO3 or MnO).The presence of the peroxide (O2^2-)active sites on the Li2O2,revealed by Raman spectroscopy,may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts.The high reducibility of the CeO2 catalyst,an important factor in the CO2-OCM catalyst activity,may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobitity and oxygen vacancies in the CeO2 catalyst.raman and Fourier Transform Infra Red (FT-IR)spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks carresponding to the buld crystalline structures of Li2O,CaO,WO2 and MnO are detected.The performance of 5%MnO/15?O/CeO2 catalyst is the most potential among the CeO2-based catalysts,although lower than the 2%Li2O/MgO catalyst.The 2%Li2O/MgO catalyst showed the most promising C2 hydrocarbons selectivity and yield at 98.0%and 5.7%,respectively.     

Antibacterial study of Eucalyptus grandis fabricated zinc oxide and magnesium doped zinc oxide nanoparticles and its characterization

Mg-doped zinc oxide and zinc oxide nanoparticles were prepared by using methanolic seed extract from the Eucalyptus grandis plant via a green approach. Phytoconstituents present in seed extract act as capping and stabilizing agents for the biosynthesis of nanoparticles. Doping of Mg to zinc oxide nanoparticles increases the bandgap energy, thus enhancing its chemical, physical and optical properties. Further, it was characterized by various techniques such as scanning electron microscopy giving morphological information about the wurtzite hexagonal structure of bio-synthesized nanoparticles. X-ray diffraction technique tells about the crystalline nature of particles and the average crystallite size for zinc oxide and doped zinc oxide nanoparticles. Mg as a dopant enhances the properties of nanoparticles, thus making it more efficiently applicable as an antibacterial agent against Escherichia coli, gram-negative bacteria.     

基于纳米材料修饰的高灵敏性L-苯丙氨酸印迹溶胶-凝胶传感器的研究

将氧化锌纳米膜(ZnO-NFs)、多壁碳纳米管(MWNTs)、纳米铜颗粒(Cu-NPs)和印迹溶胶-凝胶聚合物(MIP)依次修饰到碳电极(CE)表面,制备了一种对L-苯丙氨酸具有特异识别能力的印迹电化学传感器.采用电子扫描显微镜(SEM)对各修饰电极进行形貌表征;采用循环伏安法(CV)、示差脉冲伏安法(DPV)、安培时...     

Screening of MgO- and CeO_2-Based Catalysts for Carbon Dioxide Oxidative Coupling of Methane to C_(2+) Hydrocarbons

The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may     

Thermal stability and reactivity of metal halide filled single-walled carbon nanotubes

Thermal stability and reactivity to oxidation of several nanocomposite systems obtained by encapsulation of metal halides in single-walled carbon nanotubes are studied. Thermogravimetric analysis coupled with Raman spectroscopy allows insight into the various contributing factors, such as charge transfer, strain, and defect formation, and establishing a hierarchy of reactivity for the systems studied (AgX@SWCNTs, with X = Br, I; SWCNTs = arc discharge and HiPCO). The activation energy for oxidation decreases considerably after filling, indicating that filled nanotubes are more amenable to controlled modifications based on chemical reactivity than the originating empty nanotubes. The complete removal of the carbon shell at high temperatures does not preserve the nanowire morphology of the encapsulated halides; these are freed on surfaces in the form of nanoparticles arranged in 1D patterns. Metallic nanoparticles were obtained after hydrogen reduction of the halides, and growth of silicon nanowires in the footprint of the originating nanocomposites was demonstrated from such Co seeds. MX@SWCNTs (M = Ag, Co) can thus be used as environmentally stable nanoscale containers that allow the deliverance of catalytic nanoparticles in a prepatterned and aligned way.