Efficient electro-oxidation of methanol using PtCo nanocatalysts supported reduced graphene oxide matrix as anode for DMFC

Platinum – cobalt (PtCo) alloy based highly efficient nano electro-catalysts on reduced graphene oxide (rGO) matrix have been synthesized for the electro-oxidation of methanol, by chemical reduction method. Different molar ratio of Pt (IV) and Co (II) ions along with graphene oxide (GO) were reduced using ethylene glycol to obtain PtCo nanoparticles onto rGO sheets (Pt/rGO, PtCo (1:1)/rGO, PtCo (1:5)/rGO, PtCo (1:9)/rGO and PtCo (1:11)/rGO) with 20 wt. % metal and 80 wt. % rGO. The average particle size of PtCo nanoparticles onto rGO support was observed to be 2–5 nm using XRD and TEM analysis. The PtCo (1:9)/rGO nanocomposite catalyst exhibited ～23 times higher anodic current density compare to commercially available Pt/C catalyst (1.68 mA/cm²) for methanol oxidation reaction. The peak power density of 118.4 mW/cm² was obtained for PtCo (1:9)/rGO catalyst in direct methanol fuel cell (DMFC) at 100 °C, 1 bar, and 2 M methanol as anode feed, which is ～3 times higher than that of Pt/C catalyst. The results indicate the potential application of synthesized nanocomposite catalyst in commercial DMFCs.     

Tuning surface composition of multiwalled carbon nanotubes supported Pt-Co bimetallic nanoparticles for boosting methanol oxidation catalysis

Developing catalysts with high performance and low cost for methanol oxidation reaction (MOR) is the key to promoting the industrialization of direct methanol fuel cells (DMFCs). In this work, multiwalled carbon nanotubes (MWCNTs) supported PtCo alloys catalysts with improved MOR properties and anti-CO poisoning ability are successfully prepared by integrating low temperature adsorption and high temperature reduction method. The Pt₁Co₃@NC/MWCNTs sample with moderate Co²⁺ feeding content (0.81 mA/ug_Pt) achieves a factor of 1.93 enhancement in MOR mass activity compared to the commercial Pt/C catalyst (0.42 mA/ug_Pt). In addition, the Pt₁Co₃@NC/MWCNTs sample displays a lower CO oxidation onset potential respect to pristine Pt/C catalyst (0.74 V vs. 0.82 V). Scuh improvement of MOR activity, durability and anti-CO poisoning ability of the Pt₁Co₃@NC/MWCNTs catalyst is ascribed to the moderate surface compositions, optimal electronic interaction between PtCo alloys and MWCNTs, and the protection of N-doped carbon (NC) shells. This study provides a new direction to decrease the utilization of platinum and improve the MOR activity, stability and anti-CO poisoning ability of electrocatalysts which will be potential in design and fabrication of the highly efficient electrocatalysts for DMFCs applications.     

PtCo/N-doped carbon sheets derived from a simple pyrolysis of graphene oxide/ZIF-67/H2PtCl6 composites as an efficient catalyst for methanol electro-oxidation

Many alloy catalysts have been developed for methanol electro-oxidation, but most synthetic methods are complicated. Herein, PtCo alloy catalysts supported on N-doped carbon sheets (PtCo/NCS) are successfully prepared by a simple pyrolysis of graphene oxide/ZIF-67/H₂PtCl₆ composites at different temperatures (700, 800, 900 °C) under a gas flow of H₂/Ar, in which ZIF-67 is served as Co and N sources. SEM, TEM, XRD, XPS and electrochemical characterization are employed to study as-prepared catalysts. In acidic methanol solution, the area-specific activity (1.25 mA cm⁻² Pt) of PtCo alloy catalyst obtained at 800 °C (PtCo/NCS-800) is 2.6 times of commercial Pt/C (0.48 mA cm⁻² Pt), and the area-specific activity of PtCo/NCS-800 is 3.5 times of Pt/C after 1000 cycles. Furthermore, an improved CO-tolerance of Pt is confirmed. The electronic effect and synergistic effect of metallic elements are responsible for outstanding performance of as-prepared catalysts. This work provides a simple approach to obtain high performance alloy catalysts.     

Bimetallic Pt3Mn nanowire network structures with enhanced electrocatalytic performance for methanol oxidation

Pt-based catalysts are still most attractive and could be the major driving force for facile electrochemical reactions in direct methanol fuel cells (DMFCs). In this work, a Pt₃Mn nanowire network structures (NWNs) catalyst was successfully synthesized by a soft template (CTAB) method. The morphology and elemental composition of the Pt₃Mn NWNs were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES). The electrocatalytic behavior of the synthesized Pt₃Mn NWNs catalyst towards methanol oxidation reaction (MOR) was studied by cyclic voltammetry (CV) and chronoamperometry (CA). The results reveal that the Pt₃Mn NWNs has superior MOR activity and durability compared to Pt NWNs and commercial Pt/C. The mass and specific activities of Pt₃Mn NWNs are 0.843 A mg⁻¹ and 1.8 mA cm⁻² respectively, which are twice that of commercial Pt/C. Additionally, the results of CA test indicate that the Pt₃Mn NWNs possesses better durability than Pt NWNs and commercial Pt/C catalysts in acidic media, which is expected to be a new alternative anode material in DMFCs.     

A novel co-precipitation method for preparation of Pt-CeO2 composites on multi-walled carbon nanotubes for direct methanol fuel cells

Ceria (CeO₂) as co-catalytic material with Pt on multi-walled carbon nanotubes (Pt-CeO₂/MWCNT) is synthesized by a co-precipitation method. The physicochemical characterizations of the catalysts are carried out by using transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) techniques. Electrocatalytic activities of the catalysts for methanol oxidation is examined by cyclic voltammetry and chronoamperometry techniques and it is found that Pt-CeO₂/MWCNT catalysts exhibited a better activity and stability than did the unmodified Pt/MWCNT catalyst. CO-stripping results indicate the facile removal of intermediate poisoning species CO in the presence of CeO₂, which is helpful for CO and methanol electro-oxidation.     

Syntheses, characterization, and catalytic oxygen electroreduction activities of carbon-supported PtW nanoparticle catalysts

Carbon-supported PtW (PtW/C) alloy nanoparticle catalysts with well-controlled particle size, dispersion, and composition uniformity, have been synthesized by wet chemical methods of decomposition of carbonyl cluster complexes, hydrolysis of metal salts, and chemical reactions within a reverse microemulsion. The synthesized PtW/C catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy, and energy-dispersive spectroscopy. The catalytic oxygen electroreduction activities were measured by the hydrodynamic rotating disk electrode technique in an acidic electrolyte. The influence of the synthesis method on PtW particle size, size distribution, composition uniformity, and catalytic oxygen electroreduction activity, have been investigated. Among the synthesis methods studied, PtW/C catalysts prepared by the decomposition of carbonyl cluster complexes displayed the best platinum mass activity for oxygen reduction reaction under the current small scale production; a 3.4-fold catalytic enhancement was achieved in comparison to a benchmark Pt/C standard.     

Enhanced activity of Pt(HY) and Pt–Ru(HY) zeolite catalysts for electrooxidation of methanol in fuel cells

The investigation describes the synthesis of Pt and Pt–Ru catalysts by a new method using a HY zeolite support. The catalysts are used to study the anodic oxidation of methanol in an acidic medium to investigate their suitability for use in direct methanol fuel cells (DMFCs). The catalysts prepared in a HY zeolite support display significantly enhanced electrocatalytic activity in the order: HY<Pt/C<Pt(HY)<Pt–Ru/C<Pt–Ru(HY). The enhanced electrocatalytic activity is explained on the basis of the formation of specific CO clusters in zeolite cages.     

Nanoporous PtCo and PtNi alloy ribbons for methanol electrooxidation

Nanoporous (NP) PtCo and PtNi alloy ribbons with predetermined bimetallic compositions are easily fabricated by one step of mild dealloying, which are characterized by uniform three-dimensional bicontinuous network architecture with the ligament size as small as 3 nm. Compared with E-TEK Pt/C catalyst, the as-made NP-PtCo(Ni) alloys exhibit superior specific activity with the lower peak potential and enhanced CO-tolerance toward methanol electrooxidation. More importantly, these nanomaterials also show much higher structure stability with little loss of the electrochemical surface area of Pt upon 5000 potential cycles in acid solution. X-ray photoelectron spectroscopy and DFT calculations revealed that alloying with Co or Ni modifies the electronic structure of Pt with the downshift of Pt d-band center, thus resulting in the improved methanol oxidation activity and decreased CO poisoning.     

Structural designing of Pt-CeO2/CNTs for methanol electro-oxidation

In an attempt to utilize CeO₂ as a co-catalyst with Pt for methanol electro-oxidation, Pt-CeO₂/CNTs were prepared through structural designing by adsorbing Pt nanoparticles on CeO₂ coated CNTs. X-ray Diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) were used to analyze the composition of the prepared catalysts. Zeta potential analysis, high resolution transmission electron microscopy (HRTEM) and cyclic voltammetry (CV) methods indicated that Pt nanoparticles are selectively adsorbed on CNTs other than CeO₂ surface. Pt-CeO₂/CNTs were compared with Pt supported on CNTs in terms of electrochemical active surface (EAS) areas, methanol electro-oxidation activity, and chronoamperometry, results indicating that CeO₂ can enhance the catalytic activity of Pt for methanol electro-oxidation with no apparent decrease of EAS. The CO stripping test showed that CeO₂ can make CO stripped at a lower potential, which is helpful for CO and methanol electro-oxidation.     

Platinum/vivianite bifunction catalysts for DMFC

Bi-functional catalysts are used to solve the poisoning problem caused by carbon monoxide (CO) which is the intermediate of direct methanol fuel cells (DMFCs). Flower-like vivianite (Fe₃(PO₄)₂·8H₂O) spheres with diameter around 10 μm are originally used as supports of Pt to form bifunction catalysts. The cyclic voltammetry in 1 M H₂SO₄ indicates that the electrochemical surface area (ECSA) of Pt reduced on as-prepared vivianite (Pt/Vi) was 105, greater than 91 m² g⁻¹ for the commercial Pt/C. Besides, Pt/Vi reveals the less CO poisoning effects, including the greater mass activity in methanol oxidation and the lower onset potential in CO-stripping than Pt/C. These excellent performances on electrolyzes are related to the chemical state of Fe³⁺ and the coexistence of Pt⁰ and Pt²⁺ in Pt/Vi. The former activates the water and yields Fe-OH_ads at lower potential and the latter may offer an easy way of electron transition.     

Graphene supported platinum–cobalt nanocomposites as electrocatalysts for borohydride oxidation

In the study presented herein a rapid microwave heating method was used to prepare the graphene supported PtCo catalysts with Pt:Co molar ratio 1:7, 1:22 and 1:44. The transmission electron microscopy was employed to characterize the catalysts. Inductively coupled plasma optical emission spectrometry was used for estimation of Pt and Co metal loadings. The electrocatalytic activity of the synthesized catalysts towards the oxidation of borohydride was investigated by means of cyclic voltammetry and chronoamperometry. The kinetics of the catalytic hydrolysis of NaBH₄ in the presence of the synthesized catalysts was investigated.     

Pt and PtRu nanoparticles deposited on single-wall carbon nanotubes for methanol electro-oxidation

Platinum (Pt) and platinum–ruthenium (PtRu) nanoparticles supported on Vulcan XC-72 carbon and single-wall carbon nanotubes (SWCNT) are prepared by a microwave-assisted polyol process. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The PtRu nanoparticles, which are uniformly dispersed on carbon, have diameters of 2–6 nm. All the PtRu/C catalysts display the characteristic diffraction peaks of a face centred cubic Pt structure, excepting that the 2θ values are shifted to slightly higher values. The results from XPS analysis reveal that the catalysts contain mostly Pt(0) and Ru(0), with traces of Pt(II), Pt(IV) and Ru(IV). The electrooxidation of methanol is studied by cyclic voltammetry, linear sweep voltammetry, and chronoamperometry. Both PtRu/C catalysts have high and more durable electrocatalytic activities for methanol oxidation than a comparative Pt/C catalyst. Preliminary data from a single direct methanol fuel cell using the SWCNT supported PtRu alloy as the anode catalyst delivers high power density.     

Durability studies of unsupported Pt cathodic catalyst with working time of direct methanol fuel cells

Life tests of direct methanol fuel cells (DMFCs) were carried out with three individual single cells for three different times. X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS) were used to evaluate the cathodic Pt black catalysts prior to and after the life tests. XRD results showed that the particle sizes of cathodic catalysts increased from an original value of 7.3–8.3, 8.7, and 9.2 nm, whereas their lattice parameters first increased and then decreased from an original value of 3.9188–3.9210, 3.9197, and 3.9196 Å before and after 117, 210, and 312 working hours, respectively. XPS results indicated that the metal content gradually decreased with test time, but the contents of Pt oxides in cathodic catalysts increased. Hydrogen adsorption–desorption cyclic voltammetry were employed to test the performances of three individual fuel cells and the electrochemically active surface areas (S_EAS) of cathodic catalysts before and after the life tests. It is found that both S_EAS of cathodic catalysts and their utilization decreased markedly. This indicates that the change of S_EAS and utilization of cathodic catalysts are the main factors affecting the performance decay of DMFC. The dissolution/agglomeration of Pt metal from cathodic catalysts also plays an important role in the performance decay of DMFC. The sintering/degradations of cathodic Pt nanoparticles were accelerated due to crossover of methanol to form the mixed potentials. The agglomeration of cathodic Pt nanoparticles may be illustrated with dissolution/deposition mechanism.     

Methanol electrooxidation on carbon supported Aucore–Ptshell nanoparticles synthesized by an epitaxial growth method

Au_core–Pt_shell (Au@Pt) nanoparticles supported on activated carbon (Au@Pt/C) are synthesized by an epitaxial growth method using HCOONa as a reducing agent. Through the characterization of the transmission electron microscope (TEM), high resolution TEM (HRTEM), high angle annular dark-field scanning TEM (HAADF-STEM) and X-ray powder diffraction (XRD), the Pt atoms grow epitaxially on the surface of the Au nanoparticles to form Pt shells with Au fcc structure. According to the results of the X-ray photoelectron spectroscopy (XPS), electrons transfer from Pt to Au. Cyclic voltammetry is employed to investigate the catalytic activities of the Au@Pt/C catalysts for the methanol electrooxidation (MEO) and the CO stripping. The results of the electrochemical measurements indicate that, the Au fcc structure of the Pt shell and the decrease in the electronic effect are propitious to the increases in the catalytic activity for the MEO and the CO tolerance of the Au@Pt/C catalysts.     

Synthesis and characterization of H5PMo10V2O40 deposited Pt/C nanocatalysts for methanol electrooxidation

Pt/C(a) catalysts are firstly prepared by modified impregnation method. In order to enhance the ability of Pt/C catalysts for methanol electrooxidation, H₅PMo₁₀V₂O₄₀ (PMV) is adsorbed on Pt/C catalysts to obtain the PMV-Pt/C catalysts. The Pt/C(a) and PMV-Pt/C are characterized by transmission electron microscopy (TEM) and X-ray diffractometry. It is shown that Pt particles with small average size are uniformly disperesed on carbon. Cyclic voltammetry and chronoamperometry show that the PMV-Pt/C catalysts exhibit excellent catalytic activity and stability for methanol electrooxidation.     

A novel TiN coated CNTs nanocomposite CNTs@TiN supported Pt electrocatalyst with enhanced catalytic activity and durability for methanol oxidation reaction

The application of direct methanol fuel cells (DMFCs) is hampered by not only low activity but also poor stability and poor CO tolerance by the Pt catalyst. Herein, a novel titanium nitride coated multi-walled carbon nanotubes (CNTs@TiN) hybrid support was successfully synthesized by a facile solvothermal process followed by a nitriding process, and this hybrid support was used as Pt support for the oxidation of methanol. The structure, morphology and composition of the synthesized CNTs@TiN exhibits a uniform particle perfect coating with high purity and interpenetrating network structure. Notably, Pt/CNTs@TiN also showed excellent stability, experiencing only a slight performance loss after 5000 potential cycles. The onset potential (0.34 V) of CO oxidation on Pt/CNTs@TiN is obviously more negative than that on the Pt/TiN (0.38 V) and Pt/CNTs (0.48 V) in the first forward scan. In the Pt 4f XPS spectra, plentiful Pt atoms existed as Pt(II) in the Pt/CNTs and Pt/TiN catalysts, while a relatively smaller amount of Pt(II) was observed in the Pt/CNTs@TiN catalyst. The synthetic Pt/CNTs@TiN catalyst was studied with respect to its electrocatalytic activity and durability and CO tolerance toward methanol oxidation might be mainly attributed to the strongly coupled Pt–TiN and the fast electron-transport network structure. This work may provide more insight into developing novel catalyst supports of various transition metal nitrides coated CNTs for DMFCs with high activity and good durability and excellent CO tolerance.     

Polyol-synthesized PtRu/C and PtRu black for direct methanol fuel cells

PtRu/C and PtRu black catalysts with nominal Pt:Ru atomic ratio of 1:1 are prepared by a modified polyol process (co-reduction of metal precursor salts) as anode catalysts for direct methanol fuel cells (DMFCs). Without the carbon support, PtRu nanoparticles tend to agglomerate, while the PtRu nanoparticles in PtRu/C have a good dispersion as shown by TEM. Both PtRu black and PtRu/C have the almost same alloy degree indicated by XRD, but PtRu supported on carbon could improve the influence of Ru on Pt toward methanol oxidization as shown by cyclic voltammetry. The microstructure of PtRu/C is further studied by high-resolution transmission electron microscopy (HRTEM), and the results indicate that the lattice constant of Pt in PtRu electrocatalyst has contracted despite a few parts of Pt not alloyed with Ru due to the lattice constant of Pt without contracting, which is further proved by the results of temperature-programmed reduction (TPR). Such parts of unalloyed Ru are further proved to have ability to reduce the methanol oxidation potential on Pt by comparing the catalytic behaviors of Pt/C and Pt + Ru/C prepared by mixing carbon with separately prepared Pt and Ru colloids. Moreover, the catalytic behaviors of PtRu black and PtRu/C are also compared with those of commercial ones.     

Carbon supported Pt-shell modified PdCo-core with electrocatalyst for methanol oxidation

A catalyst for anode oxidation of methanol, carbon supported pseudo-core-shell PdCo@Pt particles with Pt shell is prepared via a two-step procedure, which consists of an organic colloid method and a surface replacement reaction step. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) are used for the catalysts characterization. The electrochemical surface areas (ECSA) are 6 and 4 times as large as those of Pt/C and PtRu/C catalysts, respectively. Furthermore, based on the Pt mass, the cyclic voltammetry (CV) and chronoamperometry results demonstrate that the electrocatalytic activity and stability of the PdCo@Pt/C catalyst for methanol oxidation are much higher than those of the Pt/C and PtRu/C catalysts. The PdCo@Pt/C catalyst is better utilization of Pt than pure Pt and Pt-based alloy catalysts.     

One-step synthesis in deep eutectic solvents of PtV alloy nanonetworks on carbon nanotubes with enhanced methanol electrooxidation performance

We report a simple one-step chemical reduction strategy in deep eutectic solvents (DESs) for the fabrication of a PtV alloy nanonetwork (ANN)/multiwalled carbon nanotube (MWCNT) nanohybrid, which exhibits excellent electrocatalytic performance in both activity and stability for the methanol oxidation reaction (MOR). The as-synthesized nanohybrid was characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy, confirming the formation of a porous nanonetwork structure composed of smaller PtV alloy nanoparticles (~3.8 nm) and the presence of strong electronic transfer interactions between Pt and alloyed V. The electrochemical properties of catalysts for the MOR were evaluated by using cyclic voltammetry and chronoamperometry techniques. The electrocatalytic activity, durability and CO tolerance ability of PtV ANNs/MWCNTs toward the MOR are found to be considerably higher than those of the Pt/MWCNT and commercial Pt/C catalysts. This investigation of the effect of several reaction parameters (e.g., scan rate and methanol concentration) indicates that the electrocatalytic oxidation of methanol on PtV ANNs/MWCNTs is a diffusion-controlled electrochemical process. The performance enhancement mechanism of MOR on the PtV ANN/MWCNT catalyst is analyzed based on the structure and electrochemical studies.