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1.
Nitrogen doped carbon nanotubes (N-CNTs) have been synthesized by the chemical vapour deposition (CVD) floating catalyst method using either 4-ferrocenylaniline or mixtures of varying concentrations of ferrocene/aniline together with toluene as added carbon source. The N-CNTs produced are less stable (thermal gravimetric analysis measurements), less graphitic and more disordered (transmission electron microscope measurements) than their undoped counterparts. The ratio of the Raman D- and G-band intensities increase with the nitrogen concentration used during the CNT growth. Furthermore, the transmission electron microscope (TEM) studies reveal that the CNTs are multi-walled (MW), and that the diameters of the N-MWCNTs can be controlled by systematically varying the concentrations of the nitrogen source. The TEM analysis also revealed that when ferrocenylaniline and ferrocene/aniline reactions are compared at similar Fe/N ratios, higher N doping levels are achieved (ca. 2-5×) when ferrocenylaniline is the catalyst.  相似文献   

2.
刘京  宋平  阮明波  徐维林 《催化学报》2016,(7):1119-1126
目前,开发高效的阴极氧还原反应(ORR)电催化剂是实现燃料电池和金属-空气电池商业化发展急需完成的目标。在过去的几十年中,人们在探索廉价高效的 ORR电催化剂(如 N掺杂的非金属及非铂电催化剂)领域做了广泛的研究。在 N掺杂的碳基 ORR催化剂中,已知的 N基活性位点主要分为四类,即吡啶类氮(P-N)、吡咯类氮(Py-N)、石墨化氮(G-N)和氧化类氮(O-N)。尽管人们对这四种类型氮的活性位点做了大量的研究,但是它们在催化反应中起到的 ORR催化作用以及催化机理和活性位点本身结构的关系仍不够明确。早期的研究中有人认为 P-N或者 Py-N是 ORR催化活性位点,也有人认为是 G-N起作用。最近也有研究表明, P-N和 G-N都是 ORR催化活性位点,只是在 ORR中所起的催化能力不同。因此,很有必要认清这些问题。
  本文通过 Hummer法酸性氧化一次和两次碳黑 Vulcan XC-72(VXC-72)以及随后高温热处理,制备了一系列 ORR催化剂 VXCO-1, VXCO-2, VXCO-1(900)和 VXCO-2(900),采用场发射扫描电子显微镜(SEM), N2吸附脱附法,元素分析仪(EA), X射线光电子能谱(XPS),拉曼光谱仪(Raman), X射线衍射能谱(XRD),电化学循环伏安法和线性伏安法测试等手段研究 Hummers法酸氧化和高温热处理对 VXC-72形貌组成的影响,以及这些碳基中成分和其催化 ORR能力的关系。
   SEM结果表明, Hummer法酸性氧化处理 VXC-72一次和两次后可以逐层剥落其最外边的碳层结构,最终得到表面光滑的类片层状结构的碳材料(VXCO-1和 VXCO-2)。这种表面光滑的类片层状结构的碳材料比表面积大于处理前的 VXC-72,而高温热处理之后的碳材料(VXCO-1(900)和 VXCO-2(900))由于类石墨层碎片结构蒸发损失暴露出更多内部的微孔和介孔结构使比表面积增加。 Raman和 XRD结果表明,氧化处理使碳材料的石墨化程度增加,而高温热处理则降低了其石墨化程度。
   EA和 XPS结果表明, Hummer法酸性氧化处理可以使在碳材料中掺入的 N以石墨化的为主,高温热处理却使得石墨化氮转变为吡啶类的氮。 ORR结果发现,活性的石墨化氮倾向于使 ORR反应经历两电子过程,从而生成 H2O2为主要产物;而吡啶类氮的活性位点更倾向于使 ORR反应经过四电子过程,主产物是水。该结果有助于新型碳基氧还原催化剂的设计和分析。  相似文献   

3.
Nitrogen doped zinc oxide (ZnO) nanoparticles have been synthesized using a colloidal route and low temperature nitridation process. Based on these results, 200 nm thick transparent ZnO thin films have been prepared by dip-coating on SiO2 substrate from a ZnO colloidal solution. Zinc peroxide (ZnO2) thin film was then obtained after the chemical conversion of a ZnO colloidal thin film by H2O2 solution. Finally, a nitrogen doped ZnO nanocrystalline thin film (ZnO:N) was obtained by ammonolysis at 250 °C. All the films have been characterized by scanning electron microscopy, X-ray diffraction, X-Ray photoelectron spectroscopy and UV–Visible transmittance spectroscopy.  相似文献   

4.
There is limited information on changes cause by nitrogen (N) fertilizers and biochar (BC) application in soil carbon and nitrogen availability, leaching and microbial activity at different growth stages in rice. This is first comprehensive study conducted in early and late seasons during 2019 to evaluate efficiency of various traditional N fertilizers (i) Urea (ii) Ammonium nitrate and (iii) Ammonium sulfate (315 kg N ha−1) with or without biochar (30 t ha−1). Results illustrated that all N fertilizers sources applied with biochar significantly increased soil organic carbon (SOC) content by an average 48.44% and 50.63%, soil total nitrogen (Nt) by 4.56% and 4.94%, reduction in total nitrogen leaching by 42.63% and 76.16%, while dissolved organic carbon leaching (DOC) augmented by 39.87% and 38.38% than non-applied treatments in early and late season, respectively. Additionally, soil microbial biomass C and N progressively increased with growth stages and was found higher than non-applied treatments in both seasons. Furthermore, combined application of N fertilizers and biochar, facilitated soil N transformation and the net concentration of NH4+–N and NO3–N was relatively higher than non-charred treatments. Similarly, in both early and late seasons, urease enzyme activity increased by an average 13.52% and 13.55%, β-glucosidase by 15.99% and 19.27% however, catalase activity decreased by 14.58% and 12.38%, correspondingly. Moreover, no significant difference (p < 0.05) was recorded among N fertilizers sources in both seasons.  相似文献   

5.
Boron and nitrogen compounds are added in the acetone/hydrogen gas mixture to deposit hot filament chemical vapor deposition (HFCVD) diamond films on the cobalt cemented tungsten carbide (WC–Co) substrate under the pressure of 1–4 kPa. The as‐deposited diamond films are characterized by field emission scanning electron microscope (FESEM), atomic force microscopy (AFM), X‐ray diffraction (XRD) spectroscopy and Raman spectroscopy. The results reveal that the surface morphology, growth rate, structure and quality of the diamond films vary with the pressure and the type of the impurity addition. The diamond grains tend to develop into the nanometer scale with the decrease of the pressure. However, adding of boron or nitrogen impurities in the gas mixture will weaken the nanocrystallization effect by reducing the carbon supersaturation. Density functional theory (DFT) calculations indicate that co‐adsorption of B and N containing radicals can favor the adsorption of CH3 on diamond (100) surface. Thus, at low pressure of 1 kPa, large grained cubic (100) facet diamond rather than typical nanometer diamond is produced for B–N co‐addition gas mixture. The present results appear to be useful to efficiently synthesize high quality doped diamonds with desirable properties for mechanical application. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

6.
Graphite paste electrode modified with nitrogen doped porous carbon (NDPC) is used for the detections of paracetamol (PCM), ascorbic acid (AA) and p-aminophenol (PAP) at relatively low concentration. NDPC is synthesized by direct carbonization of Zn(OAc)2 incorporated melamine-formaldehyde resin microsphere. The NDPC shows small pore diameters centered at 3.14 nm and 8.12 nm and has a pseudo graphitic structure with reasonable porous matrix. The lower limit of detections (S/N = 3) for PCM, AA, and PAP are found to be 30 nM, 720 nM and 10 nM respectively. Under optimized experimental condition, the linear ranges of determination for PCM and AA are 1–400 μM, 10–2700 μM respectively in mixture. Similarly for PCM and PAP mixture, the linear ranges of determination are found to be 1–90 μM. It is also used for the analysis of urine and pharmaceutical products with better sensitivity.  相似文献   

7.
We present here the application of the energy-filtered transmission electron microscopy (EFTEM) in the tomographic mode to determine the precise 3D distribution of nitrogen within nitrogen-doped carbon nanotubes (N-CNTs). Several tilt series of energy-filtered images were acquired on the K ionization edges of carbon and nitrogen on a multiwalled N-CNT containing a high amount of nitrogen. Two tilt series of carbon and nitrogen 2D maps were then calculated from the corresponding energy-filtered images by using a proper extraction procedure of the chemical signals. Applying iterative reconstruction algorithms provided two spatially correlated C and N elemental-selective volumes, which were then simultaneously analyzed with the shape-sensitive reconstruction deduced from Zero-Loss recordings. With respect to the previous findings, crucial information obtained by analyzing the 3D chemical maps was that, among the two different kind of arches formed in these nanotubes (transversal or rounded ones depending on their morphology), the transversal arches contain more nitrogen than do the round ones. In addition, a detailed analysis of the shape-sensitive volume allowed the observation of an unexpected change in morphology along the tube axis: close to the round arches (with less N), the tube is roughly cylindrical, whereas near the transversal ones (with more N), its shape changes to a prism. This relatively new technique is very powerful in the material science because it combines the ability of the classical electron tomography to solve 3D structures and the chemical selectivity of the EFTEM imaging.  相似文献   

8.
Ru and Pd (2 wt%) loaded on pure and on Ndoped carbon nanotubes (NCNTs) were prepared and tested using the isopropyl alcohol decomposition reaction as probe reaction. The presence of nitrogen functionalities (pyridinic, pyrrolic, and quaternary nitrogen) on the nitrogen doped support induced a higher metal dispersion: Pd/NCNT (1.8 nm) Pd/CNT (4.9 nm), and Ru/NCNT (2.4 nm) Ru/CNT (3.0 nm). The catalytic activity of the supports was determined first. Isopropyl alcohol conversion produces acetone on CNTs while on NCNTs it led to both dehydration and dehydrogenation products. At 210 °C and in the presence of air, the isopropyl alcohol conversion was higher on the NCNTs (25%) than on the CNTs (11%). The Pd loaded catalysts were more active and more selective than the Ru ones. At 115 °C, the Pd catalysts were 100% selective towards acetone for a conversion of 100%, whereas the Ru catalysts led to dehydration and dehydrogenation products. The nitrogen doping induced the appearance of redox properties when oxygen is present in the reaction mixture.  相似文献   

9.
The hydrogen adsorption energies for nitrogen-containing carbon nanotubes (N-CNTs) and for bare carbon nanotubes were calculated using the density functional theory methods at the B3LYP/6–31-G(d) level, including dispersion force corrections. The N-CNTs were finite saturated and non-saturated single-walled carbon nanotubes that contained one or more pyrimidine units, the relative positions of which defined the different configurations of the nanotube. The chemisorption of atomic hydrogen to a full exocyclic monolayer of zigzag, armchair, and chiral N-CNTs was studied as a function of the structural parameters. Zigzag N-CNTs of any configuration, with a larger number of nitrogen atoms, a small diameter and a small length, are more reactive compared to chiral and armchair N-CNTs. The presence of nitrogen in the carbon nanotubes enhances their reactivity to chemisorb atomic hydrogen, showing exothermic energy values. In contrast, the physisorption of molecular hydrogen was endothermic for most of the studied saturated N-CNTs, even when including corrections for van der Waals interactions. The endothermicity was greatest for zigzag nanotubes, then decreased for chiral nanotubes and decreased again for armchair nanotubes. In general, the endothermicity decreased for longer nanotubes, which have larger diameters, and a small number of nitrogen atoms. The results of this study suggest that, with saturated bare carbon nanotubes, saturated, and unsaturated N-CNTs could potentially have a higher capacity as hydrogen-storage media than the corresponding unsaturated carbon nanotubes.  相似文献   

10.

In this research, it is aimed to enhance the heat transfer properties of the carbon nanotubes through nitrogen doping. To this end, nitrogen-doped multiwall carbon nanotubes (N-CNTs) were synthesized via chemical vapor deposition method. For supplying carbon and nitrogen during the synthesis of N-CNTs, camphor and urea were used, respectively, at 1000 °C over Co–Mo/MgO nanocatalyst in a hydrogen atmosphere. N-CNTs with three different nitrogen loadings of 0.56, 0.98, and 1.38 mass% were synthesized, after which, water/N-CNT nanofluids of these three samples with concentrations of 0.1, 0.2, and 0.5 mass% were prepared. To obtain a stable nanofluid, N-CNTs were functionalized by nitric acid followed by stabilizing in water by employing the ultrasonic bath. Investigation on the stability of the samples showed a high stability level for the prepared water/N-CNT nanofluids in which the zeta potential of ??43.5 mV was obtained for the best sample. Also for studying the heat transfer properties, the thermal conductivity in the range of 0.1–0.5 mass% and convection heat transfer coefficients of nanofluids in the range of 0.1–0.5 mass%, and Reynolds number in the range of 4000–9000 were evaluated. The results showed 32.7% enhancement of the convection heat transfer coefficients at Reynolds number of 8676 and 27% increase in the thermal conductivity at 0.5 mass% and 30 °C.

  相似文献   

11.
《先进技术聚合物》2018,29(1):319-328
The equilibrium adsorption isotherms of carbon dioxide and nitrogen on the nitrogen doped activated carbon (NAC) prepared by the chemical activation of a pine cone‐based char/polyaniline composite were measured using a volumetric technique. CO2 and N2 adsorption experiments were done at three different temperatures (298, 308, and 318 K) and pressures up to 16 bar, and correlated with the Langmuir, Freundlich, and Sips models. The Sips isotherm model presented the best fit to the experimental data. The N‐doped adsorbent showed CO2 and N2 adsorption capacity of 3.96 mmol·g−1 and 0.86 mmol·g−1, respectively, at 298 K and 1 bar. The selectivity predicted by ideal adsorbed solution theory (IAST) model was achieved 47.17 for NAC at 1 bar and yN2 = 0.85 which is a composition similar to flue gas. The results showed that NAC adsorbent has a high CO2‐over‐N2 selectivity in a binary mixture. The relatively fast sorption rate of CO2 on NAC compared to N2 indicates the stronger affinity between CO2 and amine groups. The isosteric heat of adsorption of CO2 by the NAC demonstrated the physico‐chemical adsorption of CO2 on the adsorbent surface. These data showed that prepared NAC could be successfully applied in separation of CO2 from N2.  相似文献   

12.
Nitrogen doped TiO2 (N-TiO2) nanoparticles with about 30 nm in size were produced by a sol–gel method and characterized respectively by UV–vis, X-ray diffraction (XRD), Transmission electron microscopy, X-ray photoelectron spectroscopy (XPS). Their photocatalytic antibacterial properties were evaluated by the antibacterial ratio against Escherichia coli in dark and under simulated sunlight respectively. The XRD pattern showed that the doped nano-TiO2 was mainly composed of anatase phase. The XPS spectra of the N-TiO2 sample indicated that TiO2 was doped by nitrogen atom. The nitrogen doping created a new N 2p state slightly above the valence band top consists of O 2p state, and this pushes up the valence band top and decreased the band gap. Which leaded to the absorption edge was red-shifted to the visible light region of UV–vis spectra of nitrogen doped nano-TiO2 comparing with pure nano-TiO2. The antibacterial percentage of N-TiO2 against E. coli reached to 90 % under simulated sunlight for 2 h, which was much better than that in dark, also than that of pure nano-TiO2. The photo-catalytic antibacterial activity was activated under visible light. The structure and integrity of cell wall and cell membrane were destructed, and even caused the bacteria death.  相似文献   

13.
A calorimetric technique is described for measuring the enthalpy of dissociation liberated from solid hydrates. In this study, the enthalpies of dissociation were determined at T =  273.65 K andp =  0.1 MPa for simple and mixed hydrates of carbon dioxide, nitrogen, (carbon dioxide  +  nitrogen), and (carbon dioxide  +  nitrogen  +  tetrahydrofuran) using an isothermal microcalorimeter. The addition of tetrahydrofuran (THF) promoted hydrate stability and increased the number of guest molecules encaged in the small and large cavities of the hydrate lattice, resulting in lower enthalpy of dissociation, compared with structure II hydrate. The composition ratio of guest molecules did not affect the enthalpy of dissociation, which was found to be nearly constant for the same mixture.  相似文献   

14.
Carbocatalysts doped with heteroatoms such as nitrogen or sulphur have been reported to be useful in persulfate-based advanced oxidation processes for organic pollutant removal. However, there is limited research on the effect of doping with phosphorus atoms on degradation performance. In this work, a new nitrogen and phosphorus-doped carbocatalyst (N, P-HC) was designed using hydrothermal carbonization followed by pyrolysis at 700 °C, with olive pomace as a carbon source, to degrade organic pollutants in the presence of peroxydisulfate (PDS). Experimental results showed that N, P-HC, with its large specific surface area (871.73 m2.g−1), high content of N-pyridinic and N-pyrrolic groups, and the presence of P-O-C and O-P-C bonds, exhibited high degradation performance (98% degradation of Rhodamine B (RhB) in 40 min, with an apparent rate constant (kapp) of 0.055 min−1 and an excellent turnover frequency (TOF) of 0.275 min−1). Quenching study and EPR analysis revealed that singlet oxygen generation (1O2) and direct electron transfer were the main reaction pathways for the non-radical pathway in the degradation of RhB. The improved catalytic efficiency in the N, P-HC/PDS/RhB system can be attributed to the synergistic effect between N and P atoms in the graphitic structure of the carbocatalyst, its high surface area, and the presence of oxygenated functional groups on the surface of the N, P-HC. The used N, P-HC carbocatalyst can also be efficiently recovered by heat treatment at 500 °C. Overall, this study presents a simple and environmentally friendly method for synthesizing a high-performance N, P co-doped olive pomace-based carbocatalyst for water decontamination through PS-AOPs processes.  相似文献   

15.
《Arabian Journal of Chemistry》2020,13(11):7809-7819
Nitrogen doped carbon nanodots (NDCNDs) and nanosized cobalt tetra aminophenoxy phthalocyanines (CoTAPhPcNPs) modified glassy carbon electrodes have been successfully used in the simultaneous detection of aspirin (ASA), ibuprofen (IBU) and indomethacin (INDO). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–Vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to probe the nature of the synthesized nanomaterials. Sequential deposition of the nanomaterials on the glassy carbon electrode yielded CoTAPhPcNPs-NDCNDs-GCE with remarkable electrocatalytic performance. Electro-oxidation of the drugs at the electrode surface was first order. This work demonstrates the synergic effect of the two nanomaterials towards simultaneous electrocatalytic detection of the drugs. Superior detection limits of ASA, IBU and INDO being 9.66 × 10−9 M, 4.19 × 10−9 M and 7.2 × 10−9 M, respectively, were obtained using differential pulse voltammetry. The developed sensor could detect two of the three (ibuprofen and indomethacin) simultaneously at significantly different potentials and exhibited remarkable reproducibility after a regeneration step.  相似文献   

16.
《化学:亚洲杂志》2017,12(14):1816-1823
Heteroatom‐doped carbon materials have been considered as potential substitutes for Pt‐based electrocatalysts for the oxygen reduction reaction (ORR) in alkaline fuel cells. Here we report the synthesis of oxygen‐containing nitrogen‐doped carbon (ONC) nanosheets through the carbonization of a mixture that contained glucose and dicyandiamide (DCDA). In situ formed graphitic carbon nitride (g‐C3N4) derived from DCDA provided a nitrogen‐rich template, thereby facilitating the formation of ONC nanosheets. The resultant ONC materials with high nitrogen content, high specific surface areas, and highly mesoporous total volume displayed excellent electrochemical performance, including a similar ORR onset potential, half‐potential, a higher diffusion‐limited current, and excellent tolerance to methanol than that of the commercial Pt/C catalyst, respectively. Moreover, the ONC‐850 nanosheet displayed high long‐term durability even after 1000 cycles as well as a high electron transfer number of 3.92 (4.0 for Pt/C). Additionally, this work provides deeper insight into these materials and a versatile strategy for the synthesis of cost‐effective 2D N‐doped carbon electrocatalysts.  相似文献   

17.
Single-layer (SL) carbon tubes were produced by arc evaporation of graphite rods containing iron-group metals (Fe, Co, Ni, Fe/Co, Co/Ni, Fe/Ni) under He and Ar gas. Transmission electron microscopy (TEM) revealed that these elemental and binary metals, excluding Fe which need a special atmosphere (a mixture of Ar and CH4), showed catalytic activity producing SL tubes under pure inactive gases. Fe/Ni alloy was the most effectual catalysts for producing SL tubes. The highest abundance of SL tubes in raw soot was estimated to be ~ 10% from TEM observation. Smoke particles directly caught on TEM grids near an evaporation source during arcburning were also investigated, and it was suggested that small metal particles were first formed in the gas phase and then SL tubes grew from them.  相似文献   

18.
The bamboo‐shaped nitrogen‐doped carbon nanotubes (CNx) with different nitrogen content were synthesized using Fe‐containing SBA‐15 molecular sieve as catalyst with thermal decomposition. The CNx nanotubes prepared were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X‐ray diffraction (XRD) and Raman spectroscopy. The results suggest that there are a larger amount of defective sites on CNx nanotubes surfaces due to the nitrogen doping and CNx nanotube with higher nitrogen content possesses lower graphitic ordering in the framework. Furthermore the effects of nitrogen content on the electrochemistry of CNx modified electrodes were investigated by cyclic voltammetry (CV). CNx modified electrodes exhibit better electrocatalytic activities to the oxidation of hydroquinone. Moreover CNx with lower nitrogen content is in favor of the electron transfer between dihydroxybenzene and electrode surface, while CNx with higher nitrogen content possesses high surface adsorptive ability. CNx modified electrodes can be applied to determine dihydroxybenzene isomers directly and simultaneously by linear sweep voltammetry technique without previous separation.  相似文献   

19.
SrTaO2N heated in a helium atmosphere began to release nitrogen of approximately 30 at% at 950 °C while maintaining the perovskite structure and its color changed from orange to dark green. Then it decomposed above 1200 °C to a black mixture of Sr1.4Ta0.6O2.73, Ta2N, and Sr5Ta4O15. The second decomposition was not clearly observed when SrTaO2N was heated in a nitrogen atmosphere below 1550 °C. After heating at 1500 °C for 3 h under a 0.2 MPa nitrogen atmosphere, the perovskite product became dark green and conductive. Structure refinement results suggested that the product was a mixture of tetragonal and cubic perovskites with a decreased ordering of N3−/O2−. The sintered body was changed to an n-type semiconductor after a partial loss of nitrogen to be reduced from the originally insulating SrTaO2N perovskite lattice. LaTiO2N was confirmed to have a similar cis-configuration of the TiO4N2 octahedron as that of TaO4N2 in SrTaO2N. It also released some of its nitrogen at 800 °C changing its color from brown to black and then decomposed to a mixture of LaTiO3, La2O3, and TiN at 1100 °C. These temperatures are lower than those in SrTaO2N.  相似文献   

20.
FeMoO4 nanorods and their rare earth (Eu3+ and Tb3+) doped composites with nitrogen doped graphene (NG) were synthesized by facile hydrothermal method in aqueous medium. X-ray diffraction (XRD) analysis of the as-synthesized samples was done to study the phase purity and crystalline nature. FTIR and Raman Spectroscopy have been studied for investigating the bonding in nanostructures. The surface morphology of the samples was investigated with field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The photolumniscent nature of the samples was investigated by the using the fluorescence spectrophotometer. The photocatalytic degradation efficiency of the prepared pure FeMoO4 and its rare earth doped composites with nitrogen doped graphene was evaluated as function of visible light irradiation versus concentration of methylene blue (MB dye). The prepared nanocomposites show enhanced photocatalytic efficiency as compared to the bare FeMoO4 nanorods.  相似文献   

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