Finned Zn-MFI zeolite encapsulated noble metal nanoparticle catalysts for the oxidative dehydrogenation of propane with carbon dioxide

Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existing catalyst is limited due to the poor activity and stability,which hinders its industrialization.Herein,we design the finned Zn-MFI zeolite encapsulated noble metal nanoparticles(NPs)as bifunctional catalysts(NPs@Zn-MFI)for CO_(2)-ODP.Characterization results reveal that the Zn2+species are coordinated with the MFI zeolite matrix as isolated cations and the NPs of Pt,Rh,or Rh Pt are highly dispersed in the zeolite crystals.The isolated Zn2+cations are very effective for activating the propane and the small NPs are favorable for activating the CO_(2),which synergistically promote the selective transformation of propane and CO_(2)to propylene and CO.As a result,the optimal 0.25%Rh0.50%Pt@Zn-MFI catalyst shows the best propylene yield,satisfactory CO_(2)conversion,and long-term stability.Moreover,considering the tunable synergetic effects between the isolated cations and NPs,the developed approach offers a general guideline to design more efficient CO_(2)-ODP catalysts,which is validated by the improved performance of the bifunctional catalysts via simply substituting Sn4+cations for Zn2+cations in the MFI zeolite matrix.

Characterization of carbon encapsulated Fe-nanoparticles prepared by confined arc plasma

Carbon encapsulated Fe nanoparticles were successfully prepared via confined arc plasma method. The composition, morphology, microstructure, specific surface area and particle size of the product were characterized via X-ray diffraction, transmission electron microscopy, high resolution transmission electron microscopy, energy dispersive X-ray spectrometry and Brunauer-Emmett-Teller N2 adsorption. The experiment results show that the carbon encapsulated Fe nanoparticles have clear core-shell structure. The core of the particles is body centered cubic Fe, and the shell is disorder carbons. The particles are in spherical or ellipsoidal shapes. The particle size of the nanocapsules ranges from 15 to 40 nm, with the average value of about 30 nm. The particle diameter of the core is 18 nm, the thickness of the shells is 6-8 nm, and the specific surface area is 24 m2/g.

Heat transfer enhanced inorganic phase change material compositing carbon nanotubes for battery thermal management and thermal runaway propagation mitigation

Developing technologies that can be applied simultaneously in battery thermal management(BTM)and thermal runaway(TR)mitigation is significant to improving the safety of lithium-ion battery systems.Inorganic phase change material(PCM)with nonflammability has the potential to achieve this dual function.This study proposed an encapsulated inorganic phase change material(EPCM)with a heat transfer enhancement for battery systems,where Na_(2)HPO_(4)·12H_(2)O was used as the core PCM encapsulated by silica and the additive of carbon nanotube(CNT)was applied to enhance the thermal conductivity.The microstructure and thermal properties of the EPCM/CNT were analyzed by a series of characterization tests.Two different incorporating methods of CNT were compared and the proper CNT adding amount was also studied.After preparation,the battery thermal management performance and TR propagation mitigation effects of EPCM/CNT were further investigated on the battery modules.The experimental results of thermal management tests showed that EPCM/CNT not only slowed down the temperature rising of the module but also improved the temperature uniformity during normal operation.The peak battery temperature decreased from 76℃to 61.2℃at 2 C discharge rate and the temperature difference was controlled below 3℃.Moreover,the results of TR propagation tests demonstrated that nonflammable EPCM/CNT with good heat absorption could work as a TR barrier,which exhibited effective mitigation on TR and TR propagation.The trigger time of three cells was successfully delayed by 129,474 and 551 s,respectively and the propagation intervals were greatly extended as well.

Iron-based catalysts encapsulated by nitrogen-doped graphitic carbon for selective synthesis of liquid fuels through the Fischer-Tropsch process

Fischer‐Tropsch synthesis(FTS)has the potential to be a powerful strategy for producing liquid fuels from syngas if highly selective catalysts can be developed.Herein,a series of iron nanoparticle catalysts encapsulated by nitrogen‐doped graphitic carbon were prepared by a one‐step pyrolysis of a ferric L‐glutamic acid complex.The FeC‐800 catalyst pyrolyzed at 800°C showed excellent catalytic activity(239.4μmolCO gFe–1 s–1),high C5–C11 selectivity(49%),and good stability in FTS.The high dispersion of ferric species combined with a well‐encapsulated structure can effectively inhibit the migration of iron nanoparticles during the reaction process,which is beneficial for high activity and good stability.The nitrogen‐doped graphitic carbon shell can act as an electron donor to the iron particles,thus promoting CO activation and expediting the formation of Fe5C2,which is the key factor for obtaining high C5–C11 selectivity.

Carbon film encapsulated Fe_2O_3: An efficient catalyst for hydrogenation of nitroarenes

Iron catalysis has attracted a wealth of interdependent research for its abundance,low price,and nontoxicity.Herein,a convenient and stable iron oxide(Fe2O3)‐based catalyst,in which active Fe2O3nanoparticles(NPs)were embedded into carbon films,was prepared via the pyrolysis of iron‐polyaniline complexes on carbon particles.The obtained catalyst shows a large surface area,uniform pore channel distribution,with the Fe2O3NPs homogeneously dispersed across the hybrid material.Scanning electron microscopy,Raman spectroscopy and X‐ray diffraction analyses of the catalyst prepared at900°C(Fe2O3@G‐C‐900)and an acid‐pretreated commercial activated carbon confirmed that additional carbon materials formed on the pristine carbon particles.Observation of high‐resolution transmission electron microscopy images also revealed that the Fe2O3NPs in the hybrid were encapsulated by a thin carbon film.The Fe2O3@G‐C‐900composite was highly active and stable for the direct selective hydrogenation of nitroarenes to anilines under mild conditions,where previously noble metals were required.The synthetic strategy and the structure of the iron oxide‐based composite may lead to the advancement of cost‐effective and sustainable industrial processes.

Chemoselective Catalytic Hydrogenation of Nitroarenes Using MOF-Derived Graphitic Carbon Layers Encapsulated Ni Catalysts

Replacement of precious noble metal catalysts with cost-effective,non-noble heterogeneous catalysts for chemoselective hydrogenation of nitroarenes holds tremendous promise for the clean synthesis of nitrogen-containing chemicals.Graphitic carbon layers encapsulated Ni catalysts(Ni@CN)are generated by a facile,scalable and straightforward strategy via the pyrolysis of 2,5-pyridinedicarboxylic acid coordinated Ni-MOF acting as the precursor.Physicochemical properties of the Ni@CN catalysts have been investigated by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,elemental analysis and N2 adsorption-desorption analysis.The Ni@CN catalysts were found to be highly efficient in the chemoselective hydrogenation of various nitroarenes with other functional groups towards corresponding anilines under mild reaction conditions(85℃,1.0 MPa of H2 pressure).Based on the results of controlled tests,the catalytic activity can be attributed to the Ni NPs,while the presence of graphitic carbon layers favors the preferential adsorption of the nitro groups.The recyclability and anti-sulfur poisoning capability of Ni@CN were also investigated.

Decoration of carbon encapsulated nitrogen-rich MoxN with few-layered MoSe2 nanosheets for high-performance sodium-ion storage

Transition metal nitrides have become the focus of research in sodium ion batteries(SIBs)due to their unique metal properties and high theoretical capacity.However,the low actual capacity is still the main bottleneck for their application.Herein,using Mo-aniline frameworks as precursors,the carbon encapsulated nitrogen-rich Mo_(x)N is decorated by few-layered MoSe_(2) nanosheets(MoSe_(2)@Mo_(x)N/C-I)after the facile calcinating,selenizing,and nitriding.The carbon encapsulation can effectively strengthen the structural stability of Mo_(x)N.The nitrogen-rich Mo_(x)N and decoration of few-layered MoSe_(2) can create rich heterointerfaces and extra active sites for rapid sodium-ion storage,thus promoting reaction kinetics and improving actual capacity.The MoSe_(2)@Mo_(x)N/C-I as an anode achieves a large reversible capacity of 522.8 mAh g^(-1)at 0.1 A g^(-1),and 254.3 mAh g^(-1)capacity is obtained after 6000 cycles at 5.0 A g^(-1),showing signally improved sodium-ion storage properties.The storage mechanisms and kinetic behaviors are described systematically via the advanced testing techniques and density functional theory(DFT)calculations.It is found that the nitrogen-rich Mo_(x)N as the substrate is the basis of long cycling stability,and the few-layered MoSe_(2) are the key to improving actual capacity.This work indicates that the decoration of few-layered selenides has a broad application prospect in high-performance metal-ion batteries.

A Novel Method for Synthesis of Homogeneous Carbon Encapsulated Fe Nanoparticles Based on Natural Biopolymer

A novel and efficient route for preparing carbon encapsulated metal nanomaterials using staple biopolymer-starch as the carbon precursor was presented. Fe particles can be effectively encapsulated inside carbon shells by carbonizing composite of starch and iron oxide under hydrogen in a controllable way. Transmission electron microscopy (TEM), energy dispersive X-ray (EDX) and X-ray diffraction (XRD) were employed to characterize carbon encapsulated nanomaterials. The α-Fe and γ-Fe phases were clearly identified in those carbon encapsulated nanoparticles. The growth mechanism of carbon encapsulated metal nanoparticles was briefly discussed.

Theoretical prediction of half-metallicity of the encapsulated zigzag single walled carbon nanotube by NO,O_2 and NO_2 molecules

Finding half-metallic behavior in one-dimensional structure is a challenge for technological applications at the nanometer scale.In the present work,the investigation was performed on the structural,electronic,and magnetic properties of encapsulated zigzag carbon nanotube (CNT) with various sizes by the NO,NO2,and O2 molecules using spin-polarized density functional theory (DFT).It was found that the encapsulations of the three molecules inside the CNT are energetically favorable.The calculated adsorption energies are strongly dependent on the tube diameter and the orientation between the encapsulated molecules and tube axis,while the structures of both CNTs and encapsulated molecules are nearly unchanged.Interestingly,the encapsulated CNTs by the three molecules exhibit half-metallicty in terms of the opposite local gating effect of the spin states.

Carbon encapsulated magnetic nanoparticles produced by hydrothermal reaction

Carbon encapsulated magnetic nanoparticles （CEMNs） were synthesized by heating an aqueous glucose solution containing Fe-Au （Au coated Fe nanoparticles） nanoparticles at 160-180 ℃ for 2 h. This novel hydrothermal approach is not only simple but also provides the surface of CEMNs with functional groups like--OH. The formation of carbon encapsulated magnetic nanoparticles was not favored when using pure Fe nanoparticles as cores because of the oxidation of Fe nanoparticles by 1-120 during the reaction and, therefore, the surfaces of the naked Fe nanoparticles had to be coated by Au shell in advance. TEM, XRD, XPS and VSM measurments characterized that they were uniform carbon spheres containing some embedded Fe-Au nanoparticles, with a saturation of 14.6 emu/g and the size of the typical product is -350 nm.

Preparation of Carbon Encapsulated Iron Nanoparticles with Very Thin Shells by DC Arc Discharge

Carbon encapsulated iron nanoparticles （CEINPs） with very thin shells and good core-shell structures were prepared by DC arc discharge at argon intake temperature （AIT） of 800 ℃. The results of high resolution transmission electron microscope （HRTEM）, energy dispersive X-ray （EDX） spectroscope, X-ray diffraction （XRD）, and X-ray photoelectron spectroscope （XPS） characterizations on the product B show that the thickness of the carbon shells of CEINPs in the product B is in the range of ca. 0.5-5.3 nm, i. e., which can be as thin as only two layers of graphite. The average diameter of the CEINPs is about 24. 7 nm. The total content of Fe element in the product B is 77.0 wt%. The saturation magnetization （Ms） and coercivity （Hc） of the product B are 107.4 emu/g and 143 Oe. resnectivelv. The formation of the CEINPs in the oroduct B is discussed briefly.

Eelectrical Transport Properties of C₅₉N Azafullerene Encapsulated Double-Walled Carbon Nanotube

Electrical transport properties of double-walled carbon nanotubes (DWNTs) are modulated by encapsulating the azafullerene C59N which is synthesized via a plasma ion-irradiation method. The encapsulation of C59N molecules inside DWNTs has been confirmed by both transmission electron microscopy and Raman spectroscopy. The pristine DWNTs with outer diameter 4 - 5 nm are found to exhibit an ambipolar semiconducting behavior due to their small band gap. It is found that C60 fullerene encapsulated DWNTs exhibit a unipolar p-type semiconducting behavior. By comparison, C59N encapsulated DWNTs display an n-type semiconducting behavior. Our findings demonstrate that C59N operates as an electron donor compared with the acceptor behavior of C60, which is further clarified by photoelectron emission spectroscopy.

Anti-aggregation growth and hierarchical porous carbon encapsulation enables the C@VO_(2) cathode with superior storage capability for aqueous zinc-ion batteries

Self-aggregation and sluggish transport kinetics of cathode materials would usually lead to the poor electrochemical performance for aqueous zinc-ion batteries(AZIBs).In this work,we report the construction of C@VO_(2) composite via anti-aggregation growth and hierarchical porous carbon encapsulation.Both of the morphology of composite and pore structure of carbon layer can be regulated by tuning the adding amount of glucose.When acting as cathode applied for AZIBs,the C@VO_(2)-3:3 composite can deliver a high capacity of 281 m Ah g^(-1) at 0.2 A g^(-1).Moreover,such cathode also exhibits a remarkably rate capability and cyclic stability,which can release a specific capacity of 195 m Ah g^(-1) at 5 A g^(-1) with the capacity retention of 95.4%after 1000 cycles.Besides that,the evolution including the crystal structure,valence state and transport kinetics upon cycling were also deeply investigated.In conclusion,benefited from the synergistic effect of anti-aggregation morphology and hierarchical porous carbon encapsulation,the building of such C@VO_(2) composite can be highly expected to enhance the ion accessible site,boost the transport kinetics and thus performing a superior storage performance.Such design concept can be applied for other kinds of electrode materials and accelerating the development of highperformance AZIBs.

Novel in-capsule synthesis of metal-organic framework for innovative carbon dioxide capture system

Metal-Organic Frameworks(MOFs)have been developed as solid sorbents for CO_(2) capture applications and their properties can be controlled by tuning the chemical blocks of their crystalline units.A number of MOFs(e.g.,HKUST-1)have been developed but the question remains how to deploy them for gas-solid contact.Unfortunately,the direct use of MOFs as nanocrystals would lead to serious problems and risks.Here,for the first time,we report a novel MOF-based hybrid sorbent that is produced via an innovative in-situ microencapsulated synthesis.Using a custom-made double capillary microfluidic assembly,double emulsions of the MOF precursor solutions and UV-curable silicone shell fluid are produced.Subsequently,HKUST-1 MOF is successfully synthesized within the droplets enclosed in the gas permeable microcapsules.The developed MOF-bearing microcapsules uniquely allow the deployment of functional nanocrystals without the challenge of handling ultrafine particles,and further,can selectively reject undesired compounds to protect encapsulated MOFs.

Temperature Dependent Surface Resistivity Measures of Commercial, Multiwall Carbon Nanotubes (MWCNT), and Silver Nano-Particle Doped Polyvinyl Alcohol (PVA) Films

Pure and doped Polyvinylidene difluoride (PVDF) films, for the detection of infrared radiation, have been well documented using the mechanism of pyroelectricity. Alternatively, the electrical properties of films made from Polyvinyl Alcohol (PVA) have received considerable attention in recent years. The investigation of surface resistivities of both such films, to this point, has received far less consideration in comparison to pyroelectric effects. In this research, we report temperature dependent surface resistivity measurements of commercial, and of multiwall carbon nanotubes (MWCNT), or Ag-nanoparticle doped PVA films. Without any variation in the temperature range from 22°C to 40°C with controlled humidity, we found that the surface resistivity decreases initially, reaches a minimum, but rises steadily as the temperature continues to increase. This research was conducted with the combined instrumentation of the Keithley Model 6517 Electrometer and Keithley Model 8009 resistivity test fixture using both commercial and in-house produced organic thin films. With the objective to quantify the suitability of PVDF and PVA films as IR detector materials, when using the surface resistivity phenomenon, instead of or in addition to the pyroelectricity, surface resistivity measurements are reported when considering bolometry. We found that the surface resistivity measurements on PVA films were readily implemented.

Zr-MOF固载聚离子液体对CO_(2)环加成反应的催化性能

通过无溶剂限域封装,将二溴对二甲苯和4,4′-联吡啶吸附至UiO-67材料微孔中,并原位聚合成聚离子液体PBpy-Br,得到兼具Br^(-),Zr-OH/Zr-OH_(2)和N杂环3种活性中心的复合材料PBpy-Br@UiO-67.采用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、^(13)C核磁共振波谱(^(13)C NMR)、比表面积分析(BET)和热重分析(TGA)等手段对材料进行了表征,并将其应用于催化CO_(2)与环氧氯丙烷的环加成反应中.在单因素实验基础上,通过响应面优化确定的最佳反应条件为反应温度100℃、p_(CO_(2))=0.1 MPa、催化剂用量(质量分数)0.22%以及反应时间22 h.在该条件下,环氧氯丙烷转化率达99.6%,催化剂循环使用5次后,转化率仅下降2.3%.此外,对PBpy-Br@UiO-67的普适性进行了研究,将其用于催化其它环氧化物与CO_(2)反应,转化率均在50%以上.研究结果表明,PBpy-Br@UiO-67催化剂具有反应条件温和及催化效率高的特点,为CO_(2)的固定与转化提供了新催化体系.

氮掺杂碳包覆的氧化镍和钼酸镍复合材料用于尿素氧化电催化

通过分步水热以及退火的方法合成了氮掺杂碳包覆的氧化镍和钼酸镍复合材料(CN@NiO-NiMoO_(4)),并将其负载于泡沫镍(NF)上,直接用作催化尿素氧化反应UOR的电极材料。实验表明:氮掺杂碳包覆结构以及C-N@NiO与NiMoO_(4)的协同作用可以增强催化剂的导电性、电荷转移能力、抗中毒能力并增大电活性表面积,显著提高了C-N@NiO-NiMoO_(4)的电催化活性和长期稳定性。研究还发现,C-N@NiO-NiMoO_(4)/NF在1.8 V的电流密度是NiMoO_(4)/NF的1.7倍,C-N@NiO/NF的3.6倍,在10 mA·cm^(-2)的电流密度下催化UOR 57 h,催化性能无显著变化。综上,C-N@NiO-NiMoO_(4)具有良好的实际应用前景。

Efficient hydrothermal deoxygenation of methyl palmitate to diesel-like hydrocarbons on carbon encapsulated Ni–Sn intermetallic compounds with methanol as hydrogen donor

Porous carbon-encapsulated Ni and Ni-Sn intermetallic compound catalysts were prepared by the one-pot extended Stöber method followed by carbonization and tested for in-situ hydrothermal deoxygenation of methyl palmitate with methanol as the hydrogen donor.During the catalyst preparation,Sn doping reduces the size of carbon spheres,and the formation of Ni-Sn intermetallic compounds restrain the graphitization,contributing to larger pore volume and pore diameter.Consequently,a more facile mass transfer occurs in carbon-encapsulated Ni-Sn intermetallic compound catalysts than in carbonencapsulated Ni catalysts.During the in-situ hydrothermal deoxygenation,the synergism between Ni and Sn favors palmitic acid hydrogenation to a highly reactive hexadecanal that easily either decarbonylate to n-pentadecane or is hydrogenated to hexadecanol.At high reaction temperature,hexadecanol undergoes dehydrogenation-decarbonylation,generating n-pentadecane.Also,the C-C bond hydrolysis and methanation are suppressed on Ni-Sn intermetallic compounds,favorable for increasing the carbon yield and reducing the H_(2) consumption.The npentadecane and n-hexadecane yields reached 88.1%and 92.8%on carbon-encapsulated Ni_(3) Sn_(2) intermetallic compound at 330℃.After washing and H_(2) reduction,the carbon-encapsulated Ni_(3) Sn_(2) intermetallic compound remains stable during three recycling cycles.This is ascribed to the carbon confinement that effectively suppresses the sintering and loss of metal particles under harsh hydrothermal conditions.

工业放大碳包覆镍催化剂在催化加氢芳硝基化合物中的应用

基于金属羧酸络合物前体热解法,实现碳包覆镍(Ni@C)纳米复合材料的工业放大生产。考察了Ni@C催化剂在芳硝基化合物选择性加氢反应中的性能,通过分析加氢反应的中间产物并以苯基羟胺为模型化合物开展加氢评价及循环套用实验。实验结果表明,Ni@C可在温和的反应条件下(50℃,1 MPa H_(2))高选择性(高于99%)加氢4-硝基氯苯(4-NCB)、4-硝基苯酚、1,3-二硝基苯等多种芳硝基化合物,合成对应的芳香胺类化合物;Ni@C催化加氢4-NCB的过程为直接路径与缩合路径并存的反应路径,且Ni@C催化剂具有较好的稳定性;Ni@C还具有抗噻吩等硫化物中毒的特性,并可用于硫代芳胺的合成。

面向未来高性能电子器件的石墨烯纳米带

石墨烯纳米带具有可调节的带隙和较高的载流子迁移率,是未来高性能纳米电子器件的理想候选材料之一。然而,可用于电子器件的高质量石墨烯纳米带的制备一直是一个巨大挑战。文章关注高质量石墨烯纳米带的制备,重点介绍近年来采用金属纳米颗粒催化生长纳米带方面的重要进展,尤其是运用该技术在六方氮化硼层间嵌入式生长超高质量石墨烯纳米带的最新成果。基于这种层间纳米带的场效应晶体管表现出优异的性能,有望在将来的碳基纳米电子器件中扮演重要的角色。最后讨论该领域未来可能面临的机遇与挑战。