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.     

Facile synthesis of Pd-Ru-P ternary nanoparticle networks with enhanced electrocatalytic performance for methanol oxidation

Liquid fuel cells have attracted broad research interests for past several decades, especially for direct methanol fuel cells (DMFCs) because of their compact volume, environmentally benign and easy storage. Exploring cost-effective electrocatalysts toward methanol electrooxidation is meaningful for the development of (DMFCs). Herein, a series of PdRu/P network catalysts have been fabricated and modified via a facile and reproducible method taking benzyl alcohol, hydrazine hydrate as solvent and reducing agents, respectively. Profiting from the 3D network structure, the synergistic effect together with the increased electron mobility induced by the addition of nonmetal phosphorous (P). The PdRu/P catalysts display markedly improved efficient electrocatalytic activity with excellent current peak, more negative onset potential, as well as superior long-term stability compared to commercial Pd/C, PdRu and Pd/P prepared under the same condition. In this work, we highlight the effect of the incorporation of nonmetals P on the electrocatalytic performance of PdRu binary catalysts, which will contribute to broadening the application of nonmetal P or even for other nonmetals for electrooxidation. Our efforts will dedicate to accelerating the commercialization of efficient and stable anode catalysts in fuel cells by means of doping transition metals or nonmetals into Pd.     

Enhanced electrocatalytic methanol oxidation properties by photo-assisted Fe2O3 nanoplates

In this paper, visible-light-driven two-dimensional (2D) Fe₂O₃ nanoplates with exposed (001) facets were first adopted to act as Pt support for photo-assisted electrocatalytic methanol oxidation. Under simulated solar light and visible light illumination Pt-2D Fe₂O₃ nanoplates displayed 2.32 and 1.30 times higher electrocatalytic activities for methanol oxidation than in dark condition, respectively. Besides, 2D Fe₂O₃ nanoplates owns much better electrocatalytic activities for methanol oxidation than Fe₂O₃ particles whether in dark, visible light or simulated solar light illumination. The nice photo-assisted electrocatalytic methanol oxidation activities of Pt-2D Fe₂O₃ nanoplates can be attributed to 2D structure enhanced the oxidation activities of photogenerated holes to oxidize OH⁻ to hydroxyl radical (·OH) as well as its large specific surface area. Our experimental results suggest that photo-assisted and two-dimensional strategy of semiconductors are promising ways to further improve the electrocatalytic activities for methanol oxidation in DMFCs.     

Preparation of PtNi hollow nanospheres for the electrocatalytic oxidation of methanol

We report the synthesis and characterization of hollow PtNi nanospheres by chemical successive-reduction method. The results of X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) account for the alloy formation between Pt and Ni and electronic structure change of Pt in the alloy. The prepared nanospheres show a high activity and stability for electrocatalytic oxidation of methanol as compared to the commercial Pt/C catalyst and the co-reduced PtNi nanoparticles. The reasons of the high electrocatalytic activity of the hollow PtNi nanospheres were discussed.     

Crystalline nickel sulfide integrated with amorphous cobalt sulfide as an efficient bifunctional electrocatalyst for water splitting

The development of highly efficient and low-cost electrocatalysts is critical to the mass production of hydrogen from water splitting. Herein, a facile yet effective method was developed to synthesize bimetallic sulfides Ni₃S₂/CoS_x, which were aimed for use as the electrocatalysts in both HER and OER. Encouragingly, the Ni₃S₂/CoS_x demonstrated a low overpotential of 110 mV for HER at a current density of 10 mA·cm^?2. It was discovered that the surface of Ni₃S₂/CoS_x during OER process would undergo an in-situ oxidation to form MOOH (M = Co, Ni), that is, MOOH/Ni₃S₂/CoS_x were the real functioning species in catalysis, which had an excellent OER activity and a low overpotential of 226 mV. Additionally, the assembled electrolyzer required only a low cell voltage of 1.53 V to achieve a current density of 10 mA·cm^?2 in a 1 M KOH solution, and its performance was stable. Overall, this work provided a promising strategy for the facile fabrication of low-cost amorphous electrocatalysts, which is expected to promote the progress of overall water splitting.     

Highly dispersed ultrafine Pt nanoparticles on nickel-cobalt layered double hydroxide nanoarray for enhanced electrocatalytic methanol oxidation

Highly dispersed ultrafine Pt nanoparticles (NPs) were loaded on a nickel-cobalt layered double hydroxide (NiCo-LDH) nanoarray that was grown on Ni foam (NF) via an in situ redox reaction without any external agent between Co²⁺ (Co(OH)₂) in NiCo-LDH and PtCl₆^2-. The obtained Pt/NiCoLDH/NF composite was used as a catalyst for methanol oxidation in alkaline media, showing much higher electrocatalytic activity and better anti-poisoning ability and stability for methanol oxidation than commercial Pt/C, mainly because of the uniform dispersion of ultrafine Pt NPs, the synergistic effect and stable support of NiCoLDH. The NiCoLDH nanoarray effectively increased the specific surface area and location sites for supporting Pt NPs and enhanced the catalytic performance and tolerance to intermediate species. This enhancement was probably due to the synergistic effect between Pt and the NiCo-LDH nanosheets, in which the LDH can provide adequate OH^?_ads species for accelerating the methanol oxidation reaction (MOR).     

High electrocatalytic activity and stability of PtAg supported on rutile TiO2 for methanol oxidation

Rutile TiO₂ is used as a support for the PtAg nanoparticles, and the catalytic activity and stability of PtAg/TiO₂ for the electrooxidation of methanol are investigated. The PtAg nanoparticles with a Pt:Ag atomic ratio of 1:1 are prepared by the chemical co-reduction of the precursors of Pt and Ag, and physical characterizations reveal that the PtAg nanoparticles are evenly dispersed on TiO₂. PtAg/TiO₂ shows significantly higher catalytic activity and stability than PtAg/C, Pt/TiO₂ and Pt/C for methanol oxidation in both alkaline and acidic solutions, indicating that rutile TiO₂ is superior to carbon black as supports and PtAg is superior to Pt in achieving high catalytic activity. Rutile TiO₂ is also shown to be superior to anatase TiO₂ as supports for the PtAg nanoparticles. The results of this study suggest high potential of rutile TiO₂ as a support material for electrocatalysts.     

Electrodeposited Pd nanoparticles on polypyrole/nickel foam for efficient methanol oxidation

The present work describes the Ni foam (Ni–F)/polypyrrole (PPy)/palladium (Pd) (Ni–F/PPy/Pd) multilayered catalysts via a facile electrochemical technique. Potentiostatic deposition of PPy on the surface of Ni–F is followed by galvanostatic deposition of Pd nanoparticles on Ni–F/PPy acted as supports for electrochemical deposition of Pd nanoparticles. The produced catalysts are utilized for electrocatalytic methanol oxidation in alkaline media. Chronoamperometry (CA), cyclic voltammetry (CVs), and electrochemical impedance spectroscopy (EIS) techniques are used to examine the electrocatalytic performance of Ni–F/PPy/Pd based electrodes for methanol oxidation. The polypyrrole modification on Ni–F leads to an improvement in the electrocatalytic activity of the Ni-F/PPY-Pd catalysts toward methanol oxidation. As an open-pored, porous metal with high electrical conductivity, nickel foam produces a substantial amount of active area during the modification of Pd and polypyrrole, which results in significant catalytic activity and a rapid rate charge transfer reaction kinetics on methanol oxidation. The Ni–F/PPy/Pd10 catalyst exhibits enhanced specific activity than its counterparts and a reduced onset potential for methanol oxidation, as well as a low Tafel slope. Based on these results, Ni–F/PPy/Pd10 is suggested as a good material for the anode in the electrocatalytic oxidation of methanol.     

Enhanced electrocatalytic activity of high Pt-loadings on surface functionalized graphene nanosheets for methanol oxidation

Here we report a simple one-pot microwave-polyol reduced method to anchor platinum nanoparticles on graphene with the aid of poly (diallyldimethylammonium chloride) (PDDA), forming a Pt/PDDA–G hybrid (Pt/PDDA–G). High Pt metal loadings, up to 85 wt.% with a mean size of 1.4 nm, were densely in situ decorated on PDDA-modified graphene surfaces. The electrochemical tests showed that the activity and stability of Pt supported on PDDA–graphene hybrid substrates for methanol oxidation were better than that of Pt supported on graphene sheets, also better than the widely used Pt/carbon black electrocatalysts with the same Pt content on the electrode. This improved activity indicates that PDDA plays a crucial role in the highly dispersion and stabilization of Pt nanoparticles on graphene and PDDA–G are able to an alternative support for Pt immobilization in direct methanol fuel cells.     

Platinum-nickel bimetallic catalyst doped with rare earth for enhancing methanol electrocatalytic oxidation reaction

Platinum (Pt) is often used as anodic catalyst for direct methanol fuel cell (DMFC). However, platinum is difficult to achieve large-scale application because of its low stability and high cost. In this work, the electrocatalytic activity and stability of the Pt-based catalyst for methanol oxidation (MOR) are significantly improved by adding Ce and Ni to the catalyst. Additionally, the rare earth element-Pr (Dy) is also chosen to be added into the catalysts for comparison. A series of PtMNi (M = Ce, Pr, Dy) catalysts are prepared by impregnation and galvanic replacement reaction methods using carbon black as support. The electrocatalytic mass activity of PtCeNi/C, PtDyNi/C, PtPrNi/C and Pt/C is 3.92, 1.86, 1.69 and 0.8 A mg_Pt⁻¹, respectively. The mass activity of these the above four catalysts after stability measurement is 3.14, 1.49, 1.27 and 0.72 A mg_Pt⁻¹. Among them, PtCeNi/C has the highest catalytic activity. These as-prepared catalysts are also characterized by various analyzing techniques, such as TEM, HRTEM, XRD, XPS, ICP-OES, STEM, STEM-EDS elemental mapping and line-scanning etc. It shows that PtCeNi/C exhibits best catalytic activity (3.92 A mg_Pt⁻¹) among the as-obtained catalysts, 4.9 times higher than that of commercial Pt/C (0.8 A mg_Pt⁻¹). PtCeNi/C is also with excellent anti-CO poisoning ability. The outstanding catalytic performance of PtCeNi/C for the MOR is mainly attributable to uniform-sized PtCeNi nanoparticles, uniform Ni, Ce and Pt element distribution, and electron interaction among Pt-, Ni- and Ce-related species (electron transferring from Pt to CeO₂).     

High efficient electrocatalytic oxidation of methanol on Pt/polyindoles composite catalysts

Novel composite catalysts have been fabricated by the electrodeposition of Pt onto the glassy carbon electrode (GC) modified respectively with polyindole (PIn) and poly(5-methoxyindole) (PMI) and used for the electrooxidation of methanol in acid solution of 0.5 M H₂SO₄ containing 1.0 M methanol. As-formed composite catalysts are characterized by SEM, XRD and the electrochemical methods. The results of the catalytic activity for methanol oxidation show that the two composite catalysts exhibit higher catalytic activity and stronger poisoning-tolerance than Pt/polypyrrole/GC (Pt/PPy/GC) and Pt/GC. Electrochemical impedance spectroscopy indicates that the methanol electrooxidation on the composite catalysts at various potentials shows different impedance behaviors. At the same time, the charge-transfer resistance for electrooxidation of methanol on Pt/PIn/GC and Pt/PMI/GC is smaller than those on Pt/PPy/GC and Pt/GC. The present study shows a promising choice of Pt/PIn and Pt/PMI as composite catalysts for methanol electrooxidation.     

Construction of carboxyl functional groups and their enhancement effect for methanol electrocatalytic oxidation reaction

In this paper, we investigated the effect of ozone oxidation on properties of commercial carbon black supported platinum (Pt) nanoparticles for the methanol electro-oxidation reaction. The results indicated that the oxygenated functional groups could be introduced on the carbon black evenly with the increase of processing time. Apparently, mainly introduced oxygenated functional group is carboxyl. Platinum nanoparticles could be uniformly immobilized on the surfaces of carbon black treated with ozone, which has significant high electro-catalytic activity and stability for methanol electrooxidation. This phenomenon is attributed to the fact that oxygen-containing groups (mainly for carboxyl functional groups) produced by ozone oxidation are good for improving the dispersion and strengthening the interaction between support and platinum nanoparticles. The ozone oxidation conditions had significant effects on the defects properties of carbon black which showed a positive correlation between the defect levels and methanol electro-oxidation performances. This paper also fully demonstrated the positive relationship between carboxyl functional groups and the performance of methanol electrocatalytic oxidation.     

Pt nanoparticles modified Au dendritic nanostructures: Facile synthesis and enhanced electrocatalytic performance for methanol oxidation

A facile and simple method is presented for the synthesis of bimetallic composites, Pt nanoparticles modified dendritic Au nanostructures (PtNPs/DGNs), in which dendritic Au was deposited on a glassy carbon electrode via a potentiostatic method and sphere-like Pt nanoparticles were decorated on Au substrates through a chemical reduction reaction. The compositions, morphologies, and structures of the PtNPs/DGNs were characterized by X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and energy dispersive X-ray spectroscopy. Results indicated that bimetallic composites were successfully synthesized and spherical Pt nanoparticles were dispersed evenly on dendritic Au substrates. The number of Pt nanoparticles on Au surface was regulated by controlling the chemical reduction deposition time, allowing the electrocatalytic properties of the composite towards methanol oxidation to be tuned. Electrochemical measurements, including cyclic voltammetry and chronoamperometry, were performed to investigate the electrochemical properties and electrocatalytic behaviors of the PtNPs/DGNs towards methanol oxidation. Pt nanoparticles partially covered dendritic Au exhibited dramatically enhanced electrocatalytic activity (3.947 mA cm^?2), which was 2.65 times that of commercial carbon-supported Pt nanoparticles (1.487 mA cm^?2), along with much improved poisoning tolerance (current decline: 70.85% vs 99.36%). These enhanced performances were likely caused by the large active electrochemical area of the bimetallic nanocomposites and the change in the electronic structure of Pt when the Au surface was modified with fewer Pt nanoparticles.     

TiC supported Pt-based nanoparticles: Facile sonochemical synthesis and electrocatalytic properties for methanol oxidation reaction

In this study, we synthesized Pt nanoparticles (NPs) with small amounts of Mn (≤11.4 at%) included, hence Pt(Mn) NPs, on titanium carbide (TiC) support (denoted as Pt(Mn)/TiC) in three different Pt loadings (16.0–33.2 wt%) and investigated their electrocatalytic performance for methanol oxidation reaction (MOR) in acidic media. The syntheses were achieved via one-pot sonochemical reactions of Pt(acac)₂ and Mn(acac)₂ (acac = acetylacetonate) in ethylene glycol in the presence of TiC particles and without any other additives. The Pt(Mn) NPs were uniform in size (4–6 nm) and were evenly deposited on the TiC surface. The electronic structure of Pt in Pt(Mn)/TiC samples, probed by X-ray photoelectron spectroscopy (XPS) and other techniques, is systematically changed with the Pt loading, by which enhanced electrocatalytic properties from pure Pt are expected. In addition, the TiC support contributes to enhancing the electrocatalytic properties of Pt(Mn) NPs through its high conductivity, chemical resistance to corrosion, and the TiO₂ formed on the surface which exerts the bifunctional mechanism to reduce the CO poisoning on Pt. The electrochemical performance of Pt(Mn)/TiC was investigated by the rotating disk electrode (RDE) technique. The specific and mass MOR currents are, respectively, 1.6–2.2 and 0.9–1.4 times higher in Pt(Mn)/TiC samples than in commercial Pt/C. All Pt(Mn)/TiC samples show 93–98% of the initial electrochemical surface areas after 3000 potential cycles, superior electrochemical stability to commercial Pt/C (86%).     

Cobalt nickel boride nanocomposite as high-performance anode catalyst for direct borohydride fuel cell

Similar to MXene, MAB is a group of 2D ceramic/metallic boride materials which exhibits unique properties for various applications. However, these 2D sheets tend to stack and therefore lose their active surface area and functions. Herein, an amorphous cobalt nickel boride (Co–Ni–B) nanocomposite is prepared with a combination of 2D sheets and nanoparticles in the center to avoid agglomeration. This unique structure holds the 2D nano-sheets with massive surface area which contains numerous catalytic active sites. This nanocomposite is prepared as an electrocatalyst for borohydride electrooxidation reaction (BOR). It shows outstanding catalytic activity through improving the kinetic parameters of BH₄^? oxidation, owing to abundant ultrathin 2D structure on the surface, which provide free interspace and electroactive sites for charge/mass transport. The anode catalyst led to a 209 mW/cm² maximum power density with high open circuit potential of 1.06 V at room temperature in a miniature direct borohydride fuel cell (DBFC). It also showed a great longevity of up to 45 h at an output power density of 64 mW/cm², which is higher than the Co–B, Ni–B and PtRu/C. The cost reduction and prospective scale-up production of the Co–Ni–B catalyst are also addressed.     

Facile preparation of Pt-based cage-bell structured nanoarchitectures for enhanced methanol oxidation electrocatalysis

The porous Pt-based nanomaterials are highly desired for their superb methanol oxidation reaction (MOR) activity. In this work, an effective method was proposed to synthesize Pd@mesoporous PtAu cage-bell structured nanomaterials (Pd@mPtAu CBs). In the synthetic process, Pd@SiO₂ nanoparticles and F127 were used as template and structure directing agent, respectively. The obtained Pd@mPtAu CBs are evenly distributed in size with highly porous surface and interconnected micro-structure. Significantly, the prepared Pd@mPtAu CBs exhibit outstanding catalytic activity and stability toward MOR, which is confirmed as a promising electrocatalyst of direct methanol fuel cells. Furthermore, the proposed method is also suitable for the preparation of other Pt-based nanomaterials with cage-bell architecture, such as Pd@mPt CBs.     

Electrodeposition of platinum microparticle interface on conducting polymer film modified nichrome for electrocatalytic oxidation of methanol

A simple and “green” approach for fabrication of platinum microparticle interface on conducting polymer film modified nichrome matrix (Pt/PAn/Nc) for methanol oxidation was investigated. The Pt microparticles were grown directly on the polyaniline precursor film modified nichrome matrix (PAn/Nc) in dilute chloroplatinic acid solution by cyclic voltammetry. The SEM revealed that the deposits were composed of spherical Pt microparticles. Cyclic voltammetry and chronoamperometry were used for characterization of the electrode properties. Results showed that the spherical Pt/PAn/Nc electrode enhanced the catalytic activity and promoted methanol electrooxidation. The catalytic activity of Pt/PAn/Nc electrode was 15 times higher than that obtained from pure platinum under the same conditions. Moreover, the deposited Pt microparticles improved the electrochemical properties of nichrome and reduced the dosage of noble metal platinum, remarkably. The cost could be reduced dramatically by decreasing the contents of platinum. The Pt/PAn/Nc are likely a promising electrocatalyst for methanol electrooxidation.     

Promotion of the electrocatalytic activity of a bimetallic platinum-ruthenium catalyst by repetitive redox treatments for direct methanol fuel cell

Pt-Ru/C catalyst (12 wt%) was prepared by the incipient wetness impregnation method followed by a redox heat-treatment. Transmission electron microscopy (TEM) results revealed uniformly distributed metallic crystallites of Pt-Ru alloy nanoparticles (d_PtRu = 2.1 ± 1.0 nm). The effect of redox treatments of the impregnated catalysts on methanol oxidation reaction (MOR) was examined by cyclic voltammetry (CV). The MOR activity of the PtRu/C was significantly improved after each oxidation step of the redox treatment cycles. The enhanced catalytic activity was found to be quite stable in chronoamperometry (CA) measurements. CV, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) results strongly suggested that the improved catalytic activity was due to the formation of a stable c-RuO_x (x = 2-3) domain during the oxidation treatments. A bifunctional based mechanism was proposed for the MOR on the oxidized PtRu/C catalysts. Formation of Ru-OH species on the surface of c-RuO_x domains was suggested as stale sites for the oxidation of carbon monoxide adsorbed on the Pt catalytic sites.     

Carbon supported PtPdCr ternary alloy nanoparticles with enhanced electrocatalytic activity and durability for methanol oxidation reaction

In this work, the trimetallic PtPdCr nanoparticles with low platinum loading (~5 wt%) supported on Vulcan carbon (PtPdCr/C) were synthesized through a facile two-step co-reduction method and showed superior methanol oxidation activity. The particle size distribution, morphology and elemental composition of the PtPdCr/C were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. The electrochemical performance for methanol oxidation of the PtPdCr/C was found to be higher with the mass activity of 969 mA·mg⁻¹_Pt compared to Pt/C (581 mA·mg⁻¹ _Pt) and PtRu/C (725 mA·mg⁻¹ _Pt). Moreover, the stability studies confirmed the enhanced durability of PtPdCr/C over Pt/C and PtRu/C catalysts after the accelerated durability test (ADT) and chronoamperometry (CA) analysis. The increased methanol oxidation activity and durability of the trimetallic PtPdCr/C in acid medium can be attributed to the change in binding energy of Pt and the induced synergistic effect from Pd and Cr atoms to Pt, which demonstrated a promising strategy for the preparation and utilization of ternary alloy catalysts towards methanol electrooxidation.     

Platinum nanoparticles anchored on aminated silica@PEDOT-PSS hybrid for enhanced methanol oxidation electrocatalysis

Direct methanol fuel cell (DMFC) with near-zero pollution emission, large energy density, and low operating temperature provides a beneficial and sustainable way for alleviating fossil energy crisis and ecological pollution issues. In this work, a systematic protocol was explored for the design of novel electrocatalyst based on PEDOT-PSS coated amino-functionalized SiO₂ microspheres (SiO₂–NH₂@PEDOT-PSS) support, and then Pt nano-particles (NPs) were uniformly anchored for the anodic process of DMFCs. Characterization techniques, e.g. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed that the dispersity and homogeneity of Pt NPs on the surface of SiO₂–NH₂@PEDOT-PSS were markedly improved due to PEDOT-PSS modification, and the distribution of Pt NPs was in a smaller mean-size ~2.8 nm. Subsequently, X-ray photoelectron spectroscopy (XPS) study exposed fast electron shift phenomenon from SiO₂–NH₂@PEDOT-PSS support to Pt NPs in the catalyst. The various electrochemical tests such as cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (EIS) revealed that the prepared Pt/SiO₂–NH₂@PEDOT-PSS catalyst presented higher electrocatalytic efficacy, excellent durability with improved CO-tolerance towards methanol oxidation reaction rather than commercial Pt/C catalyst. These distinctive physical and chemical features of designed catalyst raise the spirit to design an efficient electrocatalyst based on Pt/SiO₂–NH₂@PEDOT-PSS in DMFC applications.