Onion-like carbon-encapsulated Co,Ni, and Fe magnetic nanoparticles with low cytotoxicity synthesized by a pulsed plasma in a liquid

We synthesized onion-like carbon-encapsulated Co, Ni, and Fe (Co–C, Ni–C, and Fe–C) magnetic nanoparticles with low cytotoxicity using pulsed plasma in a liquid. The pulsed plasma is induced by a low-voltage spark discharge submerged in a dielectric liquid. The face-centered cubic Co and Ni, and body-centered cubic Fe core nanoparticles showed good crystalline structures with an average size between 20 and 30 nm were encapsulated in onion-like carbon coatings with a thickness of 2–10 nm. Vibrating-sample magnetometer measurements revealed the ferromagnetic properties of as-synthesized samples at room temperature (Co–C = 360 Oe, Fe–C = 380 Oe, and Ni–C = 211 Oe). Raman-spectroscopy analysis found onion-like carbon shells composed of well-organized graphitic structures. Thermal gravimetric analysis showed a high stability of the as-synthesized samples under thermal treatment and oxidation. Cytotoxicity measurements showed higher cancer cell viability than samples synthesized by different methods.     

Properties and rapid consolidation of nanostructured TiC-based hard materials with various binders by a high-frequency induction heated sintering

The densification of hard TiC–10 vol.% binder (Co, Ni, Fe) materials was accomplished within 2 min using a high-frequency induction heated sintering (HFIHS) method. The advantage of this process is not only rapid densification to almost the theoretical density but also the prevention of grain growth of the nano-structured materials. Highly dense TiC–binder (Co, Ni, Fe) composites with a relative density of up to 99.9% were obtained within 2 min by HFIHS under 80 MPa. The average grain size of TiC in the TiC–10 vol.% Ni composite was approximately 44 nm. The hardness and fracture toughness of the dense TiC–10 vol.% binder (Co, Ni, Fe) composite produced by HFIHS were also investigated.     

The effect of a tin oxide buffer layer for the high yield synthesis of carbon nanocoils

In this paper, we show that the efficiency in the growth of carbon nanocoils is significantly improved by introducing a SnO₂ buffer layer. Carbon nanocoils were synthesized by chemical vapor deposition using an Fe–Mg–Co or Fe–Mg–Co–Sn catalyst supported on an Al₂O₃ substrate coated with a 30 nm SnO₂ buffer layer. The carbon nanocoil growth rate improved by more than 200% compared with the non-coated substrate when using Fe–Mg–Co–Sn or Fe–Mg–Co catalyst layers 600 or 300 nm thick, respectively. The byproduct layer was also reduced significantly, which results in more than 50% gain in the consumption of carbon source gas during the synthetic process. The role for an external Sn supply from the buffer layer is discussed based on the experimental results.     

High coercivity magnetic multi-wall carbon nanotubes for low-dimensional high-density magnetic recording media

Fe-embedded multi-wall carbon nanotubes (MWCNTs) were fabricated using Fe-catalyst by the chemical deposition method. Microscopic characterizations showed that the well-aligned MWCNTs were ～ 80 mm in length, with outer diameter of 20–50 nm and inner diameter of 10–20 nm. Magnetic properties were characterized in temperatures of 5 K and 305 K, which revealed that the MWCNTs exhibited high coercivity of 2600 Oe at 5 K and 732 Oe at 305 K. These values are much higher than that of bulk iron (～ 0.9 Oe) and Fe/Co/Ni nanoparticles or nano-wire arrays (～ 200–500 Oe) at the room temperature. This high coercivity and the structure of single-domain Fe nanoparticles isolated by anti-ferromagnetic MWCNTs make it a promising candidate for low-dimensional high-density magnetic recording media.     

Fabrication of porous carbon monoliths with a graphitic framework

Macro/mesoporous carbon monoliths with a graphitic framework were synthesized by carbonizing polymeric monoliths of poly(benzoxazine-co-resol). The overall synthesis process consists of the following steps: (a) the preparation of polymeric monoliths by co-polymerization of resorcinol and formaldehyde with a polyamine (tetraethylenepentamine), (b) doping the polymer with a metallic salt of Fe, Ni or Co, (c) carbonization and (d) the removal of inorganic nanoparticles. The metal nanoparticles (Fe, Ni or Co) formed during the carbonization step catalyse the conversion of a fraction of amorphous carbon into graphitic domains. The resulting carbon monoliths contain >50 wt.% of graphitic carbon, which considerably improves their electrical conductivity. The use of tetraethylenepentamine in the synthesis results in a nitrogen-containing framework. Textural characterization of these materials shows that they have a dual porosity made up of macropores and mesopores (∼2–10 nm), with a BET surface area in the 280–400 m² g⁻¹ range. We tested these materials as electrodes in organic electrolyte supercapacitors and found that no conductive additive is needed due to their high electrical conductivity. In addition, they show a specific capacitance of up to 35 F g⁻¹, excellent rate and cycling performance, delivering up to 10 kW kg⁻¹ at high current densities.     

Novel method for synthesis of Fe core and C shell magnetic nanoparticles

Using a newly developed method, carbon-encapsulated iron (Fe) nanoparticles were synthesized by plasma due to ultrasonication in toluene. Fe core with carbon shell nanoparticles were characterized using Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM). Fe nanoparticles of diameter 7–115 nm are encapsulated by 7–8 nm thick carbon layers. There was no iron carbide formation observed between the Fe core and the carbon shell. The Fe nanoparticles have body centered cubic (bcc) crystal structure. Synthesized nanoparticles showed a saturation magnetization of 9 A m²/kg at room temperature. After thermal treatment crystalline order of the nanoparticles improved and saturation magnetization increased to 24 A m²/kg. We foresee that the carbon-encapsulated Fe nanoparticles are biologically friendly and could have potential applications in Magnetic Resonance Imaging (MRI) and photothermal cancer therapy.     

Oxidative desulfurization of dibenzothiophene over Fe promoted Co–Mo/Al_2O_3 and Ni–Mo/Al_2O_3 catalysts using hydrogen peroxide and formic acid as oxidants

This work reports the enhancing effect of a highly cost effective and efficient metal, Fe, incorporation to Co or Ni based Mo/Al_2O_3 catalysts in the oxidative desulfurization(ODS) of dibenzothiophene(DBT) using H_2O_2 and formic acid as oxidants. The influence of operating parameters i.e. reaction time, catalyst dose, reaction temperature and oxidant amount on oxidation process was investigated. Results revealed that 99% DBT conversion was achieved at 60 °C and 150 min reaction time over Fe–Ni–Mo/Al_2O_3. Fe tremendously enhanced the ODS activity of Co or Ni based Mo/Al_2O_3 catalysts following the activity order: Fe–Ni–Mo/Al_2O_3 NFe–Co–Mo/Al_2O_3 NNi–Mo/Al_2O_3 NCo–Mo/Al_2O_3, while H_2O_2 exhibited higher oxidation activity than formic acid over all catalyst systems. Insight about the surface morphology and textural properties of fresh and spent catalysts were achieved using scanning electron microscopy(SEM), X-ray diffraction(XRD), energy dispersive X-ray(EDX)analysis, Atomic Absorption Spectroscopy(AAS) and BET surface area analysis, which helped in the interpretation of experimental data. The present study can be deemed as an effective approach on industrial level for ODS of fuel oils crediting to its high efficiency, low process/catalyst cost, safety and mild operating condition.     

NO SCR with propane and propene on Co-based alumina catalysts prepared by co-precipitation

Homogeneous dispersions and small size of deposited high-content cobalt on alumina were achieved by the co-precipitation method and were well maintained on the cobalt-based binary alumina catalysts with Zn, Ag, Fe, Cu or Ni as modifiers. The component and concentration of deposited cobalt species were characterized by UV–vis, EDX and XPS spectra and found to be greatly related to the Co loading, calcination temperatures and the type of additive metals. The optimal Co loading of 8 wt% and calcination temperatures of 800 °C were demonstrated. With respect to the single cobalt-based alumina catalyst, the surface concentration of Co²⁺ on the binary catalysts with addition of Fe, Cu, Ag or Ni was all reduced and accompanying with part conversion of Co²⁺ to Co₃O₄ on the Fe and Ni-modified catalysts. A slight enhanced surface Co²⁺ concentration was only achieved on the Zn-promoted catalyst. It was also demonstrated that for the case of Cu and Fe the additive metals themselves participated in the activation of propene. The octahedral and tetrahedral Co²⁺ ions were suggested as the common active sites. A maximum deNOx activity of 96% was observed on the 8Co4ZnA800 catalyst at the reaction temperatures of 450 °C, and the catalytic performance on the cobalt-based binary alumina catalysts can be described as fellows: CoZn > CoAg, CoNi > Co Cu > CoFe. Based on the in situ DRIFT spectra, different reaction intermediates R–ONO and –NCO besides –NO₂ were formed on the 8Co4ZnA800 and 8Co4FeA800 samples, respectively, demonstrating their dissimilar reaction mechanisms.     

Comparison of Co/MgO and Ni/MgO catalysts for the steam reforming of naphthalene as a model compound of tar derived from biomass gasification

The catalytic performances of 12 wt.% Co/MgO catalyst pre-calcined at 873 K and of Ni catalysts for the steam reforming of naphthalene were investigated. The results of characterizations (TPR, XRD, and CO adsorption) for Ni catalysts showed that Ni metal particles were formed over the catalysts pre-calcined at 873 K with high Ni loading via reduction of NiO–MgO phases. A few Ni metal particles were obtained over the catalysts pre-calcined at 1173 K with all Ni loading values.The catalytic performance data showed that Co/MgO catalyst had higher activity (conv., 23%, 3 h) than any kinds of Ni/MgO catalysts tested in this study, under lower steam/carbon mole ratio (0.6) and higher concentration of fed naphthalene (3.5 mol%) than those used in the other works. The steam reforming of naphthalene proceeded when there was a stoichiometric ratio between the carbon atoms of naphthalene and H₂O over Co catalyst; however, the activation of excess H₂O happened over the Ni catalyst and this phenomenon can lead to having lower activity than Co catalyst. We concluded that these observations should be attributed to different catalytic performances between Co/MgO and Ni/MgO catalysts.     

Modulating the electronic properties of graphdiyne nanoribbons

By ab initio calculation, Au, Cu, Fe, Ni, and Pt adatoms were proposed for modulating the electronic property of graphdiyne naoribbons (GDNRs). GDNRs of 1–4 nm in width were found to be stable at room temperature, and the thermal rates of Au, Cu, Fe, Ni, and Pt adatoms escaping from GDNR are slower than 0.003 atoms per hour even at 900 K. According to the calculation, Au and Cu-decorated GDNRs are metallic with carrier concentrations close to that of graphene at room temperature, while Fe, Ni, and Pt-decorated GDNRs are n-type semiconductors with impurity states below Fermi energy. Heterojunction composed by doping Au, Cu, or Fe atom on one side of GDNR was proposed as metal–semiconductor rectifier with rectification ratio of 2.8, 1.5, or 2.5 at 1.0 V, respectively.     

Platinum–tin bimetallic nanoparticles for methanol tolerant oxygen-reduction activity

Carbon-supported Pt–Sn/C bimetallic nanoparticle electrocatalysts were prepared by the simple reduction of the metal precursors using ethylene glycol. The catalysts heat-treated under argon atmosphere to improve alloying of platinum with tin. As-prepared Pt–Sn bimetallic nanoparticles exhibit a single-phase fcc structure of Pt and heat-treatment leading to fcc Pt₇₅Sn₂₅ phase and hexagonal alloy structure of the Pt₅₀Sn₅₀ phase. Transmission electron microscopy image of the as-prepared Pt–Sn/C catalyst reveals a mean particle diameter of ca. 5.8 nm with a relatively narrow size distribution and the particle size increased to ca. 20 nm when heat-treated at 500 °C due to agglomeration. The electrocatalytic activity of oxygen reduction assessed using rotating ring disk electrode technique (hydrodynamic voltammetry) indicated the order of electrocatalytic activity to be: Pt–Sn/C (as-prepared) > Pt–Sn/C (250 °C) > Pt–Sn/C (500 °C) > Pt–Sn/C (600 °C) > Pt–Sn/C (800 °C). Kinetic analysis reveals that the oxygen reduction reaction on Pt–Sn/C catalysts follows a four-electron process leading to water. Moreover, the Pt–Sn/C catalyst exhibited much higher methanol tolerance during the oxygen reduction reaction than the Pt/C catalyst, assessing that the present Pt–Sn/C bimetallic catalyst may function as a methanol-tolerant cathode catalyst in a direct methanol fuel cell.     

Photoluminescent carbon nanoparticles produced by confined combustion of aromatic compounds

We report new photoluminescent carbon nanoparticles having an average particle size of 50 nm. When dispersed in chloroform and excited with 325 nm wavelength, the solution showed strong photoluminescence at 475 nm with 12–13% quantum yield. A well dispersed photoluminescent solution can also be prepared with ethanol, xylene or hexane using the nanoparticles. The nanoparticles were prepared by a simple confined combustion of an aromatic compound such as benzene, toluene, xylene or a mixture thereof in air.     

Microstructure and corrosion properties of Ni-TiN nanocoatings prepared by jet pulse electrodeposition

Ni–TiN nanocoatings were successfully prefabricated by jet pulse electrodeposition. The effect of jet rate on cross-sectional composition, microstructure, microhardness, and corrosion properties of nanocoatings was examined by X-ray photoelectron spectroscopy, high-resolution transmission electron microscope, atomic force microscopy, microhardness tester and electrochemical workstation. Results illustrated that Ni–TiN nanocoatings deposited at jet rate of 3 m/s exhibited high concentration of Ni and Ti with average concentrations of Ni and Ti of 54.5 at% and 19.8 at%, respectively. Average diameters of Ni grains and TiN nanoparticles in Ni–TiN nanocoatings prepared at 3 m/s were 47.8 nm and 30.5 nm, respectively. Nanocoatings deposited at 1 m/s, 3 m/s and 5 m/s showed surface root-mean-square roughness value of 95.431, 30.091 and 58.454 nm, respectively, and presented maximum microhardness of 789.5, 876.2, and 849.9 HV, respectively. Ni–TiN nanocoating obtained at 3 m/s demonstrated minimum I_corr and E_corr values of 1.02 × 10⁻³ mA/cm² and − 0.551 V, respectively, signifying to offer the best corrosion resistance.     

Catalytic conversion of CO,NO and SO2 on the supported sulfide catalyst: I. Catalytic reduction of SO2 by CO

Catalytic reduction of SO₂ to elemental sulfur by CO has been systematically investigated over γ-Al₂O₃-supported sulfide catalysts of transition metals including Co, Mo, Fe, CoMo and FeMo with different loadings of the metals. The sulfided CoMo/Al₂O₃ exhibited outstanding activity: a complete conversion of SO₂ was achieved at a temperature of 300°C. The reaction proceeds catalytically and consistently over time and most efficiently at a molar feed ratio CO/SO₂ = 2. A precursor CoMo/Al₂O₃ oxide which experienced sulfurization through the CO–SO₂ reaction yielded a working sulfide catalyst having a yet lower activity than the CoMo catalyst sulfided before reaction (pre-sulfiding). The catalytic activity of various metal sulfides decreased in order of 4% Co 16% Mo > 4% Fe15% Mo > 16% Mo ≥ 25% Mo > 14% Co ≥ 4% Co > 4% Fe. A DRIFT study showed that CO adsorbs exclusively on CoMo phase and that SO₂ predominantly on γ-Al₂O₃. It is suggested that the Co–Mo–S structure is more adequate than the other metal-sulfur structures for the formation of a carbonyl sulfide (COS) intermediate because of the proper strength of metal–sulfur bond, and catalytically works with γ-Al₂O₃ for the COS–SO₂ reaction.     

Increased CNT growth density with an additional thin Ni layer on the Fe/Al catalyst film

Density of 3 × 10¹¹/cm² and diameter of CNTs of 9–12 nm were successfully controlled by using the multi-layered catalyst film consisting of an additional Ni layer on Fe/Al catalyst film. EDS analysis for the annealed catalyst films revealed that the increase of the density of Fe catalyst particles corresponded with the decrease of Ni in the films, which strongly suggested that the additional thin Ni layer on the Fe/Al multi-layered catalyst films prevented the fine Fe catalyst particles from agglomeration, resulting in the growth of high-density, and uniform diameter of CNTs.     

Reactive spark plasma sintering of Ti3SnC2, Zr3SnC2 and Hf3SnC2 using Fe,Co or Ni additives

This work studied the effect of adding 10 at% Fe, Co or Ni to M-Sn-C mixtures with M = Ti, Zr or Hf on MAX phases synthesis by reactive spark plasma sintering. Adding Fe, Co or Ni assisted the formation of 312 MAX phases, i.e., Ti₃SnC₂, Zr₃SnC₂ and Hf₃SnC₂, while their 211 counterparts Ti₂SnC, Zr₂SnC and Hf₂SnC formed in the undoped M-Sn-C mixtures. The lattice parameters of the newly synthesized Zr₃SnC₂ and Hf₃SnC₂ MAX phases were determined by X-ray diffraction. Binary MC carbides were present in all ceramics, whereas the formation of intermetallics was largely determined by the selected additive. The effect of adding Fe, Co or Ni on the MAX phase crystal structure and the microstructure of the produced ceramics was investigated in greater detail for the case of M = Zr. A mechanism is herein proposed for the formation of M₃SnC₂ MAX phases.     

Extraction of cadmium from solutions containing various heavy metal ions by Amberlite LA-2

In present study, selective extraction of cadmium from acidic leach solutions, containing various heavy metal ions, by emulsion liquid membrane (ELM) is studied. For this reason, the zinc plant copper cake was leached with sulfuric acid and main acidic leach solution containing Zn(II), Cu(II), Fe(II), Cd(II), Co(II) and Ni(II) ions was obtained. After Zn(II), Cu(II), Fe(II) and Cd(II) ions in the acidic leach solution were separated, the important parameters influencing the extent of cadmium extraction were investigated and optimum conditions were determined. Cadmium extraction was influenced by number of parameters like initial metal ion concentration, mixing speed, phase ratio, extractant concentration, surfactant concentration, the stripping solution type and concentration, and the feed solution acid concentration. The optimum values of parameter above mentioned were used and cadmium in the acidic leach solution containing 650 mg Cd/L, 365 mg Co/L, 535 mg Ni/L, and 1260 mg Zn/L was almost completely extracted within 10 min. The results showed that it is possible to extract 99% of cadmium after 10 min contact time by using ELM from aqueous solutions, containing Fe(II), Al(III), Cu(II), Zn(II), Pb(II), Co(II) and Ni(II) ions, at the optimum operating conditions.     

Synthesis of hollow carbon nano-onions and their use for electrochemical hydrogen storage

In this study, we report an efficient method for synthesis of well-graphitized hollow carbon nano-onions (CNOs). CNOs were firstly fabricated by chemical vapor deposition (CVD) method at 850 °C using an Fe–Ni alloy catalyst with diameters of 10–15 nm. Then hollow CNOs were obtained by annealing as-prepared CNOs at 1100 °C for 3 h. It is found that during the CVD growth, the presence of nickel retards the deactivation of Fe–Ni–C austenite, providing the possibility for the growth of up to two hollow CNOs from each alloy particle. The subsequent high-temperature annealing led to the escaping of the Fe–Ni alloy from the graphitic layers, and the re-catalysis of precipitation and graphitization of the carbon atoms previously dissolved in the alloy particle (Fe_0.64Ni_0.36) to form hollow CNOs. The hollow CNOs exhibit good performance as materials for electrochemical hydrogen storage, with a discharge capacity of 481.6 mAh/g under a current density of 500 mA/g, corresponding to a hydrogen storage capacity of 1.76 wt.%. Our results demonstrate that the hollow CNOs are promising materials as a storage medium for hydrogen as a fuel source.     

Catalytic hydrogen production from 2-propanol in supercritical water: Comparison of some metal catalysts

The gasification of organics in supercritical water is a promising method for the direct production of hydrogen at high pressures, and in order to improve the hydrogen yield or selectivity, activities of various catalysts are evaluated. In this study, hydrogen production from 2-propanol over Ni/Al₂O₃ and Fe–Cr catalysts was investigated in supercritical water. The experiments were carried out in the temperature range of 400–600 °C and in the reaction time range of 10–30 s, under a pressure of 25 MPa. The hydrogen yields and selectivities of Ni/Al₂O₃ and Fe–Cr used in this study, and those of Pt/Al₂O₃ and Ru/Al₂O₃ used in our previous work were compared. The hydrogen contents of the gaseous products obtained by using Ni/Al₂O₃ and Fe–Cr were measured as 62 mol% and 70 mol%, respectively, at low temperatures and reaction times. However, the hydrogen yields remained in low levels when compared with that of Pt/Al₂O₃ used in previous study. Pt/Al₂O₃ was established to be the most effective and selective catalyst for hydrogen production. During the catalytic gasification of a 0.5 M solution of 2-propanol, hydrogen content up to 96 mol% and hydrogen yield of 1.05 mol/mol 2-propanol were obtained.     

One-step preparation of amorphous iron nanoparticles by laser ablation

Amorphous Fe nanoparticles are always difficult to prepare by physical gas-phase methods though rapid cooling rates are applied. Here we report a physical preparation of pure amorphous Fe nanoparticles by laser ablation of a 0.5-mm-diameter Fe wire and the investigation of their formation mechanism. Amorphous Fe nanoparticles with a shell of γ-Fe₂O₃ and the sizes of 1–3 nm are obtained at the laser power densities above the ablation threshold. Finally, the as-prepared nanoparticles are characterized by XRD, TEM, XPS and VSM to discover the structure, morphology, surface composition, crystallization and magnetic property in detail. We find that the holistic explosive evaporation induced by the small-size target not by the processing parameters determines the nature of the amorphous Fe nanoparticles. The as-prepared amorphous Fe nanoparticles are crystallized at 400 °C with an increase of particle size to about 10 nm.