PtRu nanoparticles supported on nitrogen-doped multiwalled carbon nanotubes as catalyst for methanol electrooxidation

Nitrogen-doped carbon nanotubes (N-CNT) obtained by plasma treatment were compared to the conventional acid-treated carbon nanotubes (O-CNT) as catalyst support for platinum-ruthenium (PtRu) nanoparticles in the anodic oxidation of methanol in direct methanol fuel cells. PtRu catalysts were prepared by an impregnation-reduction method from chloride precursors with metal loadings of 20 wt.%, and were characterised by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical methods. Voltammetry and chronoamperometry studies showed that the performance of PtRu/N-CNT was significantly higher compared to PtRu/O-CNT and also to the commercial E-TEK PtRu/C catalyst, indicating that N-CNT are an interesting support material for fuel cell electrocatalyst. Nitrogen plasma treatment produced pyridinic and pyrrollic species on the CNT surface, which acts as the anchoring sites for the deposition of PtRu particles. A mechanism for the deposition of PtRu on N-CNT is tentatively proposed and discussed.     

Preparation and electrochemical performance of polyaniline-based carbon nanotubes as electrode material for supercapacitor

Nitrogen-containing carbon nanotubes (CNTs) with open end and low specific surface area were prepared via the carbonization of polyaniline (PANI) nanotubes synthesized by a rapidly mixed reaction. On the basis of analyzing the morphologies and structures of the original and carbonized PANI nanotubes, the electrochemical properties of PANI-based CNTs obtained at different temperatures as electrode materials for supercapacitors using 30 wt.% aqueous solution of KOH as electrolyte were investigated by galvanostatic charge/discharge and cyclic voltammetry. It was found that the carbonized PANI nanotubes at 700 °C exhibit high specific capacitance of 163 F g⁻¹ at a current density of 0.1 A g⁻¹ and excellent rate capability in KOH solution. Using X-ray photoelectron spectroscopy measurement the nitrogen state and content in PANI-CNTs were analysed, which could play important roles for the enhancement of electrochemical performance. When the appropriate content of nitrogen is present, the presence of pyrrole or pyridone and quaternary nitrogen is beneficial for the improvement of electron mobility and the wettability of electrode.     

Mechanochemically assisted fabrication of ultrafine Pd nanoparticles on natural waste-derived nitrogen-doped porous carbon for the efficient formic acid decomposition

Utilizing natural waste as carbon source to prepare porous carbon with ultrahigh surface area and developing a facile protocol to synthesize supported metal nanoparticles toward an efficient formic acid (FA) decomposition are vital but remains challenging. Here, discarded ginkgo leaves were utilized as carbon source to prepare ginkgo leaf-derived porous carbon (GLPC) with an ultrahigh surface area of 3851 m²/g. Based on the as-prepared nitrogen-doped GLPC (N-GLPC) after “soft” nitriding, a facile solid-state reduction strategy with mortar-pestle grinding and without the use of any organic solvent and stabilizing ligand was developed to synthesize ultrafine and well-distributed Pd nanoparticles (NPs) with a diameter of 2.7 ± 0.7 nm. The “soft” nitriding temperature and addition of base during preparation played vital roles in the activity of the fabricated catalysts. The Pd/N-GLPC-350 exhibited the highest catalytic activity toward decomposing FA, achieving a high turnover frequency of 2952 h^?1 at 333 K. The Pd/N-GLPC-350 was quite stable and could be reused at least five times without evident activity loss. This study provides a facile solid-state reduction protocol with mortar-pestle grinding to synthesize metal NPs by using natural waste-derived porous carbon as support toward efficient FA decomposition.     

Doping of nitrogen into biomass-derived porous carbon with large surface area using N2 non-thermal plasma technique for high-performance supercapacitor

A novel and facile modified method using non-thermal plasma is proposed to insert N active sites into biomass-derived porous carbon as high-performance electrode materials for supercapacitor. Large surface areas up to 3040.3 and 2662.5 m²/g with mesopore-dominant hierarchical porous carbons are produced from biomass of lilac and lotus seedpods via KOH activation, respectively. The lilac and lotus seedpods derived porous carbon electrodes present good specific capacitances of 214.5 and 201.1 F/g, respectively. N₂ non-thermal plasma modification successfully increases N-containing groups on lilac and lotus seedpods derived porous carbons, where the corresponding N atomic contents are increased by 10.2 and 3.6 times, respectively. As supercapacitor electrodes, their specific capacitances are improved greatly after plasma modification and up to 342.5 F/g (increased by 59.7%) and to 332.1 F/g (increased by 65.2%) at 0.5 A/g in 6 M KOH electrolyte with excellent cycling stability of 85.2% and 95.4% at 10 A/g after 5000 cycles, respectively.     

Effective improvement of photocatalytic hydrogen evolution via a facile in-situ solvothermal N-doping strategy in N-TiO2/N-graphene nanocomposite

Nanocomposite NTNG composed of nitrogen-doped titanium dioxide (N-TiO₂) and nitrogen-doped graphene (N-graphene) is synthesized to increase the photocatalytic efficiency for hydrogen production through a convenient in-situ solvothermal nitrogen-doping strategy. TEM and AFM images suggested that NTNG nanosheet consists of approximately 1–5 layers by folding its own sheet and that the wrinkled multilayer textures are stretched to a large extent due to the uniformly anchored N-TiO₂ nanoparticles on N-graphene surface effectively avoiding the aggregation. XPS results indicated that the in-situ solvothermal nitrogen-doping not only allows the nitrogen-doping of TiO₂ but also further changes the nitrogen-doping state of N-graphene including the nitrogen content and the ratio of dopant types. Raman spectroscopy told us that N-graphene in NTNG is more ordered than separate N-graphene due to fewer defects from the improved sp²-hybridized nitrogen. As a result, the photocatalytic efficiency of NTNG under ultraviolet irradiation is improved about 13.1 times compared to commercial P25.     

Construction and preparation of nitrogen-doped porous carbon material based on waste biomass for lithium-ion batteries

Biomass derived carbon materials have been widely studied as electrodes in energy storage devices due to their renewable nature, low-cost and tunable physical/chemical properties. However, the influences of different treatments for biomass derived carbon materials are still lack of in-depth discussion. In this work, we investigate the effects of the treatment for biomass on the structure and composition of the resulted carbon materials. Especially, the optimal N-doped porous carbon (NPCCS), which was fabricated by H₂SO₄-assisted hydrothermal treatment and subsequent pyrolysis process using corn silk as raw material, shows a unique interconnected layered nanostructure with ultra-high nitrogen content (18.79 at%). As a result, the NPCCS electrode displays excellent cycling stability and outstanding rate performance in lithium-ion half-cell test and shows high first reversible specific capacity of 523.6 mAh g^?1 in full-cell test. This work provides some guidance for preparing biomass derived carbon materials with superior electrochemical performance for the applications in advanced energy storage devices.     

Fourier transform infrared spectroscopic study of nitrogen-doped ultrananocrystalline diamond/hydrogenated amorphous carbon composite films prepared by pulsed laser deposition

Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) composite films, which possess n-type conduction with enhanced electrical conductivities, were prepared by pulsed laser deposition and they were structurally studied by Fourier transform infrared (FTIR) spectroscopy. The film with a nitrogen content of 7.9 at.% possessed n-type condition with an electrical conductivity of 18 S/cm at 300 K. The FTIR spectra revealed peaks due to nitrogen impurities, C = N, C-N, and CH_n (n = 1, 2, 3) bands. The sp²-CH_n/(sp²-CH_n + sp³-CH_n), estimated from the area-integration of decomposed peaks, were 24.5 and 19.4% for undoped and 7.9 at.% doped films, respectively. The nitrogen-doping not only form the chemical bonds between carbon and nitrogen atoms such as C = N and C-N bonds but also facilitate the formation of both sp² and sp³ bonds, in particular, the sp³-CH_n bond is preferentially formed. From the analysis of the FTIR spectra, it was found that the hydrogen content in the film is increased with an increase in the nitrogen content. The increased hydrogen content might be owing to the enhanced volume of grain boundaries (GBs) between UNCD grains, and those between UNCD grains and an a-C:H matrix, which is caused by a reduction in the UNCD grain size. The CH_n peaks predominantly come from an a-C:H matrix and GBs. Since the nitrogen-doping for a-C:H has been known to be hardly effective, the n-type conduction with the enhanced electrical conductivities might be attributed to the sp²-CH_n formation at the GBs.     

Nanocomposite of graphene oxide with nitrogen-doped TiO2 exhibiting enhanced photocatalytic efficiency for hydrogen evolution

The application of hydrogen energy potentially addresses energy and environmental problems. In order to improve the photocatalytic efficiency, nanocomposite of N-doped TiO₂ with graphene oxide (NTG) is prepared and characterized with Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), photoluminescent spectra. The application of NTG to hydrogen evolution exhibits high photocatalytic efficiency of 716.0 or 112.0 μmol h⁻¹ g⁻¹ under high-pressure Hg or Xenon lamp, which is about 9.2 or 13.6 times higher than P25 photocatalyst. This is mainly attributed to the N-doping of TiO₂ and the incorporation of graphene oxide resulting in narrow band gap, together with the synergistic effect of fast electron-transporting of photogenerated electrons and the efficient electron-collecting of graphene oxide retarding charge recombination. These results provide a significant theoretical foundation for the potential application of N-doping photocatalysts to hydrogen evolution.     

Carbon-sensitized and nitrogen-doped TiO2 for photocatalytic degradation of sulfanilamide under visible-light irradiation

A novel carbon-sensitized and nitrogen-doped TiO₂ (C/N-TiO₂) was synthesized by a facile sol-gel method using titanium butoxide as both titanium precursor and carbon source, and nitric acid as nitrogen source. The calcination temperature had a great effect on the crystal phase structure, nitrogen incorporation into the TiO₂ lattice and content of carbonaceous species. The incorporated carbonaceous species could serve as photosensitizer, while the nitrogen doping could lead to the remarkable red shift of absorption edge of C/N-TiO₂. The C/N-TiO₂ calcinated at 300 °C (T300) exhibited the highest photocatalytic activity for sulfanilamide (SNM) degradation under irradiation of visible-light-emitting diode (vis-LED). The SNM photocatalytic degradation and mineralization were more efficient in acidic conditions due to the carbon photosensitizing effect. Insignificant inhibitory effects were observed in the presence of chloride, nitrate and sulfate, while bicarbonate, phosphate and silica could inhibit the SNM mineralization to different degrees. Acetate, ammonium and sulfate were released during SNM mineralization. T300 exhibited good photochemical stability and could be reused for 5 times with less than 10% decrease in the SNM removal efficiency. The acute toxicity of SNM solution could be reduced over prolonged photocatalysis according to the Microtox assay.     

Novel nitrogen-doped anatase TiO2 mesoporous bead photocatalysts for enhanced visible light response

This work reports the synthesis and characterization of a novel, high surface area N-doped anatase TiO₂ mesoporous bead as a photocatalyst for visible light photodegradation. The beads were prepared using a two-cycle microwave-assisted hydrothermal method using three different types of nitrogen dopants: diaminohexane, triethylamine, and urea. In the first cycle, TiO₂mesoporous beads with controlled structures were synthesized at 200 °C without further calcination. The obtained beads were then subjected to a second cycle of microwave -assisted hydrothermal process for nitrogen doping. The photocatalytic activity of the N-doped mesoporous TiO₂ beads was determined by measuring the decomposition of a methyl blue aqueous solution under UV and visible light. It was found that different precursors lead to different degrees of doping which enhances the light absorption primarily in the visible light region. We demonstrate that the photocatalytic activity or photodegradation is enhanced in the visible light region.