High loading and monodispersed Pt nanoparticles on multiwalled carbon nanotubes for high performance proton exchange membrane fuel cells

Composite electrodes consisting of Pt nanoparticles-supported on multiwalled carbon nanotubes grown directly on carbon paper (Pt/CNTs/carbon paper) have been synthesized by a new method using glacial acetic acid as a reducing agent. Transmission electron microscopy (TEM) images show that the Pt nanoparticles with high density and relative small in size (2–4 nm) were monodispersed on the surface of CNTs. X-ray photoelectron spectroscopy (XPS) analysis indicates that the glacial acetic acid acts as a reducing agent and has the capability of producing a high density of oxygen-containing functional groups on the surface of CNTs that leads to high density and monodispersion of Pt nanoparticles. Compared with standard Pt/C electrode, the Pt/CNT/carbon paper composite electrodes exhibit higher electrocatalytic activity for methanol oxidation reaction and higher single-cell performance in a H₂/O₂ fuel cell.     

Enhanced catalytic properties from platinum nanodots covered carbon nanotubes for proton-exchange membrane fuel cells

An efficient fabrication method for carbon nanotube (CNT)-based electrode with a nanosized Pt catalyst is developed for high efficiency proton-exchange membrane fuel cells (PEMFC). The integrated Pt/CNT layer is prepared by in situ growth of a CNT layer on carbon paper and subsequent direct sputter-deposition of the Pt catalyst. Both scanning electron microscopy (SEM) and transmission electron microscopy (TEM) demonstrate that this Pt/CNT layer consists of a highly porous CNT layer covered by well-dispersed Pt nanodots with a narrow size distribution. Compared with conventional gas-diffusion layer assisted electrodes, the CNT-based electrode with a Pt/CNT layer acting as a combined gas-diffusion layer and catalyst layer shows pronounced improvement in polarization tests. A high maximum power density of 595 mW cm⁻² is observed for a low Pt loading of 0.04 mg cm⁻² at the cathode.     

Electrocatalytic properties improvement on carbon-nanotubes coated reaction surface for micro-DMFC

In this paper, the enhancement of electrocatalytic performance of carbon nanotubes (CNTs) grown on silicon substrate was demonstrated as compared with the conventional reaction surfaces including bare silicon wafer, carbon cloth and carbon paper, and all were with a thin Pt film (10 nm) coating. The peak current density was doubled by the Pt film/CNTs electrode comparing to Pt film/carbon cloth and about six times comparing to silicon wafer because of the large reaction surface area and excellent CO₂ microbubble removal capability by the CNTs nanostructure. The results indicated that the electrocatalytic performance of catalyst was significantly improved for the peak current density on better linear relationship to methanol concentration and square root of sweeping-rate, better exponential relationship to temperature and higher peak current density on different substrate tiling angles, which greatly attribute to the rapid microbubbles removal on nanostructured hydrophilic CNTs surface. These conclusions can be taken as references to designing micro-DMFC in the future.     

Electrochemical activity and stability of Pt catalysts on carbon nanotube/carbon paper composite electrodes

This article reports a facile microwave-assisted approach to synthesize Pt catalysts on carbon nanotube (CNT)/carbon paper (CP) composite through catalytic chemical vapor deposition. The Pt deposits, with an average size of 3–5 nm were uniformly coated over the surface of oxidized CNTs. The electrochemical activity and stability of the Pt–CNT/CP electrode were investigated in 1 M H₂SO₄ using cyclic voltammetry (CV) and ac electrochemical impedance spectroscopy. The Pt catalysts showed not only fairly good electrochemical activity (electrochemically active surface area) but also durability after a potential cycling of >1000 cycles. The analysis of ac impedance spectra associated with equivalent circuit revealed that the presence of CNTs significantly reduced both connect and charge transfer resistances, leading to a low equivalent series resistance ˜0.22 Ω. With the aid of CNTs, well-dispersed Pt catalysts enable the reversibly rapid redox kinetic since electron transport efficiently passes through a one-dimensional pathway. Thus, the CNTs do not only serve as carbon support, they also charge transfer media between the Pt catalysts and the gas diffusion layer. The results shed some light on the use of CNT/CP composite, offering a promising tool for evaluating high-performance gas diffusion electrodes.     

Pt and Pt–Ag nanoparticles supported on carbon nanotubes (CNT) for oxygen reduction reaction in alkaline medium

In this work, we investigated the effect of the carbon nanotubes (CNT) as alternative support of cathodes for oxygen reduction reaction (ORR) in alkaline medium. The Pt and Pt–Ag nanomaterials supported on CNT were synthesized by sonochemical method. The crystalline structure, morphology, particle size, dispersion, specific surface area, and composition were investigated by XRD, SEM-EDS, TEM, HR-TEM, N₂ adsorption-desorption and XPS characterization. The electrochemical activity for ORR was evaluated by cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) in alkaline medium. The electrochemical stability was researched by an accelerated degradation test (ADT). Pt/CNT showed the better electrocatalytic activity towards ORR compared with Pt–Ag/CNT and Pt/C. Pt/CNT exhibited higher specific activity (1.12 mA cm^?2 _Pt) than Pt/C (0.25 mA cm^?2 _Pt) which can be attributed to smaller particle size, Pt-CNT interaction, and Pt load (5 wt%). The Pt monometallic samples supported on CNT and Vulcan showed higher electrochemical stability after ADT than Pt–Ag bimetallic. The ORR activity of all materials synthesized proceeded through a four-electron pathway. Furthermore, the EIS results showed that Pt/CNT exhibited the lower resistance to the transfer electron compared with conventional Pt/C and Pt–Ag/CNT.     

Methane decomposition with some CO2 as co-feed: Co-production of syngas and carbon fibers/microspheres by using a hybrid of K2CO3 and coal char

Co-production of hydrogen and valuable carbonaceous materials by catalytic methane decomposition (CMD) is a promising process. However, nowadays it is still difficult for various carbon catalysts to make it. Here CMD with addition of some CO₂ as co-feed was proposed and evaluated by using a hybrid of K₂CO₃ and coal char (CC). Effect of the additional CO₂ as co-feed was investigated on methane conversion, the outlet gas composition, and the deposited carbon morphology. The results show that co-production of syngas (H₂ and CO) and carbon fibers/microspheres could be obtained along with high and stable methane (around 80%) and CO₂ conversion (up to about 100%) in the process. Stable molar ratios of H₂/CO (ranging from 0.6:1 to 5:1) as well as different carbon morphologies (amorphous, fibrous or microspherical) can be regulated and controlled by the molar ratio of CH₄/CO₂ (from 75:10 to 75:75) in the feedstock. Quantitative and qualitative analysis of the products show that there is probably a synergy between K₂CO₃ and CC during the reaction process.     

High performance of low electrocatalysts loading on CNT directly grown on carbon cloth for DMFC

This study demonstrated the feasibility of a high-performance membrane-electrode-assembly (MEA), with low electrocatalyst loading on carbon nanotubes (CNTs) grown directly on carbon cloth as an anode. The direct growth of CNTs was synthesized by microwave plasma-enhanced chemical vapor deposition using CH₄/H₂/N₂ as precursors. The cyclic voltammetry and electrochemical impedance measurements with 1 mM Fe(CN)₆^3−/4− redox reaction reveal a fast electron transport and a low resistance of charge transfer on the direct growth of CNT. The electrocatalysts, platinum and ruthenium, were coated on CNTs by sputtering to form Pt-Ru/CNTs-CC with carbon cloth for CC. Pt-Ru electrocatalysts are uniformly dispersed on the CNT, as indicated by high-resolution scanning electron microscopy (HRSEM) and transmission electron microscopy (TEM), because the nitrogen doped in the CNT acts as active sites for capturing electrocatalysts. The MEA, the sandwiched structure which comprises 0.4 mg cm⁻² Pt-Ru/CNTs-CC as the anode, 3.0 mg cm⁻² Pt black as the cathode and Nafion 117 membrane at the center, performs very well in a direct methanol fuel cell (DMFC) test. The micro-structural MEA analysis shows that the thin electrocatalyst layer is uniform, with good interfacial continuity between membrane and the gas diffusion layer.     

Nitrogen doped carbon layer coated platinum electrocatalyst supported on carbon nanotubes with enhanced stability

Enhancement in durability of electrocatalyst is still one of the most important issues in polymer electrolyte fuel cells (PEFCs). Here, we report a structurally coated electrocatalyst supported on carbon nanotubes (CNT), in which platinum (Pt) nanoparticles are coated by nitrogen doped carbon (NC) layers. CNT/NC/Pt/NC shows comparable electrochemical surface area (ECSA) and oxygen reduction reaction (ORR) activity to the non-coated electrocatalyst (CNT/NC/Pt), indicating that NC layer on Pt nanoparticles almost negligibly affects the activities of electrocatalyst; while, CNT/NC/Pt/NC exhibits a higher Pt stability due to the unique structure, in which the Pt nanoparticles are stabilized by the NC layers and Pt aggregation is decelerated proved by TEM measurement. Maximum power density of CNT/NC/Pt/NC reached 604 mW cm^?2 with Pt loading of 0.1 mg_Pt cm^?2, which only decreases by 7% compared to CNT/NC/Pt (650 mW cm^?2). The electrochemical analysis and fuel cell test illustrate that NC layer on Pt nanoparticles enhances the durability without serious deterioration of fuel cell performance.     

Performance of direct methanol fuel cell using carbon nanotube-supported Pt–Ru anode catalyst with controlled composition

The performance of a single-cell direct methanol fuel cell (DMFC) using carbon nanotube-supported Pt–Ru (Pt–Ru/CNT) as an anode catalyst has been investigated. In this study, the Pt–Ru/CNT electrocatalyst was successfully synthesized using a modified polyol approach with a controlled composition very close to 20 wt.%Pt–10 wt.%Ru, and the anode was prepared by coating Pt–Ru/CNT electrocatalyst on a wet-proof carbon cloth substrate with a metal loading of about 4 mg cm⁻². A commercial gas diffusion electrode (GDE) with a platinum black loading of 4 mg cm⁻² obtained from E-TEK was employed as the cathode. The membrane electrode assembly (MEA) was fabricated using Nafion^® 117 membrane and the single-cell DMFC was assembled with graphite endplates as current collectors. Experiments were carried out at moderate low temperatures using 1 M CH₃OH aqueous solution and pure oxygen as reactants. Excellent cell performance was observed. The tested cell significantly outperformed a comparison cell using a commercial anode coated with carbon-supported Pt–Ru (Pt–Ru/C) electrocatalyst of similar composition and loading. High conductivity of carbon nanotube, good catalyst morphology and suitable catalyst composition of the prepared Pt–Ru/CNT electrocatalyst are considered to be some of the key factors leading to enhanced cell performance.     

Graphene nanosheet–CNT hybrid nanostructure electrode for a proton exchange membrane fuel cell

This work demonstrates two-step growth of graphene nanosheets (GNS), in which carbon nanotubes (CNTs) are grown directly on a carbon cloth. GNS are subsequently constructed on the CNT surface, revealing the stand-up structure of the GNS–CNT hybrid nanostructure. The GNS–CNT hybrid nanostructure shows Nernstian and fast electron-transfer kinetics for electrochemical reactions of Fe(CN)₆^3−/4−. A 0.1 mg cm⁻² Pt/GNS–CNT is used in the cathode of a proton membrane exchange fuel cell, in which the maximum power density is 1072 mW cm⁻² at 80 °C under H₂/O₂. In addition to a low-resistance electron-transfer pathway, the GNS–CNT hybrid nanostructure also provides numerous edge planes with strong electrochemical activity, ultimately enhancing electrochemical activity and fuel cell performance.     

Carbon nanotube-supported Pt-HxMoO3 as electrocatalyst for methanol oxidation

Carbon nanotube (CNT)-supported platinum modified with H_xMoO₃ (Pt-H_xMoO₃/CNT) was prepared and used as an electrocatalyst for methanol oxidation. In the preparation of this electrocatalyst, a platinum precursor was loaded on CNTs and reduced by sodium borohydride in ethylene glycol, resulting in CNT-supported platinum without modification (Pt/CNT), and then the Pt/CNT was modified with H_xMoO₃ that was formed by hydrolysis and subsequent reduction of ammonium molybdate. The surface morphology, structure and composition of Pt-H_xMoO₃/CNT and Pt/CNT as well as their activity toward methanol oxidation were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive spectrometry (EDS), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), chronoamperometry (CA), chronopentiometry (CP), and electrochemical impedance spectroscopy (EIS). The results, obtained from TEM, XRD, EDS, and FTIR, indicate that the platinum loaded on CNTs has a face-centered cubic structure with particle sizes of 2–5 nm, and the modification of H_xMoO₃ on platinum with an atom ratio of Pt:Mo = 2:1 has little effect on the particle size, distribution and structure of the platinum. The results, obtained from CV, CA, CP, and EIS, show that the Pt-H_xMoO₃/CNT exhibits higher electrocatalytic activity toward methanol oxidation and better carbon monoxide tolerance than Pt/CNT.     

Investigation of the effect of graphitized carbon nanotube catalyst support for high temperature PEM fuel cells

In this study, it is aimed to investigate the graphitization effect on the performance of the multi walled carbon nanotube catalyst support for high temperature proton exchange membrane fuel cell (HT-PEMFC) application. Microwave synthesis method was selected to load Pt nanoparticles on both CNT materials. Prepared catalyst was analyzed thermal analysis (TGA), Transmission Electron Microscopy (TEM) and corrosion tests. TEM analysis proved that a distribution of Pt nanoparticles with a size range of 2.8–3.1 nm was loaded on the Pt/CNT and Pt/GCNT catalysts. Gas diffusion electrodes (GDE) were manufactured by an ultrasonic spray method with synthesized catalyst. Polybenzimidazole (PBI) membrane based Membrane Electrode Assembly (MEA) was prepared for observe the performance of the prepared catalysts. The synthesized catalysts were also tested in a HT-PEMFC environment with a 5 cm² active area at 160 °C without humidification. This study demonstrates the feasibility of using the microwave synthesis method as a fast and effective method for preparing high performance Pt/CNT and Pt/GCNT catalyst for HT-PEMFC. The HT-PEMFC performance evaluation shows current densities of 0.36 A/cm²0.30 A/cm² and 0.20 A/cm² for the MEAs prepared with Pt/GCNT, Pt/CNT and Pt/C catalysts @ 0.6 V operating voltage, respectively. AST (Accelerated Stress Test) analyzes of MEAs prepared with Pt/GCNT and Pt/CNT catalysts were also performed and compared with Pt/C catalyst. According to current density @ 0.6 V after 10,000 potential cycles, Pt/GCNT, Pt/CNT and Pt/C catalysts can retain 61%, 67% and 60% of their performance, respectively.     

High-performance and low platinum loading Pt/Carbon black counter electrode for dye-sensitized solar cells

Pt/Carbon black counter electrode for dye-sensitized solar cells (DSSCs) was prepared by reducing H₂PtCl₆ with NaBH₄ in carbon black. The Pt/Carbon black electrode had a high electrocatalytic activity for iodide/triiodide redox reaction. Using the Pt/Carbon black counter electrode, DSSC achieved 6.72% energy conversion efficiency under one sun illumination. Pt/Carbon black electrode shows the same energy conversion efficiency and lower cost compared with Pt electrode, which makes it available in DSSCs practical applications.     

Microbial fuel cell performance of multiwall carbon nanotubes on carbon cloth as electrodes

Microbial fuel cell (MFC), which can produce electricity during treatment of wastewater, has become one of the emerging technologies in the field of environmental protection and energy recovery. Of all parts of MFC, the electrode materials play a crucial role in the electricity generation. In this study, we investigate the performance of carbon nanotube (CNT) modified carbon cloth electrodes in single-chamber MFC. The MFC is first inoculated with bacteria in wastewater and then its capability of using acetate sodium as fuel is examined. The results show that the MFC with CNT coated onto carbon cloth electrode improves the power density. In this study, the obtained maximum power density is 65 mW m⁻², the highest chemical oxygen demand (COD) removal efficiency is 95%, and the maximum Coulombic efficiency is 67%. Compared with other reported studies, the CNT/carbon cloth composite electrode has demonstrated high potential for the use of MFC.     

Design and preparation of highly active carbon nanotube-supported sulfated TiO2 and platinum catalysts for methanol electrooxidation

A novel electrocatalyst structure of carbon nanotube-supported sulfated TiO₂ and Pt (Pt-S-TiO₂/CNT) is reported. The Pt-S-TiO₂/CNT catalysts are prepared by a combination of improved sol-gel and ethylene glycol reduction methods. Transmission electron microscopy and X-ray diffraction show that the sulfated TiO₂ is amorphous and is coated uniformly on the surface of the CNTs. Pt nanoparticles of about 3.6 nm in size are homogenously dispersed on the sulfated TiO₂ surface. Fourier transform infrared spectroscopy analysis proves that the CNT surfaces are modified with sulfated TiO₂ and a high concentration of SO_x, and adsorbed OH species exist on the surface of the sulfated TiO₂. Electrochemical studies are carried out using chronoamperometry, cyclic voltammetry, CO stripping voltammetry and impedance spectroscopy. The results indicate that Pt-S-TiO₂/CNT catalysts have much higher catalytic activity and CO tolerance for methanol electrooxidation than Pt/TiO₂/CNTs, Pt/CNTs and commercial Pt/C.     

Solvent effect in the synthesis of nanostructured Pt–Sn/CNT as electrocatalysts for the electrooxidation of ethanol

Pt and Pt–Sn nanoparticles were synthesized and supported onto carbon nanotubes (CNT), the electrocatalytic activity towards the ethanol oxidation reaction was analyzed. The effect of the solvent employed for the synthesis was evaluated. Metal nanoparticles synthesis was made using water (Pt–Sn/CNT-W) or ethanol (Pt–Sn/CNT-E) as a solvent. Pt–Sn/CNT-W material presented only Pt–Sn alloy nanoparticles homogeneously distributed on the carbon nanotubes support. Pt–Sn/CNT-E sample showed non well-dispersed nanoparticles forming agglomerates along the CNTs surface with predominantly Sn⁴⁺ superficial species (SnO₂) as show the XPS, FTIR and electrochemical results. These surface arrangements had important effects on the electrocatalytic properties. Pt–Sn/CNT-W shows higher ethanol electrooxidation activity than the Pt–Sn/CNT-E, which is attributed to: a) the double catalytic effect and the intrinsic electronic mechanism favored by the presence of Sn; b) the good particle dispersion of the bimetallic active phase on the CNT and; c) the absence of SnO₂ species.     

Electrochemical micro-capacitors of patterned electrodes loaded with manganese oxide and carbon nanotubes

MnO₂ and carbon nanotubes (CNT) composite electrodes have been built on the interdigital stack layers of Fe-Al/SiO₂ and Fe-Al/Au/Ti/SiO₂ for the electrochemical micro-capacitors, using photolithography and thin-film technologies. The electrode properties and the performance of micro-cells are measured and analyzed with cyclic voltammetry (CV), impedance spectroscopy, and galvanostatic charge/discharge test in 0.1 M Na₂SO₄ electrolyte. The vertically aligned CNT, grown on Fe-Al/SiO₂, is more suitable for supporting the pseudocapacitive MnO₂ than the random CNT on Fe-Al/Au/Ti/SiO₂, but ohmic resistance of the former electrode is higher. We have prepared three cells on each stack layer with different electrode materials. The Ragone plot shows systematic variations in power and energy performance, reflecting their differences in electrode structure and polarization loss. The asymmetric cell of a pseudocapacitive positive electrode, loaded with MnO₂ and CNT, exhibits a small IR drop and a high specific energy during discharge. Built on Fe-Al/SiO₂, this asymmetric cell discharges at specific power 0.96 kW kg⁻¹ with specific energy 10.3 Wh kg⁻¹; while on Fe-Al/Au/Ti/SiO₂, the asymmetric cell discharges at power 1.16 kW kg⁻¹ with energy 5.71 Wh kg⁻¹.     

ZIF-8/PEDOT @ flexible carbon cloth electrode as highly efficient electrocatalyst for oxygen reduction reaction

Design and fabrication of highly efficient and low-cost oxygen reduction reaction (ORR) electrocatalysts is of paramount importance for practical applications. Herein, we proposed a cost-effective, metal-free catalyst based on ZIF-8 metal-organic framework nanoparticles/electro-polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) film on the surface of flexible carbon cloth (CC) electrode (ZIF-8/PEDOT/CC) via a two-step procedure. For this purpose, worm-like PEDOT nanostructures were deposited on the surface of carbon fibers using a pulse electro-polymerization technique followed by facile growth of ZIF-8 polyhedra nanoparticles via a chemical bath deposition method. The ORR measurements in O₂-saturated KOH electrolyte solution using the modified CC electrode demonstrated that the prepared electrode exhibits remarkable electrocatalytic activity towards ORR with 8 times increase in the cathodic current density compared to bare CC (J = 0.13–1.1 mA/cm²) along with lower overpotential due to the synergetic effects between ZIF-8 nanoparticles as particularly porous nanostructure act as electrolyte reservoirs and highly conductive PEDOT film. The Kouteckey-Levich analysis for the ZIF-8/PEDOT-modified CC electrode revealed that the oxygen reduction reaction proceeds via a nearly four-electron pathway along with superior tolerance to methanol crossover as well as enhanced stability in alkaline solution compared to the gold standard commercial Pt catalyst.     

Platinum-sputtered electrode based on blend of carbon nanotubes and carbon black for polymer electrolyte fuel cell

A novel Pt-sputtered electrode based on a blend layer of carbon black (CB) and carbon nanotubes (CNTs) is developed for polymer electrolyte fuel cells. The Pt is sputtered on the surface of the blend to form a catalyst layer. The CNTs generate a pore in the blend layer, and the CB provides a high surface roughness for the blend layer. At a CNT content of 50 wt.%, the maximum value (20.6 m² g⁻¹) for the electrochemical area of the Pt is obtained, which indicates that the surface area of the blend layer exposed for Pt deposition is the largest. The power density of a membrane-electrode assembly (MEA) employing the Pt-sputtered electrodes shows a linear increase with electrochemical area. The mass activity of the optimized Pt-sputtered electrode with a Pt loading of 0.05 mg cm⁻² is 8.1 times that of an electrode with a Pt loading of 0.5 mg cm⁻² prepared using a conventional screen-printing technique. Excellent mass transfer is obtained with the Pt-sputtered electrode.     

Electrodeposited manganese oxides on three-dimensional carbon nanotube substrate: Supercapacitive behaviour in aqueous and organic electrolytes

Thin amorphous manganese oxide layers with a thickness of 3–5 nm are electrodeposited on a carbon nanotube (CNT) film substrate that has a three-dimensional nanoporous structure (denoted as MnO₂/CNT electrode). For the purpose of comparison, manganese oxide films are also electrodeposited on a flat Pt-coated Si wafer substrate (denoted as MnO₂ film electrode). The pseudocapacitive properties of the MnO₂ film and MnO₂/CNT electrodes are examined in both aqueous electrolyte (1.0 M KCl) and non-aqueous organic electrolyte (1.0 M LiClO₄ in propylene carbonate). While both types of electrode show pseudocapacitive behaviour in the aqueous electrolyte, only the MnO₂/CNT electrode does so in the organic electrolyte, due to its high oxide/electrolyte interfacial area and improved electron conduction through the CNT substrate. Compared with the MnO₂ film electrode, the MnO₂/CNT electrode shows a much higher specific capacitance and better high-rate capability, regardless of the electrolyte used. Use of the organic electrolyte results in a ∼6 times higher specific energy compared with that obtained with the aqueous electrolyte, while maintaining a similar specific power. The construction of a three-dimensional nanoporous network structure consisting of a thin oxide layer on a CNT film substrate at the nm scale and the use of an organic electrolyte are promising approaches to improving the specific energy of supercapacitors.