Investigation of Pt Catalysts Supported on Multi-Walled Carbon Nanotubes with Various Diameters and Lengths

Platinum electrocatalysts supported on multi-walled carbon nanotubes (MWCNTs) with various diameters and lengths were studied by using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) and Chronoamperometry. The results indicated that the MWCNTs with smaller diameter generated more amorphous carbon after a sonochemical oxidation treatment. Compared with the long MWCNTs, the short MWCNTs had more open ends, resulting in high-Pt dispersion and electrocatalytic activity towards methanol oxidation. Pt nanoparticles supported on short MWCNTs with a diameter of 30–50 nm exhibited the best Pt dispersion and highest methanol oxidation activity among the catalysts studied. The high activities of the catalysts based on short MWCNTs were due to both the intrinsic high activity of the ends of MWCNTs and a good Pt distribution.     

Hydrothermal synthesis of size-dependent Pt in Pt/MWCNTs nanocomposites for methanol electro-oxidation

A hydrothermal method has been developed to prepare size-controlled Pt nanoparticles dispersed highly on multiwalled carbon nanotubes (Pt/MWCNTs). It was found that the size of Pt nanoparticles was strongly dependent on the solution pH in synthesis. The Pt nanoparticles with mean size of 3.0, 4.2 and 9.1 nm were obtained at pHs 13, 12 and 10 separately. After Pt/MWCNTs composites were fabricated, the different properties of cyclic voltammetry and chronoamperometry in electro-oxidation of methanol were found. The results showed that the smaller diameter Pt deposited Pt/MWCNTs nanocomposites exhibited higher electrocatalytic activity for methanol oxidation. By characterization of X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), size-dependent activities were identified.     

Electrocatalytic performance of carbon nanotube-supported palladium particles in the oxidation of formic acid and the reduction of oxygen

We describe a simple approach for the synthesis of nanosized Pd particles supported on multiwall carbon nanotubes (MWCNTs) and their electrocatalytic performance in the oxidation of formic acid and the reduction of oxygen. The metal precursors are pre-organized on poly(diallyldimethylammonium) chloride-wrapped MWCNTs by electrostatic interaction and chemically reduced to obtain Pd nanoparticles. The MWCNT-supported nanoparticles are characterized by UV-visible spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy and electrochemical measurements. MWCNTs are uniformly decorated with closely packed array of nanoparticles. The nanoparticles on the MWCNTs have spherical and rod-like shapes with size ranging from 5 to 10 nm. XRD and selected area electron diffraction measurements of the nanoparticles show (1 1 1), (2 0 0) and (2 2 0) reflections of the Pd lattice. The electrocatalytic activity of the nanoparticles towards oxidation of formic acid and reduction of oxygen is examined in acidic solution. The MWCNT-supported particles exhibit excellent electrocatalytic activity. The electrocatalytic reduction of oxygen follows the peroxide pathway. Surface morphology and coverage of particles on the nanotubes control the electrocatalytic activity. The large surface area and high catalytic activity of the MWCNT-supported nanoparticles facilitate the electrocatalytic reactions at a favorable potential.     

Functionalized carbon nanotube-bienzyme biocomposite for amperometric sensing

An approach to design a biocomposite bienzyme biosensor with the aim of evaluating its suitability as an amperometric sensor using functionalized multiwalled carbon nanotubes (MWCNTs) is presented. The biosensor is based on a bienzyme-channelling configuration, employing the enzymes glucose oxidase (GOx) and horseradish peroxidase (HRP), which were immobilized with toluidine blue (TB) functionalized MWCNTs. The proposed method demonstrates an easy electron transfer between the immobilized enzymes and the electrode via functionalized MWCNTs in a Nafion matrix. Co-immobilization of GOx and HRP was employed to establish the feasibility of fabricating highly effective bienzyme-based biosensors for low-level glucose determination. Bienzyme immobilized TB functionalized MWCNTs were attached to a glassy carbon electrode, and the electrochemical behavior of the sensor was studied using electrochemical impedance spectroscopy, cyclic voltammetry and chronoamperometry. The excellent electrocatalytic activity of the biocomposite film resulted in the detection of glucose under reduced over potential with a wider range of determination from 1.5 × 10⁻⁸ M to 1.8 × 10⁻³ M and with a detection limit of 3 × 10⁻⁹ M. The sensor showed a short response time (within 2 s), good stability and anti-interferant ability. The proposed biosensor exhibits good analytical performance in terms of repeatability, reproducibility and shelf-life stability.     

Effective adhesion of Pt nanoparticles on thiolated multi-walled carbon nanotubes and their use for fabricating electrocatalysts

Multi-walled carbon nanotubes (MWCNTs) were functionalized via π − π interaction with benzyl mercaptan. The subsequent bonding of thiol groups with Pt offered strong adhesion of Pt nanoparticles on MWCNT surface. Thermal treatment was introduced as the essential step of the catalyst preparation. The structure and morphology of the resulting Pt/MWCNT composite were characterized by transmission electron microscopy and X-ray diffraction, the results show that Pt nanoparticles were highly dispersed and effectively adhered on MWCNTs. The excellent electrocatalytic activity of the Pt/MWCNT composite for the oxidation of methanol was demonstrated by cyclic voltammetry.     

Ultrasonic synthesis of highly dispersed Pt nanoparticles supported on MWCNTs and their electrocatalytic activity towards methanol oxidation

A new method of synthesis of highly dispersed Pt nanoparticles with large catalytic surface area on multi-walled carbon nanotubes (MWCNTs) under high-intensity ultrasonic field was developed. The method, with low processing temperature at 25 °C, took only about 5 min. The surface characterization of MWCNTs was carried out by fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy methods. The electrochemical surface area and pore volume of MWCNTs were also examined. The result showed that functional groups of the MWCNTs which favored the high loading and high dispersion of particles and electrochemical surface area of MWCNTs were reinforced in the case of high-intensity ultrasonic field. The Pt/MWCNT catalysts were characterized by energy dispersion X-ray spectra analysis (EDX), transmission electron microscopy (TEM) and X-ray diffraction (XRD) measurements. The prepared Pt nanoparticles were uniformly dispersed on the MWCNT surface. The mean size of Pt particles was 3.4 ± 0.2 nm. The electrocatalytic properties of Pt/MWCNT composites and kinetic characterization for methanol electro-oxidation were investigated by cyclic voltammetry. The Pt/MWCNT catalysts prepared for 5 min in ultrasonic field present excellent electrochemical activities. The schematic of the reaction was also introduced.     

Preparation of high loading Pt nanoparticles on ordered mesoporous carbon with a controlled Pt size and its effects on oxygen reduction and methanol oxidation reactions

A series of ordered mesoporous carbon (OMC) supported Pt (Pt/OMC) catalysts with a controlled Pt size from 2.7 to 6.7 nm at high Pt loading around 60 wt.% have been prepared and their electrocatalytic activities for the electrode reactions relevant to the direct methanol fuel cells have been investigated. The Pt/OMC catalysts with a high dispersion (Pt size around 3 nm) could be prepared by the use of a modified, sequential impregnation–reduction method. The Pt/OMC catalysts containing larger Pt particles were obtained by increasing reduction temperature under hydrogen flow and Pt loading, and by performing impregnation–reduction in a single cycle. The oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) activities of Pt/OMC catalysts as a function of Pt size were investigated at room temperature in 0.1 M HClO₄ and (0.1 M HClO₄ + 0.5 M methanol), respectively. The specific activity of Pt/OMC for ORR steeply increased up to 3.3 nm and became independent of Pt size from 3.3 to 6.7 nm, and the mass activity curve exhibited maximum activity at 3.3 nm. The MOR activity of Pt/OMC also exhibited the similar trend with the ORR activity, as the maximum of mass activity was also found at 3.3 nm. The results of the present work indicate that the Pt catalysts of ca. 3 nm is an optimum particle size for both ORR and MOR, and this information may be translated into design of high performance membrane electrode assembly.     

Electrochemical and physicochemical characterizations of methanol-tolerant platinum-macrocycle cocatalyst for oxygen reduction

Carbon supported iron tetraphenylporphyrin and platinum (FeTPP-Pt/C) cocatalysts were prepared by supporting FeTPP on Pt/C followed by a heat-treatment at temperatures ranging from 300 to 900 °C. The relationship of the electrocatalytic properties of cocatalysts and the heat-treatment temperature was studied in detail. Compared to the Pt/C counterpart, it was found that heat-treated cocatalysts exhibit a comparable catalytic activity for oxygen reduction reaction (ORR) and lower reactivity for methanol oxidation reaction (MOR). The cocatalysts treated at ca. 500-700 °C are, in our experimental conditions, the best ORR catalysts with high methanol tolerance. The physicochemical characterizations of the cocatalysts, Pt/C and FeTPP/C were performed by ICP-AES, TEM (EDX), XPS, and XRD techniques. Combined with the electrochemical results, it was revealed that the presence of Fe-N-based species surrounding the Pt sites could greatly hinder the MOR.     

Fast and clean functionalization of carbon nanotubes by dielectric barrier discharge plasma in air compared to acid treatment

Multi-walled carbon nanotubes (MWCNTs) have been functionalized by a dielectric barrier discharge plasma in air and compared to those functionalized in HNO₃. The MWCNTs were prepared by chemical vapor deposition of xylene using ferrocene as a catalyst at 850 °C. Air oxidation followed by acid treatment was used to purify the MWCNTs, which were then annealed in helium. The MWCNTs were functionalized in air in a plasma reactor at room temperature. Quantitative analyses of gases evolved during the temperature programmed desorption of the functionalized nanotubes were carried out using Fourier transform infrared spectroscopy and gas chromatography. The influence of plasma parameters, including power in the range of 8-90 W and treatment time in the range of 1-9 min, on the number of the functional groups was investigated. It is shown that the extent of functionalization increases with increasing discharge power, provided that the exposure time of the MWCNTs in the plasma atmosphere does not exceed a certain period of time. Compared to acid treatment, plasma functionalization offers the advantages of much shorter treatment time, and produces less damage.     

On the influence of Pt particle size on the PEMFC cathode performance

Colloidal suspensions of almost spherical and crystalline Pt nanoparticles between 1.6 and 2.6 nm in diameter and with narrow size distribution were synthesized using the phase transfer method (PTM) with alkylamines, C_nNH₂, as stabilizing agents. Batches of such homogenous Pt-C_nNH₂ (n = 8, 12) nanocrystals were deposited onto Vulcan XC-72 carbon powder, and the activity for the oxygen reduction reaction (ORR) of this series of Pt/C materials was evaluated under PEMFC conditions. The aim was to elucidate whether this type of stabilized Pt nanoparticles were as active for the ORR as a corresponding commercial Pt/C material, and if any difference in mass activity could be observed between catalysts with different Pt particle size. In the PEMFC experiments, i.e. voltammetry in oxygen and nitrogen, it was found that, after an initial electrode activation, the ORR activity of the catalysts prepared from the alkylamine-stabilized Pt nanoparticles deposited on carbon was as high as that of the employed commercial reference catalyst. In fact, all samples in the Pt/C series showed high and very similar ORR activity normalized to Pt-loading, without significant dependence on the initial Pt particle size. However, pre- and post-electrochemical characterization of the Pt/C material series with TEM showed that structural changes of the Pt nanoparticles occurred during electrochemical evaluation. In all samples studied the mean Pt particle size increased during the electrochemical evaluation resulting in decreased differences between the samples explaining the observed similar ORR performance of the different materials. These results emphasize the necessity of post-operation characterization of fuel cell catalysts when discussing electrocatalytic activity. In addition, employing complex preparation efforts for lowering the Pt particle size below 3 nm may have limited practical value unless the particles are stabilized from electrochemical sintering.     

Functionalization of carbon nanotubes by an effective intermittent microwave heating-assisted HF/H2O2 treatment for electrocatalyst support of fuel cells

A method is developed to effectively functionalize carbon nanotubes (CNTs) by intermittent microwave heating (IMH)-assisted HF/H₂O₂ solution treatment. CNTs functionalized by IMH-assisted HF/H₂O₂ solution treatment (CNTs-HF/H₂O₂) are characterized by high oxygen-containing groups and high graphitization degree, as compared with CNTs treated by HF (CNTs-HF) or by IMH-assisted H₂O₂ solution treatment without prior HF treatment (CNTs-H₂O₂). Pt supported on CNTs-HF/H₂O₂ (Pt/CNTs-HF/H₂O₂) has an average particle size of 2.8 nm, smaller than 2.9 nm for Pt supported on CNTs-HF, 3.3 nm for Pt supported on CNTs-H₂O₂ and 4.0 nm for Pt supported on pristine CNTs. Pt/CNTs-HF/H₂O₂ electrocatalysts display a high electrochemical surface area, high Pt utilization efficiency, a superior electrocatalytic and mass activity for the O₂ reduction reaction (ORR) with respect to other catalyst samples in the present study. The results demonstrate the efficiency and effectiveness of the IMH-assisted HF/H₂O₂ solution methods for the functionalization of CNTs, and the method could be easily scaled-up to treat CNTs in large quantities.     

A new amperometric glucose biosensor based on platinum nanoparticles/polymerized ionic liquid-carbon nanotubes nanocomposites

A new amperometric glucose biosensor has been developed based on platinum (Pt) nanoparticles/polymerized ionic liquid-carbon nanotubes (CNTs) nanocomposites (PtNPs/PIL-CNTs). The CNTs was functionalized with polymerized ionic liquid (PIL) through directly polymerization of the ionic liquid, 1-vinyl-3-ethylimidazolium tetrafluoroborate ([VEIM]BF₄), on carbon nanotubes and then used as the support for the highly dispersed Pt nanoparticles. The electrochemical performance of the PtNPs/PIL-CNTs modified glassy carbon (PtNPs/PIL-CNTs/GC) electrode has been investigated by typical electrochemical methods. The PtNPs/PIL-CNTs/GC electrode shows high electrocatalytic activity towards the oxidation of hydrogen peroxide. Taking glucose oxidase (GOD) as the model, the resulting amperometric glucose biosensor shows good analytical characteristics, such as a high sensitivity (28.28 μA mM⁻¹ cm⁻²), wide linear range (up to 12 mM) and low detection limit (10 μM).     

Formation of gold nanoparticles on multiwalled carbon nanotubes by thermal evaporation

Multiwalled carbon nanotubes (MWCNTs) were grown on W substrates by chemical vapor deposition and modified with Au nanoparticles by thermal evaporation. The resulting hybrid structures were investigated by TEM to determine the effects of evaporation rate, nominal film thickness, and substrate temperature on the nanoparticle size and distribution. The results demonstrate that as-grown MWCNTs can be used as a support for well distributed Au nanoparticles, with the size and distribution on the carbon nanotubes being primarily influenced by the nominal film thickness. The observed structures ranged from small 4 nm diameter spherical particles to 150 nm long wire-like structures. Depositions with substrates at 25 °C and 400 °C resulted in similar particle structures, except for the highest amount of deposited Au.     

Lithographically defined site-selective growth of Fe filled multi-walled carbon nanotubes using a modified photoresist

Partially Fe filled multi-walled carbon nanotubes (MWCNTs) were grown by chemical vapor deposition with propane at 850 °C using a simple mixture of iron (III) acetylacetonate (Fe(acac)₃) powder and conventional photoresist. Scanning electron microscopy revealed that catalytic nanoparticles with an average diameter of 70 nm are formed on the Si substrate which governs the diameter of the MWCNTs. Transmission electron microscopy shows that the nanotubes have a multi-walled structure with partial Fe filling. A site-selective growth of partially Fe filled MWCNTs is achieved by a simple photolithographic route.     

Electroreduction of oxygen on Pt nanoparticle/carbon nanotube nanocomposites in acid and alkaline solutions

The kinetics of O₂ reduction on novel electrocatalyst materials deposited on carbon substrates were studied in 0.5 M H₂SO₄ and in 0.1 M NaOH solutions using the rotating disk electrode (RDE) technique. Pt nanoparticles (PtNP) supported on single-walled (PtNP/SWCNT) and multi-walled carbon nanotubes (PtNP/MWCNT) were prepared using two different synthetic routes. Before use, the CNTs were cleaned to minimize the presence of metal impurities coming from the catalyst used in the synthesis of this material, which can interfere in the electrochemical response of the supported Pt nanoparticles. The composite catalyst samples were characterised by transmission electron microscopy (TEM) showing a good dispersion of the particles at the surface of the carbon support and an average Pt particle size of 2.4 ± 0.7 nm in the case of Pt/CNTs prepared in the presence of citrate and of 3.8 ± 1.1 nm for Pt/CNTs prepared in microemulsion. The values of specific activity (SA) and other kinetic parameters were determined from the Tafel plots taking into account the real electroactive area of each electrode. The electrodes exhibited a relatively high electrocatalytic activity for the four-electron oxygen reduction reaction to water.     

Synthesis of Pd-Sn nanoparticles by ultrasonic irradiation and their electrocatalytic activity for oxygen reduction

Nanoparticles of Pd-Sn were prepared under various conditions by applying ultrasonic irradiation, and their electrocatalytic activity for oxygen reduction was evaluated in 0.5 M KOH. The average size of Pd-Sn nanoparticles thus prepared was about 3-5 nm. The Pd in Pd-Sn nanoparticles was found to be mostly in the metallic state. The electrocatalytic activity of the Pd-Sn nanoparticles for the oxygen reduction reaction (ORR) is greater than Pt or Pd nanoparticles in alkaline media. The molar ratio of Pd to Sn metal ions in the synthesizing solution, their initial concentrations, the concentration of ethanol, which increases primary hydrogen radicals during sonolysis, and the concentration of citric acid were found to affect the size distribution of the Pd-Sn nanoparticles, and therefore, those factors controlled the electrocatalytic activity for ORR. Particularly, the concentration of citric acid was found to be important for controlling the surface property on Pd-Sn particles to adjust the electrocatalytic activity for ORR.     

Catalytic activity, stability and structure of multi-walled carbon nanotubes in the wet air oxidation of phenol

Multi-walled carbon nanotubes (MWCNTs), with no supported metal, were used as catalysts in the wet air oxidation of phenol. The MWCNTs were chemically modified using HCl or HNO₃-H₂SO₄. They were characterized by BET, SEM, TEM, FT-IR and Raman spectroscopy. The functionalized MWCNTs exhibited both high activity and good stability in the wet air oxidation of phenol. At 160 °C and 2.0 MPa with an initial phenol concentration of 1000 mg/L, 100% phenol conversion and 76% total organic carbon abatement could be achieved after 120 min reaction. Upon reaction, the short chain carboxylic acids mainly maleic/fumaric, malonic, oxalic, formic and acetic acid were produced. Surface functional groups (-COOH) were shown to play a key role in the high activity of the functionalized MWCNTs. A mechanism for the CWAO of phenol was proposed.     

Fabrication of CNTs with controlled diameters and their applications as electrocatalyst supports for DMFC

A facile synthesis procedure based on chemical vapor deposition (CVD) process has been developed to fabricate carbon nanotubes (CNTs) with controlled diameters and high yields utilizing Fe-containing ordered hexagonal mesoporous silicas (HMSs) such as MCM-41 and SBA-15 having varied pore sizes as the catalysts as well as the templates. It is found that unlike Fe/HMS catalysts prepared by co-precipitation method, samples prepared by the impregnation method gave rise to multi-wall CNTs with uniform diameters, which were largely dictated by the pore size of the Fe/HMS catalysts. Among these uniform MWCNTs, sample with a larger diameter (≥ 8 nm) was found to be more favorable as support for Pt catalyst, leading to a homogeneous dispersion of metal nanoparticles. Consequently, the Pt/CNT electrocatalysts so prepared gave rise to superior methanol oxidation activities as well as tolerances for CO poisoning compared to Pt supported on commercial single-wall CNT (Pt/SWCNT) and XC-72 activated carbon (Pt/XC-72) having a similar metal loading.     

Functionalization of multi-walled carbon nanotubes with furan and maleimide compounds through Diels-Alder cycloaddition

Functionalization of multi-walled carbon nanotubes (MWCNTs) is performed through Diels-Alder (DA) reaction, using either furfuryl alcohol (a diene) or N-(4-hydroxyphenyl)maleimide (NHMI, a dienophile) as a functionalization agent. The structures of the functionalized MWCNTs are characterized with Fourier-transform infrared spectroscopy and Raman spectroscopy. Thermogravimetric analysis results also demonstrate the presence of organic portions of the functionalized MWCNTs. The DA reaction is further applied to incorporate polymer chains onto MWCNT surfaces, using a polyamide with maleimide pendent groups. Transmission electron microscopy images show the presence of a polymer layer of about 2-5 nm around the polymer modified MWCNTs.     

Au@Pt core-shell nanoparticles supported on multiwalled carbon nanotubes for methanol oxidation

Au@Pt core-shell nanoparticles were synthesized by a simple one-step ultraviolet irradiation method and were then assembled on functionalized multiwalled carbon nanotubes (MWCNTs) surface. This new type of Au@Pt/MWCNTs composite catalysts was characterized by UV–vis spectrometry, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning TEM, HRTEM, and electrochemical techniques. The results revealed that the Au@Pt nanoparticles with an average diameter less than 5 nm were well coated on the MWCNTs surface. As compared with commercial Pt/C catalysts, the Au@Pt/MWCNTs prepared using Au/Pt atomic ratio of 1:1 exhibited distinctly higher activity and better stability toward methanol oxidation in alkaline media.