Characterization and evaluation of Pt-Ru catalyst supported on multi-walled carbon nanotubes by electrochemical impedance

In this work the authors present the results of a systematic characterization and evaluation of the carbon nanotube supported Pt-Ru (Pt-Ru/CNT) for its use as methanol oxidation catalyst. Its activity was compared with that of Pt and Pt-Ru catalysts supported on Vulcan and synthesized from carbonyl precursors, and another commercial Pt-Ru catalyst. The cyclic voltammetry, CO stripping and electrochemical impedance techniques were employed to determine the electrocatalytic activity of the catalysts. The electrochemical studies were performed in 0.5 M H₂SO₄ containing different concentrations of methanol (0.05–1 M). The results showed a noticeable influence of the catalyst support (CNT) on the performance of the catalyst for CO oxidation. The electrochemical impedance studies allowed us to separate the different steps in the methanol oxidation reaction and to control these steps or reactions by varying the applied potential and the methanol concentration. At low methanol concentration and potentials the de-hydrogenation of methanol predominated. But, at high potential and methanol concentrations, the CO oxidation predominated. These results allowed us to clearly describe at what potential and concentration ranges the bi-functional effect of Ru becomes evident. Our results indicated that the CO oxidation occurs both on Pt and Ru. Compared to other catalysts, Pt-Ru supported on carbon nanotubes showed superior catalytic activity for CO and methanol oxidation.     

MOF-derived N-doped carbon coated CoP/carbon nanotube Pt-based catalyst for efficient methanol oxidation

Designing rational nanostructures of metal-organic frameworks to speed up the methanol oxidation reaction and promote their application in methanol oxidation is highly desired but still remains a great challenge. In this study, we report a novel N-doped carbon coated CoP nanoparticles/carbon nanotube Pt-based catalyst (Pt–CoP-NCZ/CNT). This composite is produced through in situ growth of CoZn-ZIF on carbon nanotubes, subsequent carbonization and phosphorization treatment and microwave-assisted Pt supporting synthesis. The high specific surface area and N-doped structure endow the prepared catalysts with ideal conditions for supporting of Pt as well as good electrical conductivity. In addition, the evaporation of Zn²⁺ in CoZn-ZIF not only makes a contribution to a higher specific surface area of the material but also is favorable for uniform distribution of CoP nanoparticles, which gives CoP nanoparticles an excellent co-catalysis effect. Thus, the composite exhibits wonderful mass activity in both acid (930 mA mg⁻¹) and alkaline (3622.5 mA mg⁻¹) environments. Furthermore, the Pt–CoP-NCZ/CNT catalyst also shows better CO tolerance and long-time stability compared with other catalysts in this study. Thereby, the fabrication of the composite catalyst makes wider application of metal-organic frameworks in methanol oxidation possible and provides inspiration for designing efficient catalysts for methanol oxidation.     

Influence of support’s oxygen functionalization on the activity of Pt/carbon xerogels catalysts for methanol electro-oxidation

Highly mesoporous carbon xerogels (CXs) were synthesized using two different resorcinol to catalyst, R/C, molar ratios and functionalized with different oxidation treatments. The synthesized carbon materials were used as supports for Pt particles, deposited by impregnation and reduction in formic acid. Both carbon supports and the catalysts prepared were characterized by means of N₂ physisorption, scanning and transmission electron microscopy, temperature programmed desorption and X-ray diffraction. The electrochemical activity of the catalysts towards the oxidation of carbon monoxide and methanol was assayed by means of cyclic voltammetry and chronoamperometry. Textural characterization of the materials prepared evidenced more developed and mesopore-enriched porous structure for the carbon xerogel prepared using the highest R/C molar ratio. Enhanced textural properties of this material led to the preparation of highly active Pt-catalysts, which showed increased tolerance to CO and higher activity in methanol electro-oxidation, in comparison to Pt-E-TEK and the catalysts prepared in an analogous way using Vulcan XC-72R carbon black as support. Functionalization treatments resulted in enhanced dispersion, lower Pt crystal size and improved catalytic performance in the case of the catalysts prepared using the carbon xerogel possessing a less developed porous structure. Pt agglomeration was found to strongly determine the activity of the catalysts prepared. At high potentials, i.e. 1 V vs. RHE, the catalyst prepared using the carbon xerogel submitted to the most stringent oxidation treatment showed the highest specific peak activity towards methanol electro-oxidation, probably due to the positive influence of the presence of oxygen surface groups in Pt-carbon interaction, in spite of the higher agglomeration extent confirmed by TEM. On the other hand, at 0.60 V vs. RHE, highest activity towards methanol electro-oxidation was determined for the catalysts prepared using the non-functionalized carbon xerogel which can be explained in terms of enhanced reactant/product diffusion together with intrinsic higher catalytic activity due to lower Pt crystal size. In any case, the activity of this catalyst prepared using a carbon xerogel as support was found to be more than 2 times higher than the one determined for Pt/E-TEK, confirming the considerable improvement of the electrocatalytic system by means of optimization of the carbon support employed.     

Carbon nanotubes supported Pt–Au catalysts for methanol-tolerant oxygen reduction reaction: A comparison between Pt/Au and PtAu nanoparticles

Two kinds of Pt–Au/CNT catalysts with different structures are prepared by synthesizing the formerly separated Pt/Au (Au separating Pt) in separate solutions, and PtAu nanoparticles in mixed solution using the borohydride reduction method with trisodium citrate as the stabilizing agent, and then depositing the metal colloid nanoparticles on the carbon nanotubes supporting material. The structural information and particle size are characterized by UV–vis absorption spectra, transmission electron microscopy (TEM), and X-ray diffraction (XRD). The results confirm the formation of Pt–Au nanoparticles with PtAu and separated Pt/Au structures. The catalytic activities for methanol oxidation reaction and oxygen reduction reaction are examined by electrochemical measurements. Compared with the Pt/CNT catalyst, the two Pt–Au/CNT catalysts show a lower overpotential for the oxygen reduction reaction in the presence of methanol, indicating a higher methanol tolerance on Au-modified Pt nanoparticles. Particularly, the Pt/Au/CNT catalyst with Au separating Pt nanoparticles structure exhibits the significantly higher methanol tolerance than PtAu/CNT catalyst. The enhanced methanol tolerance may be attributed to less methanol adsorption on Pt surface due to the effect of Au nanoparticles.     

Methanol oxidation efficiencies on carbon-nanotube-supported platinum and platinum-ruthenium nanoparticles prepared by pulsed electrodeposition

Dense carbon nanotubes (CNTs, 30-50 nm in diameter, 6-8 μm in length) were grown via a thermal chemical vapor deposition process on titanium treated carbon cloths. Catalysts in the form of either nano-scale platinum (Pt) or platinum-ruthenium (Pt-Ru) particles were then deposited on the CNT surfaces by pulse-mode potentiostatic electrodeposition. Surface morphologies of the prepared electrodes were examined by scanning electron microscopy and transmission electron microscopy. Well dispersed catalysts, Pt alone (particle sizes of 7-8 nm) or Pt-Ru (particle sizes of 3-4 nm) nanoparticles, were successfully electrodeposited on the CNT surfaces in citric acid aqueous solutions. In addition, electrochemical characteristics of the specimens were investigated by cyclic voltammetry in argon saturated sulfuric acid aqueous solutions and in mixed sulfuric acid and methanol aqueous solutions. The catalytic activity of the Pt-Ru/CNTs electrode for methanol oxidation was 1038.25 A g⁻¹_Pt in a mixed solution containing 0.5 M sulfuric acid and 1.0 M methanol.     

Effect of noble metal species and compositions on manganese dioxide-modified carbon nanotubes for enhancement of alcohol oxidation

By integrating the effects of alloying, chemical composition and support, a series of mono- and bi-metallic catalyst nanoparticles electrodeposited on α-manganese dioxide (MnO₂)-modified carbon nanotube (CNT) supports were synthesized to improve the efficiency of direct alcohol fuel cells. Small and dispersed nanoparticles on the CNT/MnO₂ surfaces with high electrochemically active surface area (ECSA) were successfully obtained in this work. The support materials were characterized by Fourier-transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD), while the as-prepared catalysts were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) and chronoamperometry (CA) were used to study the activity and stability of the catalysts, respectively. The results showed that a combination of Pt, Pd, Au and MnO₂ on the CNTs significantly affected the topography of the composite catalyst surfaces, and their electrochemical measurements showed excellent electrocatalytic activity toward the reaction. For methanol and ethanol oxidation in acid solution, CNT/MnO₂/1M3Pt (M = Pd or Au) catalysts revealed greater activity improvement compared to the other prepared catalysts. For the bimetallic CNT/MnO₂/xMyPt catalysts, the values of the forward peak current (I_f)) and the ratio of the forward peak current to the reverse peak current (I_f/I_b) were higher, while their onset potentials (E_o) were lower compared to those of the monometallic CNT/MnO₂/4Pt catalyst. Moreover, CO oxidation on these bimetallic catalysts was also confirmed to be poisoning resistant. These results indicate that our prepared catalyst showed excellent electrocatalytic performance, reliability, and stability. The catalytic activity improvement was based upon the unique integrated structural and functional properties and the synergistic effect of different compositions in the catalyst system.     

Catalytic activity,stability and impedance behavior of PtRu/C,PtPd/C and PtSn/C bimetallic catalysts toward methanol and formic acid oxidation

PtRu, PtPd and PtSn with weight ratios of (2:1) on carbon black (Vulcan XC-72) supported bimetallic catalysts were prepared by using microwave method via chemically reduction of H₂PtCl₆·6H₂O, RuCl₃, PdCl₂ and SnCl₂·2H₂O precursors with ethylene glycol (EG). These prepared catalysts were systematically investigated and obtained results were compared with commercial Pt black, PtRu black catalysts and with each other. The catalysts were characterized with XRD, ICP-MS, EDS and TEM. The electrocatalytic activities, stability and impedance of the catalysts were investigated in sulfuric acid/methanol and sulfuric acid/formic acid mixtures using electrochemical measurements. The results showed that PtSn/C catalyst showed comparable activity and durability with commercial Pt/C catalyst toward methanol oxidation. The synthesized PtRu/C catalyst was found to completely oxidize methanol and it showed more catalytic activity than commercial PtRu catalyst. Bimetallic PtPd/C catalyst gave better activity than both commercial Pt black and synthesized Pt/C catalyst for oxidation of formic acid. Higher electrochemical active surface areas were obtained with supported bimetallic catalysts.     

Electrochemical preparation of Pt-based ternary alloy catalyst for direct methanol fuel cell anode

The CoPtRu catalyst was prepared with electrochemical methods on carbon paper. The preparation of Co particles on the carbon paper was performed through an electrodeposition process by varying the deposition potential and time. After Co electrodeposition, Pt and Ru galvanic displacements were carried out by controlling displacement time. The bulk and surface composition of the catalysts were analyzed by using inductively coupled plasma (ICP) mass spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. It was proved that the CoPtRu catalyst was successfully synthesized using the electrochemical process. In this study, the electrochemically prepared catalysts showed superior catalytic activity for methanol oxidation and tolerance to CO poisoning compared to a commercial PtRu/C catalyst (E-tek).     

Binary Pt–Pd and ternary Pt–Pd–Ru nanoelectrocatalysts for direct methanol fuel cells

Nano-sized binary and ternary alloys are synthesized by polyol process on Vulcan XC72-R support. Nanostructured binary Pt–Pd/C catalysts are prepared either by co-deposition or by depositing on each other. Ternary Pt–Pd–Ru/C catalysts are prepared by co-deposition. The structural characteristics of the nanocatalysts are examined by TEM and XRD. Their electrocatalytic activity toward methanol oxidation and CO stripping curves were measured by electrochemical measurements and compared with that of commercial Pt/C catalyst. The results show that the binary nanocatalyst prepared by depositing the Pt precursor colloids on Pd-Vulcan XC-72R are more active toward methanol oxidation than that of the co-deposited binary alloy nanocatalyst. The co-deposited ternary Pt–Pd–Ru/C nanocatalyst based membrane electrodes assembly shows higher power density compared to the binary nanocatalysts as well as commercial Pt/C catalyst in direct methanol fuel cell. Significantly higher catalytic activity of the nanocatalysts toward methanol oxidation compared to that of the commercial Pt/C is believed to be due to lower level of catalyst poisoning.     

Fabrication of bimetallic Pt–M (M = Fe,Co, and Ni) nanoparticle/carbon nanotube electrocatalysts for direct methanol fuel cells

The electrochemical activities of three bimetallic Pt–M (M = Fe, Co, and Ni) catalysts in methanol oxidation have been investigated. An efficient approach including chemical oxidation of carbon nanotubes (CNTs), two-step refluxing, and subsequent hydrogen reduction was used to thoroughly disperse bimetallic nanopartilces on the oxidized CNTs. Three catalysts with a similar Pt:M atomic ratio, Pt–Fe (75:25), Pt–Co (75:25), and Pt–Ni (72:28), were prepared for the investigation of methanol oxidation. The Pt–M nanoparticles with an average size of 5–10 nm are uniform and cover the surface of CNTs. Cyclic voltammetry showed that the three pairs of catalysts were electrochemically active in the methanol oxidation. On the basis of the experimental results, the Pt–Co/CNT catalyst has better electrochemical activity, antipoisoning ability, and long-term cycleability than the other electrocatalysts, which can be justified by the bifunctional mechanism of bimetallic catalysts. The satisfactory results shed some light on how the use of Pt–Co/CNT composite could be a promising electrocatalyst for high-performance direct methanol fuel cell applications.     

Electrocatalysis of carbon black- or activated carbon nanotubes-supported Pd–Ag towards methanol oxidation in alkaline media

Carbon black supported bimetallic palladium–silver (Pd–Ag/C) catalysts with different Ag loadings were prepared by borohydride reduction of mixed metal salts and carbon support. Electrochemical activities of these catalysts towards methanol oxidation in alkaline media were examined and the Pd–Ag(1:1)/C catalyst (onset potential of −0.59 V) shows better catalytic activity than the Pd/C catalyst (onset potential of −0.49 V). The addition of Ag also facilitates methanol oxidation and removal of the adsorbed CO. The synthesized activated carbon nanotubes (CNTs)-supported Pd–Ag(1:1) catalyst exhibits even better catalytic activity contributed from larger electroactive surface area and better intrinsic catalytic activity than the carbon black supported bimetallic palladium–silver (Pd–Ag/C) catalyst.     

Precise control of π-conjugated polymer/carbon nanotubes heterointerfaces for oxygen reduction reactions

Nitrogen-coordinated metal catalyst has been regarded as a promising candidate for precious platinum for oxygen reduction reaction (ORR). However, controlling the structure and composition of coordinated metals in heterogeneous catalysts remains a synthetic bottleneck. Here, we design and fabricate π-conjugated polymer/CNTs heterointerfaces by polymerizing Co-BTA on CNTs. Co-BTA contains abundant Co–N₄ moieties and provides catalytic sites for ORR. CNT acts as a support and constructs the network for electron transport. Therefore, Co-BTA/CNT exhibits outstanding catalytic activity for ORR with comparable half-wave potential to commercial Pt/C. Furthermore, Co-BTA/CNT demonstrates better durability and methanol tolerance compared with Pt/C. Importantly, zinc-air batteries with Co-BTA/CNT have a maximum discharge power of 94.5 mW cm⁻² and a high energy density of 985 Wh kg⁻¹, superior to that with commercial Pt/C (51.5  mW cm⁻², 930 Wh kg⁻¹). This work paves a new avenue for precisely controlling nitrogen-coordinated metal catalysts for electrochemical energy conversion and storage.     

Methanol electrooxidation at mesoporous Pt and Pt-Ru electrodes: A comparative study with carbon supported materials

The electrochemical behaviour of fuel cell catalysts (mesoporous Pt (MPPt), MPPtRu, MPPt modified by adsorbed Ru (MPPt/Ru) and carbon supported PtRu alloy) was studied using the thin layer flow cell differential electrochemical mass spectrometry (TLFC-DEMS) technique. The catalysts present high catalytic activity towards the methanol oxidation reaction (MOR), being the PtRu/C electrode the least active for MOR, while MPPt/Ru presents higher current densities for this reaction than MPPtRu. The results suggest that the diffusion properties obtained in the porous structure of the MP electrodes and the surface atomic arrangement in the electrode are the main reasons for the higher catalytic activity achieved. Finally, TLFC-DEMS was proved to be a powerful technique which evaluates and correlates the CO₂ efficiency with the catalytic activity and the porous structure of the catalysts.     

Synthesis,characterization and 1-propanol electrooxidation application of carbon nanotube supported bimetallic catalysts

In this study, 1-propanol electrooxidation activities of Pt and Bi catalysts synthesized by NaBH₄ co-reduction and sequential reduction methods are compared. The characterization of the catalysts supported carbon nanotube (CNT) is determined by XRD, SEM-EDX, TEM, and ICP-MS analyzes. In the TEM results, it is seen that Pt and Bi metal nanoparticles are dispersed into carbon nanotubes. Electrochemical measurements of CV, CA, and EIS are applied to investigate the catalytic activities of catalysts for 1-propanol electrooxidation. Bi@Pt/CNT catalyst exhibits the highest catalytic activity (24.212 mA/cm² and 1950.06 mA/mg Pt), long-term stability and lowest resistance. As a result, it was concluded that the catalyst activity increased with the sequential reduction method and the Bi@Pt/CNT catalyst was promising with its high activity value for direct alcohol fuel cells.     

Synthesis and characterization of the Au-modified Pd cathode catalyst for alkaline direct ethanol fuel cells

Three kinds of Au-modified Pd catalysts with the alloy, core–shell and physically-mixed structures are prepared with carbon nanotubes as the support. The structural details and the particle sizes of the prepared catalysts are characterized by X-ray diffraction and transmission electron microscopy. The experimental results indicate that the Au-modified Pd catalysts show smaller particle sizes with narrower particle size distributions than the mono-Pd catalyst does. The catalytic activities of the prepared catalysts for oxygen reduction and ethanol oxidation are examined by electrochemical measurements. Compared with the mono-Pd catalyst, the Au-modified Pd catalyst with the physically-mixed structure exhibits increased catalytic activity for oxygen reduction, but decreased catalytic activity for ethanol oxidation in alkaline media. The cell performance with the Au-modified Pd as the cathode catalyst yielded a peak power density of as high as 185 mW cm⁻², which is about 1.4 times higher than that with the mono-Pd cathode.     

Investigation of PdNiO/C catalyst for methanol electrooxidation

The methanol electrooxidation reaction was studied on carbon dispersed Pd-nickel oxide nanocatalysts in KOH/CH₃OH solutions. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize PdNiO/C catalysts. The electrochemical behaviors for the methanol electrooxidation reaction were measured in a powder microelectrode by cyclic voltammetry and Tafel plots. The result showed that the adding NiO enhances the anti-poison ability of PdNiO/C catalyst, but the reaction mechanism does not change. The anti-poison ability of PdNiO/C catalyst can be enhanced by three ways: (1) the NiOOH on the surface of catalyst improves the activity of composite catalyst for methanol oxidation; (2) the catalytic role of NiO for methanol dehydration; (3) the promotion of large amount active species-PdO (low oxidation state) for methanol oxidation.     

Methanol-tolerant carbon aerogel-supported Pt-Au catalysts for direct methanol fuel cell

Pt-Au nanoparticles supported on carbon aerogel, namely 2:1 has been synthesized by the microwave-assisted polyol process. The structure of Pt-Au nanoparticles is characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The electrochemical property of Pt-Au catalysts for methanol oxidation is evaluated by cyclic voltammetry (CV). The results show that Au-modified Pt catalysts exhibit a high methanol tolerance and improved electrochemical catalytic activity, suggesting that carbon aerogel supported Pt-Au catalysts are better catalysts for the electrochemical oxidation of methanol than conventional Pt catalysts.     

The effect of CuO on a Pt−Based catalyst for oxidation in a low-temperature fuel cell

Electrocatalytic oxidation of methanol, ethanol, and formic acid has currently attracted research attention for low-temperature fuel cells. However, the efficiencies of these fuel cells mainly depend on the electrocatalytic activities of Pt-based anodic catalysts due to the problems of low kinetics for small organic molecule electro-oxidation. An anode catalyst can be developed by the addition of some metal oxides into a Pt-based catalyst, which can effectively promote the electro-oxidation of fuels based on small organic molecules. In this work, a nanocomposite catalyst consisting of multi-wall carbon nanotubes (CNTs), copper oxide (CuO) and Pt nanoparticles was synthesized and used to improve fuel cell oxidation. Due to its low cost and oxophilic character, the metal oxide can play a major role in the oxidation of CO. The synthesis of xPt?yCuO/CNT electrocatalysts was executed through two steps: supporting of CuO nanoparticles on CNTs by the alcothermal method followed by Pt loading onto the prepared CuO/CNT by chemical reduction. The as-prepared catalysts were physically characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and electrochemical measurements. The results demonstrate that CuO is well dispersed onto the CNTs and that this oxide can further interact with the active Pt present on the as-prepared catalyst composites. The activity of various xPt?yCuO/CNT electrocatalysts was determined by cyclic voltammetry (CV), where x and y are the mass ratios of Pt and CuO, respectively. The presence of CuO was found to significantly contribute to enhanced electroactivity towards oxidation reactions. The 1Pt–3CuO/CNT electrocatalyst is a capable catalyst for improving low-temperature fuel cell applications.     

Iron chelates as low-cost and effective electrocatalyst for oxygen reduction reaction in microbial fuel cells

Iron-chelated electrocatalysts for the oxygen reduction reaction (ORR) in a microbial fuel cell (MFC) were prepared from sodium ferric ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid) (FeE), sodium ferric diethylene triamine pentaacetic acid (FeD) supported on carbon Vulcan XC-72R carbon black and multi-walled carbon nanotubes (CNTs). Catalyst morphology was investigated by TEM; and the total surfaces areas as well as the pore volumes of catalysts were examined by nitrogen physisorption characterization. The catalytic activity of the iron based catalysts towards ORR was studied by cyclic voltammetry, showing the higher electrochemical activity of FeE in comparison with FeD and the superior performance of catalysts supported on CNT rather than on Vulcan XC-72R carbon black. FeE/CNT was used as cathodic catalyst in a microbial fuel cell (MFC) using domestic wastewater as fuel. The maximum current density and power density recorded are 110 (mA m⁻²) and 127 ± 0.9 (mW m⁻²), respectively. These values are comparable with those obtained using platinum on carbon Vulcan (0.13 mA m⁻² and 226 ± 0.2 mW m⁻²), demonstrating that these catalysts can be used as substitutes for commercial Pt/C.     

Methanol oxidation on hybrid catalysts: PtRu/C nanostructures promoted with cerium and titanium oxides

Hybrid catalysts comprising of ceramic, metal, and carbon phase were synthesized by incorporating titanium and cerium oxides into PtRu/C commercial catalyst using an in-situ combustion followed by heat treatment at 600 °C. The structure dependent electrochemical behavior of as-synthesized and heat-treated materials towards methanol oxidation, carbon dioxide (CO) tolerance and chemical stability was studied by XRD, HRTEM, BET, EDS, cyclic voltammetry, chronoamperometry, and CO-stripping method. As a result of heat treatment, amorphous phase of metal oxides was transformed into a crystalline phase with particle size of about 3–7 nm. Improved methanol oxidation activity of the hybrid catalysts was compared to PtRu/C catalyst as a baseline and explained by the changes in Pt electronic behavior and excess adsorption of OH-ions. When heat-treated at 600 °C, CeO₂-PtRu/C demonstrated the highest mass activity of 580 mA/mg (∼3×  that of PtRu/C) compared to TiO₂-PtRu/C (394 mA/mg). Heat-treated hybrid catalysts exhibited higher methanol oxidation activity at higher peak potentials than the corresponding as-synthesized materials. However, as-synthesized hybrid catalysts display higher CO-tolerance, lower CO-oxidation onset potentials, and better chemical stability in comparison to corresponding heat-treated catalysts. To explain the difference, a mechanism for ceramic oxide structure dependent electrochemical behavior of the hybrid catalysts is proposed and discussed.