Electrocatalytic activity and durability study of carbon supported Pt nanodendrites in polymer electrolyte membrane fuel cells

In this paper, Pt nanodendrites are synthesized, and their use as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells is examined. When the Pt nanoparticles are shape-controlled in a dendritic form, the Pt nanoparticles exhibit a high mass activity that is nearly twice as high as the commercial Pt/C catalyst for the oxygen reduction reaction. This high activity is only achieved when the Pt nanodendrites are supported on carbon. The unsupported Pt nanodendrites exhibit very poor catalytic activity due to the limited accessibility of the active sites in the catalyst layer of the fuel cells. Based on the durability study of Pt nanodendrites, however, the dendritic structure is not stable during repeated potential cycling test and its structure collapse is the primary reason for the performance loss in the fuel cells.     

Oxygen reduction on carbon supported Pt-W electrocatalysts

The catalytic activity of Pt-W electrocatalysts towards oxygen reduction reaction (ORR) was studied. Pt-W/C materials were prepared by thermolysis of tungsten and platinum carbonyl complexes in 1-2 dichloro-benzene during 48 h. The precursors were mixed to obtain relations of Pt:W: 50:50 and 80:20%w, respectively. The Pt carbonyl complex was previously synthesized by bubbling CO in a chloroplatinic acid solution. The synthesized materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV) and a rotating disk electrode (RDE). The results show that both materials (Pt₅₀W₅₀/C and Pt₈₀W₂₀/C) have a crystalline phase associated with metallic platinum and an amorphous phase related with tungsten and carbon. The particle size of the electrocatalysts depends on the relationship between platinum and tungsten. Finally, both materials exhibit catalytic activity for oxygen reduction.     

Pt overgrowth on carbon supported PdFe seeds in the preparation of core-shell electrocatalysts for the oxygen reduction reaction

In this study, a novel core-shell structured Pd₃Fe@Pt/C electrocatalyst, which is based on Pt deposited onto carbon supported Pd₃Fe nanoparticles, is prepared for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). The carbon supported Pd₃Fe nanoparticles act as seeds to guide the growth of Pt. The formation of the core-shell structured Pd₃Fe@Pt/C is confirmed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and electrochemical characterization. The higher surface area of the synthesized catalyst suggests that the utilization of Pt in the Pd₃Fe@Pt/C catalyst is higher than that in Pt/C. Furthermore, better electrocatalytic performance than that of Pt/C and Pd₃Fe/C catalyst is observed in the ORR which follows a four-electron path. Consequently, the results indicate that the Pd₃Fe@Pt/C catalyst could be used as a more economically viable alternative for the ORR of PEMFCs.     

Enhanced electrocatalytic activity of platinum supported on nitrogen modified ordered mesoporous carbon

Nitrogen-modified ordered mesoporous carbon is synthesized via the 900 °C carbonization of polyaniline-coated mesoporous carbon. The electronic states of nitrogen atoms are investigated by XPS technique. Pyridinic nitrogen and quaternary nitrogen generate disorders and curvatures on the surface of graphitic carbon layers with nitrogen atoms replacing carbon atoms at the edges and the interior of carbon stacking, and thus offering beneficial anchoring sites for PtCl₆²⁻ ions. Pyridinic nitrogen and pyrrolic nitrogen offer p electrons to the sp² hybridized graphitic carbon layers, decreasing the inner electrical resistance of the catalytic carbon layer, enhancing the rate of proton diffusion, and transporting more free electrons to oxidative platinum. Due to the advantageous modification of the electronic structure of carbon atoms, platinum nanoparticles with a narrow size distribution are homogenously dispersed onto the surface of nitrogen-modified ordered mesoporous carbon, as evidenced by TEM images. Electrochemical tests show that the samples loaded platinum calcined at the 900 °C exhibit the optimum loading performance among as-made catalysts and a gradually decreased decay in electro-catalytic activity with time, with the current density stabilized at 3.64 mA cm⁻², which is far higher than that of mesoporous carbon (0.15 mA cm⁻²).     

Nontrivial role of carbon nanofibers morphology in binderless Pt nanocatalyst supported electrode

Similar to conventional composite electrodes, developing binderless-based carbon nanostructured (CNs) electrodes for fuel cells requires particularly the optimisation of both the morphology and the density of the CNs. In this work, carbon nanofibers (CNFs) have been optimised and used as catalyst support for Pt nanoparticles (NPs). The nontrivial role of the CNFs on the catalytic behavior is clearly demonstrated. We have shown that for a similar amount, morphology and dispersion of the Pt NPs fabricated onto CNFs, the density of the latter and to a lesser extent their diameter are the main factors influencing the catalytic activity. For the particular case of CNFs considered in this work, an optimum activity toward methanol fuel cell reaction was obtained when Pt NPs were supported with CNFs synthesized with a C₂H₂/Ar ratio of 0.31.     

Preparation and characterization of Pt supported on graphene with enhanced electrocatalytic activity in fuel cell

Pt nanoparticles are deposited onto graphene sheets via synchronous reduction of H₂PtCl₆ and graphene oxide (GO) suspension using NaBH₄. Lyophilization is introduced to avoid irreversible aggregation of graphene (G) sheets, which happens during conventional drying process. Pt/G catalysts reveal a high catalytic activity for both methanol oxidation and oxygen reduction reaction compared to Pt supported on carbon black (Pt/C). The performance of Pt/G catalysts is further improved after heat treatment in N₂ atmosphere at 300 °C for 2 h, and the peak current density of methanol oxidation for Pt/G after heat treatment is almost 3.5 times higher than Pt/C. Transmission electron microscope (TEM) images show that the Pt particles are uniformly distributed on graphene sheets. X-ray photoelectron spectroscopy (XPS) results demonstrate that the interaction between Pt and graphene is enhanced during annealing. It suggests that graphene has provided a new way to improve electrocatalytic activity of catalyst for fuel cell.     

Ultrathin nitrogen doped carbon layer stabilized Pt electrocatalyst supported on N-doped carbon nanotubes

The enhancements in fuel cell performance and durability are crucial for the commercialization of polymer electrolyte fuel cells (PEFCs). Here, we deposit platinum nanoparticles on nitrogen doped carbon nanotubes (N-CNT) and continuously coat the electrocatalyst with nitrogen doped carbon (NC) layer derived from the carbonization of poly(vinyl pyrrolidone) (PVP). The NC-coated electrocatalyst shows stable electrochemical surface area (ECSA) during the potential cycling from 0.6 V to 1.0 V vs. RHE; while, the commercial and non-coated electrocatalysts lose 50% and 33% of initial ECSAs, respectively. Moreover, the NC-coated electrocatalyst shows higher oxygen reaction reduction (ORR) activity compared to non-coated electrocatalyst due to the additional nitrogen atoms in the electrocatalyst. The maximum power density of the coated electrocatalyst reaches 676 mW cm^?2 with Pt loading of 0.1 mg cm^?2, indicating that the mass power density of the electrocatalyst is one of the highest values in recently published literature. The NC layer is significantly important for simultaneous enhancements in durability and fuel cell performance.     

Flame synthesis of carbon nanostructures on stainless steel anodes for use in microbial fuel cells

Microbial fuel cells (MFCs) offer a promising alternative energy technology, but suffer from low power densities which hinder their practical applicability. In order to improve anodic power density, we deposited carbon nanostructures (CNSs) on an otherwise plain stainless steel mesh (SS-M) anode. Using a flame synthesis method that did not require pretreatment of SS-M substrates, we were able to produce these novel CNS-enhanced SS-M (CNS-M) anodes quickly (in a matter of minutes) and inexpensively, without the added costs of chemical pretreatments. During fed batch experiments with biomass from anaerobic digesters in single-chamber MFCs, the median power densities (based on the projected anodic surface area) were 2.9 mW m⁻² and 187 mW m⁻² for MFCs with SS-M and CNS-M anodes, respectively. The addition of CNSs to a plain SS-M anode via flame deposition therefore resulted in a 60-fold increase in the median power production. The combination of CNSs and metallic current collectors holds considerable promise for power production in MFCs.     

Improved thermal stability,properties, and electrocatalytic activity of sol-gel silica modified carbon supported Pt catalysts

An improvement in the thermal properties of catalysts used in PEM type fuel cells was achieved by siliceous additions. A sol-gel method was developed to deposit controlled amounts of a siliceous composition on Vulcan XC72 carbon (VC). The catalysts designated as Pt/(VC–SiO₂) were obtained by reduction of H₂PtCl₆ in an aqueous solution with NaBH₄. A nanoscale Pt particle formation was observed on the support materials having a range 2.7–5.1 nm. The thermal stability study for Pt/(VC–SiO₂) catalysts demonstrated that the presence of a siliceous phase conferred an increased resistance to Pt nanoparticle agglomeration at 600 °C. In addition, a decrease in low temperature mass loss was observed. Electrochemical properties evaluated by cyclic voltammetry coupled with a rotating disk electrode (RDE) showed improvements with moderate SiO₂ addition. The synthesized catalysts performance was as good as the performance of the control catalyst (46 wt% Pt/VC, Tanaka). Unfortunately, fuel cell performance experiments showed an unwanted hydrophillic behavior of carbon-silica composite aerogel supports at high current density values. The C–SiO₂ aerogel composite catalyst support seems suitable for low current applications.     

Pd nanoparticles supported on PDDA-functionalized carbon black with enhanced ORR activity in alkaline medium

Pd/C catalyst with small particle size, high dispersion and high wt.% of metal was in situ synthesized by a simple aqueous phase reduction method. Poly(diallyldimethylammonium chloride) PDDA-functionalized carbon black was used as a support material for the in situ deposition of Pd nanoparticles by means of electrostatic attraction. The catalysts were characterized by transmission electron microscopy, X-ray diffractometry and X-ray photoelectron spectroscopy, cyclic voltammetry and rotating disc electrode test. The results indicated that Pd nanoparticles with an average size of 2.09 nm were uniformly dispersed onto the carbon black with a metal weight percentage of ∼30 wt.%. The prepared Pd/C catalyst has showed remarkably larger electrochemical surface area and higher and more stable ORR activity as compared to commercial Pd/C catalyst and commercial Pt/C catalyst in alkaline media, which was believed to be a promising alternative to Pt-based catalyst used in alkaline fuel cell.     

Synthesis and characterization of Pt nanoparticles on sulfur-modified carbon nanotubes for methanol oxidation

Pt nanoparticles supported on carbon nanotubes (Pt/CNTs) have been synthesized from sulfur-modified CNTs impregnated with H₂PtCl₆ as Pt precursor. The dispersion and size of Pt nanoparticles in the synthesized Pt/CNT nanocomposites are remarkably affected by the amount of sulfur modifier (S/CNT ratio). The results of X-ray diffraction and transmission electron microscopy indicate that an S/CNT ratio of 0.3 affords well dispersed Pt nanoparticles on CNTs with an average particle size of less than 3 nm and a narrow size distribution. Among different catalysts, the Pt/CNT nanocomposite synthesized at S/CNT ratio of 0.3 showed highest electrochemically active surface area (88.4 m² g⁻¹) and highest catalytic activity for methanol oxidation reaction. The mass-normalized methanol oxidation peak current observed for this catalyst (862.8 A g⁻¹) was ∼ 6.5 folds of that for Pt deposited on pristine CNTs (133.2 A g⁻¹) and ∼ 2.3 folds of a commercial Pt/C (381.2 A g⁻¹). The results clearly demonstrate the effectiveness of a relatively simple route for preparation of sulfur-modified CNTs as a precursor for the synthesis of Pt/CNTs, without the need for tedious pretreatment procedures to modify CNTs or complex equipments to achieve high dispersion of Pt nanoparticles on the support.     

High stability of oxidation of methanol catalyzed by Pt supported by oxygen-incorporated bamboo-shaped CNTs grown directly on carbon cloth

Bamboo-shaped CNTs in which oxygen was incorporated were directly grown on carbon cloth (O-BCNT-CC) by microwave plasma-enhanced chemical vapor deposition. Mixed precursors CH₄/H₂/N₂/O₂ were introduced during the growth process. For comparison, bamboo-shaped CNTs without incorporated oxygen were prepared herein (BCNT-CC). Then, platinum catalysts were prepared on the as-grown O-BCNT-CC (Pt/O-BCNT-CC) and the as-grown BCNT-CC (Pt/BCNT-CC). According to TEM-EELS oxygen mapping, O atoms were uniformly distributed on the O-BCNT surface. Methanol oxidation was performed using Pt/O-BCNT-CC and Pt/BCNT-CC in 1 M methanol and 1 M sulfuric acid by cyclic voltammetry. In the initial cycle, the peak current density of Pt/O-BCNT-CC was almost equal to that of Pt/BCNT, indicating that both had nearly equal activities in the beginning. After 300 cycles, the peak current of Pt/BCNT-CC was reduced to half of the initial peak current owing to platinum-poisoning; however, the peak current of Pt/O-BCNT-CC decayed less. In Pt/O-BCNT-CC, the oxygen-containing functional groups affect the orientation index of crystalline Pt, providing a means of oxidizing methanol and stabilizing Pt catalysts for the long-term.     

Microstructure effect of carbon nanofibers on Pt/CNFs electrocatalyst for oxygen reduction

Pt nanoparticles supported on microstructure controllable carbon nanofibers (CNFs), i.e. platelet CNFs (p-CNFs), fish-bone CNFs (f-CNFs) and tubular CNFs (t-CNFs), are synthesized, and CNF microstructure effect on physio-chemical and oxygen reduction reaction (ORR) properties of Pt/CNFs is investigated. The physio-chemical properties of different Pt/CNFs electrocatalysts are characterized by high resolution transmission electron microscope (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). HRTEM results exhibit Pt nanoparticles are uniformly dispersed on CNF surface, and Pt/p-CNFs shows a smaller particle size compared with those other catalysts. XPS results reveal that CNF microstructure can influence the metal–support interaction, and Pt/p-CNFs have a higher binding energy compared with Pt/t-CNFs. From cyclic voltammetric studies, it is found that Pt/p-CNFs performed a higher ORR activity than Pt/f-CNFs and Pt/t-CNFs, which may be resulted from the smaller Pt particle size and the stronger metal–support interaction of Pt/p-CNFs. Furthermore, CNF microstructure can influence the reaction process. ORR on Pt/p-CNFs or Pt/f-CNFs is controlled by diffusion process, while on Pt/t-CNFs is surface reaction controlled.     

Fuel cell performance of Pt electrocatalysts supported on carbon nanocoils

Carbon nanocoils (CNCs) synthesized via the catalytic graphitization of resorcinol-formaldehyde gel were investigated as an electrocatalyst support in PEMFC anodes. Their textural and physical properties make them a highly efficient catalyst support for anodic hydrogen oxidation in low temperature PEMFC.     

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.     

In situ ion exchange preparation of Pt/carbon nanotubes electrode: Effect of two-step oxidation of carbon nanotubes

The in situ ion exchange method has been employed to prepare carbon nanotubes (CNT) supported Pt electrode, in which CNT is functionalized with two-step oxidation, namely electrochemical oxidation and chemical oxidation. X-ray photoelectron spectroscopy (XPS) confirms that two-step oxidation produces more carboxylic acid groups. Transmission electron microscopy (TEM) shows that Pt nanoparticles are highly dispersed on the CNT surface. Electrochemical measurements show that the resultant Pt/CNT electrode treated by two-step oxidation exhibits the largest electrochemical surface area and the highest activity for oxygen reduction reaction (ORR) among the investigated electrodes. This can be attributed to the fact that the two-step oxidation treatment produces more carboxylic acid groups which is the determining factor for Pt loading and dispersion via ion-exchange.     

Simultaneous formation of nitrogen and sulfur-doped carbon nanotubes-mesoporous carbon and its electrocatalytic activity for oxygen reduction reaction

Nitrogen and sulfur dual doped-carbon nanotubes-mesoporous carbon (D-CNTs-MPC) composite is prepared simultaneously and is used in alkaline media as an electrocatalyst for oxygen reduction reaction (ORR). D-CNTs-MPC is synthesized by casting method using nano-CaCO₃ as a template, and binuclear cobalt phthalocyanine hexasulfonate as a carbon, nitrogen and sulfur precursor as well as the catalyst for growth of CNTs. D-CNTs-MPC possesses short CNTs adhering to loosely packed carbon with mesopores. Moreover, nitrogen and sulfur are doped into the carbon framework without addition of other heteroatom-containing precursor. The electrochemical behavior shows that D-CNTs-MPC is an active, methanol-tolerant and stable electrocatalyst for ORR.     

The influence of carbon nanofiber support properties on the oxygen reduction behavior in proton conducting electrolyte-based direct methanol fuel cells

Platinum nanoparticles supported on fishbone carbon nanofibers (CNFs) were synthesized and studied for the oxygen reduction reaction (ORR). The crystalline and textural properties of the CNFs were modified by synthesizing them at different temperatures, allowing the comparison of supports with either improved graphitization degree or improved porosity. A carbon black (Vulcan XC-72R) was used for comparison. Half-cell studies determined that the ORR activity is enhanced when using a CNF with improved graphitization, in contrast with CNFs with better textural properties such as surface area or pore volume. The catalysts were tested at the cathode of a direct methanol fuel cell corroborating the suitability of using highly graphitic CNFs, and a similar behavior was found in comparison with the state of the art carbon black used in this field.     

High efficiency platinum nanoparticles based on carbon quantum dot and its application for oxygen reduction reaction

1. Download high-res image (192KB)
2. Download full-size image

     

High catalytic performance and stability of Pt/C using acetic acid functionalized carbon

Carbon (Vulcan XC-72, Cobat Corp.) is pretreated using acetic acid (HAC) before the Pt deposition by microwave assisted glycol method. TEM and XRD results indicate that 3 nm Pt nano-particles are uniformly dispersed on the surface of modified XC-72. In order to examine the interaction between Pt nano-particles and carbon, Pt/C-HAC and commercial Pt/C (Johnson Matthey Corp.) are calcined at 500 °C for 2 h under nitrogen atmosphere. The average Pt particle size of Pt/C-HAC after calcination is only 10–12 nm in diameter while commercial Pt particles grow up to 25–35 nm with a broad size distribution. Meanwhile, electrochemical studies of Pt/C-HAC reveal higher activity and stability for both methanol oxidation and oxygen reduction than that of Pt/C-JM. The pore structure and surface composition are investigated by BET and XPS, which implies that much microporous structure and carbonyl functional groups on carbon surface are obtained after HAC treatment. The high catalytic performance and stability might mainly be due to the strong interaction between Pt nano-particles and carbon by carbonyl functional groups. Therefore, HAC treatment is proved to be a facile and effective method for carbon as the support for Pt as fuel cell catalyst.