Influence of Pyridine‐Polybenzimidazole Film Thickness of Carbon Nanotube Supported Platinum on Fuel Cell Applications

Pyridine‐polybenzimidazole (PyPBI) films of different thickness (∼1.0–2.4 nm) are wrapped on the surfaces of multi‐walled carbon nanotubes (CNTs). To prepare Pt on PyPBI/CNT (Pt‐PyPBI/CNT) catalysts, Pt⁴⁺ ions are immobilized on these PyPBI wrapped CNTs (PyPBI/CNTs) via Lewis acid‐base coordination between Pt⁴⁺ and :N‐ of imidazole groups, followed by reducing Pt⁴⁺ to Pt nanoparticles. The influence of PyPBI film thickness on the Pt particle size, loading and electrochemical surface area, respectively, of Pt‐PyPBI/CNTs is investigated. Fuel cell performances of the PBI/H₃PO₄ based membrane electrode assemblies (MEAs) prepared from these Pt‐PyPBI/CNT catalysts are also evaluated at 160 °C with unhumidified H₂/O₂ gases. Among the catalysts, the Pt‐PyPBI/CNT catalyst with a PyPBI film thickness of ∼1.6 nm (which is around half of the Pt particle size), a Pt loading of ∼44 wt.%, and a Pt particle size of ∼3.3 nm exhibits the best fuel cell performance.     

Nitrogen-doped carbon nanotubes synthesized with carbon nanotubes as catalyst

Nitrogen-doped carbon (CN_x) nanotubes were synthesized with carbon nanotubes (CNTs) as catalyst by detonation-assisted chemical vapor deposition. CN_x nanotubes exhibited compartmentalized bamboo-like structure. Electron energy loss spectroscopy and elemental mapping studies indicated that the synthesized tubes contained high concentration of nitrogen (ca. 17.3 at.%), inhomogeneously distributed with an enrichment of nitrogen within the compartments. X-ray photoelectron spectroscopy analysis revealed the presence of pyridine-like N and graphitic N incorporated into the graphitic network. The catalytic activity of CNTs for CN_x nanotube growth was ascribed to the nanocurvature and opening edges of CNT tips, which adsorbed C_n/CN species and assembled them into CN_x nanotubes.     

Shortened Carbon Nanotubes as Enhanced Support for High‐performance Platinum Catalysts

Carbon nanotubes (CNTs) were shortened from 5 to 15 μm to ca. 200 nm using ball milling with ethanol as the milling aid agent, and a platinum catalyst with these shortened carbon nanotubes (SCNTs) as the support was prepared by a high‐pressure colloidal method. It was found that this catalyst with SCNTs showed much higher activity than a platinum catalyst with normal CNTs as support; for methanol anodic oxidation, the activity of the Pt/SCNTs was 50% higher than that of the Pt/CNTs, and the Pt/SCNTs also showed higher activity for the cathodic reduction of oxygen. The Pt/SCNTs were characterised by X‐ray diffraction scanning and transmission electron microscropy. It is suggested that the significant performance enhancement when SCNTs are used as support might result from the generation of new surfaces and defects, the opening of closed nanotubes in the process of milling, higher platinum dispersion on the shortened nanotubes and the interaction of platinum nanoparticles with the SCNTs.     

Facile Preparation of an Excellent Pt/RuO2‐MnO2/CNTs Nanocatalyst for Anodes of Direct Methanol Fuel Cells

RuO₂‐MnO₂ complex supported by multi‐wall carbon nanotubes (CNTs) was firstly synthesised by the oxidation–reduction precipitation of RuCl₃ and KMnO₄ in one step. Then Pt was loaded onto the obtained RuO₂‐MnO₂/CNTs to fabricate a novel anodic catalyst Pt/RuO₂‐MnO₂/CNTs for direct methanol fuel cells (DMFCs). The catalyst was characterised by transmission electron microscopy (TEM), X‐ray diffraction (XRD), temperature programmed reduction (TPR), X‐ray photoelectron spectroscopy (XPS) and BET specific surface areas (BET). Pt nanoparticles were found uniformly dispersed on the surface of CNTs, with the average diameter of about 2.0 nm. The activities of methanol and CO electrocatalytic oxidation were analysed, and the reaction mechanism of methanol electro‐oxidation on Pt/RuO₂‐MnO₂/CNTs catalyst was discussed. The MnO₂ in the catalysts improves the proton conductivity and electrochemical active surface area (EAS) for the catalysts. RuO₂ improves the CO oxidation activity and Pt dispersion. CNTs provide effectively electron channels. Thus, the Pt/RuO₂‐MnO₂/CNTs catalyst has high utilisation of the noble metal Pt, high CO oxidation ability and excellent methanol electro‐oxidation activity, being an outstanding anode catalyst for DMFC.     

Efficient tuning of microstructure and surface chemistry of nanocarbon catalysts for ethylbenzene direct dehydrogenation

A facile and scalable approach to efficiently tune microstructure and surface chemical properties of N‐doped carbocatalysts through the controlled glucose hydrothermal treatment with diverse parameters and subsequent pyrolysis of pretreated carbonaceous materials with melamine (GHT‐PCM) was presented. Various characterization techniques including high resolution transmission electron microscopy (HRTEM), N₂ adsorption desorption (BET), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), Raman spectroscopy (Raman), and fourier transform infrared spectroscopy (FTIR) were employed to investigate the effect of prior GHT on the microstructure and surface chemical properties of N‐doped carbocatalysts, as well as to reveal the relationship between catalyst nature and catalytic performance in oxidant‐ and steam‐free direct dehydrogenation (DDH) of ethylbenzene for styrene production. It was found that the GHT process and its conditions significantly affect microstructure and surface chemical properties of the N‐doped carbocatalysts, which subsequently influences their catalytic performance in DDH reaction dramatically. Interestingly, the prior GHT can remove the carbon nitride layer formed on parent nanocarbon in the process of melamine pyrolysis, produce structural defects, and tune surface element component, through the “detonation” of polysaccharide coating on nanocarbon. The as‐prepared N‐doped CNT (M‐Glu‐CNT) by the established GHT‐PCM approach demonstrates higher catalytic performance (4.6 mmol g^?1h^?1 styrene rate with 98% selectivity) to the common N‐doped CNT (M‐CNT, 3.4 mmol g^?1 h^?1 styrene rate with 98.2% selectivity) as well as to pristine CNT (2.8 mmol g^?1 h^?1 styrene rate with 96.8% selectivity), mainly ascribed to increased structural defects, enriched surface ketonic C?O groups, and improved basic properties from N‐doping on the M‐Glu‐CNT, those strongly depend on GHT conditions. The excellent catalytic performance of the developed M‐Glu‐CNT catalyst endows it with great potential for future clean production of styrene via oxidant‐ and steam‐free conditions. Moreover, the directed GHT‐PCM strategy can be extended to the other N‐doped carbonaceous materials with enhanced catalytic performance in diverse reactions by tuning their microstructure and surface chemistry. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2543–2561, 2015     

Synthesis of zinc oxide and carbon nanotube composites by CVD method: photocatalytic studies

The present work describes the synthesis of multiwall carbon nanotubes (CNT), zinc oxide (ZnO) and their photocatalytic evolutions. Nickel doped fumed SiO₂ used as substrate for the synthesis of CNT by in chemical vapour deposition method. In-situ synthesis of ZnO:CNT composites was achieved in alkaline ethanolic medium with zinc chloride and CNT. The prepared composites were investigated by the Fourier Transform Infrared spectroscopy, confocal Raman spectroscopy, diffuse reflectance UV–visible spectrophotometer (DRS), X-ray diffraction, X-ray Photoelectron Spectroscopy (XPS), Brunaur–Emmett–Teller surface area and field emission scanning/transmission electron microscopy. The composites were employed in the degradation methylene blue and Reactive red-198 under visible light irradiation. The photocatalytic activity was determined by the spectrophotometric technique. The percentage of degradation was more for ZnO:CNT composites and shows higher capacitance, when compared to that of ZnO and CNTs. The recovered and reused catalysts catalytic activity was compared with that of fresh catalyst.     

The effect of CNT content on the surface and mechanical properties of CNTs doped diamond like carbon films

The carbon nanotubes (CNTs) doped diamond like carbon films were carried out by spinning coating multi-walled carbon nanotubes (CNTs) on silicon covered with diamond like carbon films via PECVD with C₂H₂ and H₂. The results show that the I_D/I_G and sp²/sp³ ratios are proportional to the CNT contents. For wettability and hydrogen content, the increase of CNT content results in more hydrophobic and less hydrogen for CNT doped DLC films. As for mechanical properties, the hardness and elastic modulus increases linearly with increasing CNT content. The residual stress is reduced for increasing CNT content. As for the surface property, the friction coefficient is reduced for higher CNT content. For CNT doped DLC films, the inclusion of horizontal CNT into DLC films increases the hardness, elastic modulus and reduces the hydrogen content, friction coefficient and residual stress. Like the light element and metal doping, the CNT doping has effects on the surface and mechanical properties on DLC which might be useful to specific application.     

Preparation of High Performance Pt/CNT Catalysts Stabilized by Ethylenediaminetetraacetic Acid Disodium Salt

A novel method with ethylenediaminetetraacetic acid disodium salt (EDTA‐2Na) as a stabilizing agent was developed to prepare highly dispersed Pt nanoparticles on carbon nanotubes (CNTs) to use as proton exchange membrane (PEM) fuel cell catalysts. These nanocatalysts were obtained by altering the molar ratio of ethylenediaminetetraacetic acid disodium salt to chloroplatinic acid (EDTA‐2Na/Pt) from 1:2, 1:1, 2:1 to 3:1. The well‐dispersed Pt nanoparticles of around 1.5 nm in size on CNTs were obtained when the EDTA‐2Na/Pt ratio was maintained at 1:1. And the Pt/CNT catalyst exhibited large electrochemical active surface areas, very high electrocatalytic activity and excellent stability in the oxidation of methanol at room temperature. The Pt/XC‐72R catalyst with narrow size distribution was also prepared by this method for comparison purposes. Comparison of the catalytic properties of these catalysts revealed that the activity of the Pt/CNT catalyst was a factor of ∼3 times higher than that of the Johnson Matthey catalyst and ∼2 times higher than that of our Pt/XC‐72R catalyst, which can be assigned to the high level of dispersion of Pt nanoparticles and the particular properties of the CNT supports.     

In situ grown carbon nanotubes on carbon paper as integrated gas diffusion and catalyst layer for proton exchange membrane fuel cells

In situ grown carbon nanotubes (CNTs) on carbon paper as an integrated gas diffusion layer (GDL) and catalyst layer (CL) were developed for proton exchange membrane fuel cell (PEMFC) applications. The effect of their structure and morphology on cell performance was investigated under real PEMFC conditions. The in situ grown CNT layers on carbon paper showed a tunable structure under different growth processes. Scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) demonstrated that the CNT layers are able to provide extremely high surface area and porosity to serve as both the GDL and the CL simultaneously. This in situ grown CNT support layer can provide enhanced Pt utilization compared with the carbon black and free-standing CNT support layers. An optimum maximum power density of 670 mW cm⁻² was obtained from the CNT layer grown under 20 cm³ min⁻¹ C₂H₄ flow with 0.04 mg cm⁻² Pt sputter-deposited at the cathode. Furthermore, electrochemical impedance spectroscopy (EIS) results confirmed that the in situ grown CNT layer can provide both enhanced charge transfer and mass transport properties for the Pt/CNT-based electrode as an integrated GDL and CL, in comparison with previously reported Pt/CNT-based electrodes with a VXC72R-based GDL and a Pt/CNT-based CL. Therefore, this in situ grown CNT layer shows a great potential for the improvement of electrode structure and configuration for PEMFC applications.     

Preparation and Catalytic Activity of Co/CNTs Nanocomposites via Microwave Irradiation

Co nanoparticles supported on carbon nanotubes (CNTs) were prepared by microwave‐assisted heating of the hydrazine reduction in ethylene glycol (EG). The Co/CNT nanocomposites prepared by the microwave‐irradiation method (MIM‐Co/CNTs) were characterized by XRD, SEM, EDS, and BET. It was found that MIM‐Co/CNTs had compact coating, high cobalt loading, and large BET surface area. The obtained products for the thermal decomposition of ammonium perchlorate (AP) were investigated by DTA. The catalytic activity of MIM‐Co/CNTs was better than that of pure Co nanoparticles and Co/CNT nanocomposites by water‐bath method (WBM‐Co/CNTs). The addition of 5 wt.‐% MIM‐Co/CNTs decreased the high decomposition temperature of AP by 174.05 °C and increased the total DTA heat release by 0.799 kJ g⁻¹.     

Electrochemical Characteristics and Performance of Platinum Nanoparticles Supported by Vulcan/Polyaniline for Oxygen Reduction in PEMFC

We report a Pt/Vulcan carbon–polyaniline (VC–PANI) catalyst for the oxygen reduction reaction (ORR). This electrocatalyst was prepared from Pt nanoparticles supported by a VC–PANI composite substrate. Electrochemical performance was measured using potentiostat/galvanostats technique and a proton exchange membrane fuel cell (PEMFC) test station. The electrochemical properties of the electrodes were characterized using linear sweep voltammetry, AC impedance spectroscopy and chronoamperometry. Electrochemical characterization by hydrogen adsorption/desorption cyclic voltammetry and CO stripping voltammetry indicates that the electrochemical active surface areas of the Pt/VC–PANI are comparable to the commercial catalyst. The performance of the Pt/VC–PANI and Pt/C(E‐TEK) + PANI electrocatalysts were found to be 1.82 and 1.33 times higher than of the Pt/C(E‐TEK) electrode. The surface morphologies of the electrodes were characterized by using scanning electron microscopy (SEM). PANI has a fibrous structure and the improved performance was attributed to the PANI effect and synergistic effects between the carbon Vulcan and the PANI fiber. These results indicate that Pt/VC–PANI is a promising catalyst for the ORR in PEMFCs using an H₂/O₂ feed.     

Employing Nitrogen Doping as Innovative Technique to Improve Broadband Dielectric Properties of Carbon Nanotube/Polymer Nanocomposites

Undoped carbon nanotubes (CNTs) and N‐CNTs are synthesized by chemical vapor deposition using Fe catalyst, and then melt‐mixed in an APAM mixer with polyvinylidene fluoride (PVDF) to prepare the nanocomposites. The morphology, crystallinity, aspect ratio, nitrogen content, and nitrogen bonding type of CNTs, and the broadband dielectric properties of undoped CNT/PVDF and N‐CNT/PVDF nanocomposites are analyzed. The results show that while undoped CNTs present a crystalline structure with open channels, doping with nitrogen results in CNTs with a bamboo‐like configuration, inferior crystallinity, smaller length, and larger dia­meter. The N‐CNT/PVDF nanocomposites, thus, have a higher percolation threshold (≈ 3.5 wt%) compared to that of the undoped CNT/PVDF nanocomposites (≈ 0.5 wt%). Comparison of the broadband dielectric properties of the generated nanocomposites reveals that nitrogen doping improved the dielectric properties in the insulative region. This is ascribed to the role of nitrogen atoms and their sequent defects in the nanotubes, which act as scattering centers and provide additional polarization sites. For instance, 1.0 wt% N‐CNT/PVDF nanocomposites exhibit a real permittivity of ε′ = 22 and a dissipation factor of tan δ = 0.03 at 1 kHz, a combination superior to that of 0.5 wt% undoped CNT/PVDF nanocomposite with ε′ = 11.2 and tan δ = 3.8, and 1.0 wt% undoped CNT/PVDF nanocomposites with ε′ = 40 and tan δ = 1.4 × 10⁵.

     

Synthesis and activity of the Pt catalyst supported on CNT

Carbon nanotubes (CNT) were obtained by the decomposition of methane on a Ni catalyst supported on Al₂O₃. After the removal of the catalyst materials from CNT, a CNT-supported Pt catalyst was prepared, and this catalyst was characterized by XRD, XPS, and TEM. Activity of the CNT-supported Pt catalyst for hydrogenation of carbon–carbon double bonds at room temperature under the atmospheric pressure of hydrogen was examined. The CNT-supported Pt catalyst showed higher activity than the commercial Pt catalysts supported on activated carbon.     

Pure and complex nanostructures using poly[bis(triiso‐propylsilylethynyl) benzodithiophene‐bis(decyltetradecyl‐thien) naphthobisthiadiazole], carbon nanotubes and reduced graphene oxide for high‐performance polymer solar cells

Crystallization of poly[bis(triiso‐propylsilylethynyl) benzodithiophene‐bis(decyltetradecyl‐thien) naphthobisthiadiazole] (PBDT‐TIPS‐DTNT‐DT) was investigated in supramolecules based on carbon nanotubes (CNTs) and reduced graphene oxide (rGO) and their grafted derivatives. The principal peaks of PBDT‐TIPS‐DTNT‐DT crystals were in the range 3.50°–3.75°. By grafting the surface of the carbonic materials, the assembling of polymer chains decreased because of hindrance of poly(3‐dodecylthiophene) (PDDT) grafts against π‐stacking. The diameters of CNT/polymer and CNT‐g‐PDDT/polymer supramolecules were 160 and 100 nm. The rGO/polymer supramolecules had the highest melting point (T_m = 282 °C) and fusion enthalpy (ΔH_m = 25.98 J g^?1), reflecting the largest crystallites and the most ordered constituents. Nano‐hybrids based on grafted rGO (276 °C and 28.26 J g^?1), CNT (275 °C and 27.32 J g^?1) and grafted CNT (268 °C and 22.17 J g^?1) were also analyzed. T_m and ΔH_m values were significantly less in corresponding melt‐grown systems. The nanostructures were incorporated in active layers of PBDT‐TIPS‐DTNT‐DT:phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) solar cells to improve the photovoltaic features. The best results were detected for PBDT‐TIPS‐DTNT‐DT:PC₇₁BM:rGO/polymer systems having J_sc = 13.11 mA cm^?2, fill factor 60% and V_oc = 0.71 V with an efficacy of 5.58%. On grafting the rGO and CNT, efficiency reductions were 12.01% (5.58%–4.91%) and 9.34% (4.07%–3.69%), respectively. © 2019 Society of Chemical Industry     

Porous nitrogen doped carbon foam with excellent resilience for self-supported oxygen reduction catalyst

Fabrication of graphitized carbon materials (e.g. carbon nanotubes and graphene) normally entails the assistance of transition metal catalyst. In this paper, a nitrogen doped carbon foam (NCF) with both graphitized and porous carbon structure was fabricated by direct pyrolysis of melamine foam (MF) without using any transition metal catalyst. The graphitized carbon structure was possibly attributed to the triazine moieties in the MF precursor. The introduction of oxygen groups in the oxidation step resulted in the formation of large amount of micro- and mesopores and therefore high specific surface area. The NCF exhibited a three-dimensional cellular network consisting of carbon microfiber with abundant micro- and mesopores and giving rise to a specific surface area over 980 m² g⁻¹. Due to such graphitized porous structure, the NCF was demonstrated to have superior resilience, excellent electrocatalytic activity and good durability for oxygen reduction.     

Processing and properties of carbon nanotube/poly(methyl methacrylate) composite films

A systematic study of the reinforcement of single‐walled carbon nanotubes (SWNTs), multiwalled carbon nanotubes, and vapor‐grown carbon nanofibers (VGCNFs) in poly(methyl methacrylate) (PMMA) is reported. SWNT/PMMA composite films with various SWNT concentrations (from 0.5 to 50 wt % with respect to the weight of PMMA) were processed from nitromethane. Two types of SWNTs were used: SWNT‐A, which contained 35 wt % metal catalyst, and SWNT‐B, which contained about 2.4 wt % metal catalyst. Properties of different nanotubes containing composites were compared with 15 wt % carbon nanotubes (CNTs). Property enhancement included electrical conductivity, mechanical properties, and solvent resistance. The thermal degradation of PMMA in the presence of CNTs in air and nitrogen environments was studied. No variation in the thermal degradation behavior of PMMA/CNT was observed in nitrogen. The peak degradation temperature increased for the composites in air at low CNT loadings. Dynamic and thermomechanical properties were also studied. At a 35 wt % SWNT loading, a composite film exhibited good mechanical and electrical properties, good chemical resistance, and a very low coefficient of thermal expansion. Property improvements were rationalized in terms of the nanotube surface area. Composite films were also characterized with Raman spectroscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Catalyst‐Assisted Growth of Single‐Crystalline Hafnium Carbide Nanotubes by Chemical Vapor Deposition

Single‐crystalline hafnium carbide (HfC) nanotubes were synthesized by a one‐step catalyst‐assisted chemical vapor deposition (CVD) method. The typical nanotubes had uniform diameters of ~60 nm and wall thicknesses of ~15 nm and preferentially grew along [201]. From HRTEM/EELS analysis, the growth mechanism based on carbon nanotubes (CNT) tip growth and CNT‐templated reaction was proposed for explaining the formation of HfC nanotubes. According to the mechanism, CNTs were first formed by diffusion of C atoms on the surface of solid Ni catalyst particles. Then, gaseous Hf species reacted with C atoms from CNTs to form HfC nanotubes. During the entire growth process, Hf atoms did not participate in the catalytic reaction. Thus, this process was distinguished from the conventional vapor–liquid–solid process.     

Synthesis of multi-walled carbon nanotubes over tungsten-doped cobalt-based catalyst derived from a layered double hydroxide precursor

Multi-walled carbon nanotubes (CNTs) were prepared over a series of W-doped Co-based catalysts derived from layered double hydroxide precursor by catalytic chemical vapor deposition (CCVD) of acetylene. The materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption–desorption experiments and Raman spectroscopy. The effect of the proportion of W in the Co-based catalysts on the carbon yield, diameter uniformity and quality of CNTs was investigated. The results demonstrated that with the increasing W/Co molar ratio from 0 to 1.0, both the mean number of walls and the average diameter of CNT produced over catalysts increased from about 8 to 28 nm and from about 12.1 to 23.7 nm, respectively. A small amount of tungsten added to the catalyst with the W/Co molar ratio of 0.3 could facilitate the dispersion of catalytically active Co species on the surface of support, and thus uniform and high-quality CNTs with a remarkably high yield of ca. 1600% were obtained.     

An Extremely Active Pt/Carbon Nano-Tube Catalyst for Selective Oxidation of CO in H2 at Room Temperature

Pt catalyst supported on carbon nano-tube (CNT) was extremely active for the selective oxidation of CO in H₂ at room temperature, which was remarked contrast to the Pt supported on an active carbon (Vulcan carbon) and a graphite powder. Complete oxidation of CO was attained on a 5 wt.% Pt/CNT catalyst (0.8 g) at ca. 40 °C when the O₂/CO ratio in a flow of H₂ (20 mL/min) + CO (3.0 mL/min) + O₂ + N₂ was adjusted to be larger than 0.75 at the total flow rate of 100 mL/min. Specific activity of the Pt/CNT catalyst was explained by efficient provision of reactant molecules diffusing on CNT surface to Pt particles.     

Green synthesis of a Pt nanoparticle/polyoxometalate/carbon nanotube tri-component hybrid and its activity in the electrocatalysis of methanol oxidation

The easy, room temperature and environmentally friendly synthesis of Pt nanoparticle-decorated carbon nanotubes (CNTs) is reported. Polyoxometalates (POMs) were used to serve as both reducing and bridging molecules. Characterization using transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction analysis, etc. was performed and verified the structure of the prepared nanohybrid of Pt@POM/CNT. The nanohybrid showed a higher electrocatalytic activity towards methanol oxidation reaction than did a traditional Pt–C catalyst and the other reported Pt/CNT systems. The POM also serves as a co-catalyst in the nanohybrid, which plays a key role in improving the electrocatalytic activities of the catalyst.