Multi-skeletal PtPdNi nanodendrites as efficient electrocatalyst with high activity and durability towards oxygen reduction reaction

Engineering alloy nanostructures with a combination of highly active noble metals (Pt and Pd) and less electronegative non-noble metal (Ni) is found to be crucial for improving surface reactivity by enriching with active Pt sites. Herein, a multi-skeletal PtPdNi nanodendrites (NDs) was successfully formed by a simple one-pot method with structure directing agent. The modification of Pt electronic structure and their interaction due to compressive strain were explored using benchmark characterization techniques, which showed that the PtPdNi NDs possess Pt-enriched surface, corroborating to more active catalyst sites for oxygen reduction reaction (ORR) in acidic medium. The PtPdNi NDs have a higher electrochemical surface area (63 m² g^?1) and an earlier onset potential (1.01 V) than PtPd NDs, PtNi NDs, and commercial Pt/C catalysts, indicating the outstanding ORR performance. The high mass and specific activities, as well as superior durability after accelerated degradation test (ADT), highlight the remarkable electrocatalytic performance of PtPdNi NDs over others. As a result, enhancing Pt utilization through the formation of PtPdNi NDs could be a reliable strategy to improve ORR electrocatalysis for polymer electrolyte membrane fuel cell (PEMFC) applications.     

Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.     

Effect of MnOx phase on Pt-based catalyst for enhancing CO/C3H6/NO oxidation performance

To improve the fuel economy, it is crucial to promote the low-temperature performance in eliminating diesel emissions. The work investigates the impact of different MnO₂/Mn₂O₃ phase ratio on the low-temperature performance of Pt-based monolithic diesel oxidation catalyst. Near equal ratio of MnO_x phase could form the three-phase (platinum, MnO₂, Mn₂O₃) interfacial structure, leading to the smaller platinum particle size and exhibiting the higher interface rate (1.6–11.1 times) than other mono-manganese oxide with platinum. Besides, the higher oxygen mobility and more active oxygen species could be contributed to the positive effect of Pt/MnO_x interface, which are prevalent to activate the reactant and greatly enhance the TOF value (1.4–20.8 times). The results imply that the modification of multi-phase metal/oxide interface is potential in dispersing platinum for greatly enhancing the catalytic efficiency.     

Morphological influence of graphitic carbon nanofibers by N–F dual-doping on Pt electrocatalytic activity and stability for oxygen reduction reaction in polymer electrolyte membrane fuel cells

Morphology of carbon nanofibers significantly effects Pt nanoparticles dispersion and specific interaction with the support, which is an important aspect in the fuel cell performance of the electrocatalysts. This study emphasizes, the defects creation and structural evolution comprised due to N–F co-doping on graphitic carbon nanofibers (GNFs) of different morphologies, viz. GNF-linearly aligned platelets (L), antlers (A), herringbone (H), and their specific interaction with Pt nanoparticle in enhancing the oxygen reduction reaction (ORR). GNFs–NF–Pt catalysts exhibit better ORR electrocatalytic activity, superior durability that is solely ascribed to the morphological evolution and the doped N–F heteroatoms, prompting the charge density variations in the resultant carbon fiber matrices. Amongst, H–NF–Pt catalyst performed outstanding ORR activity with exceptional electrochemical stability, which shows only 20 mV loss in the half-wave potential whilst 100 mV loss for Pt/C catalyst on 20,000 potential cycling. The PEMFC comprising H–NF–Pt as cathode catalyst with minimum loading of 0.10 mg cm^?2, delivers power density of 0.942 W cm^?2 at current density of 2.50 A cm^?2 without backpressures in H₂–O₂ feeds. The H–NF–Pt catalyst owing to its hierarchical architectures, performs well in PEMFC at the minimized catalyst loading with outstanding stability that can significantly decrease total price for the fuel cell.     

The significant promotion of g-C3N4 on Pt/CNS catalyst for the electrocatalytic oxidation of methanol

This article reported a series of g–C₃N₄–CNS (g-C₃N₄ and carbon nanosheets) composite carriers formed by the hydrothermal method, and then the ethylene glycol reduction method was used to anchor Pt nanoparticles on the g–C₃N₄–CNS carrier to form the Pt/g–C₃N₄–CNS catalysts. The electrochemical test for the electrocatalytic oxidation of methanol (MOR) shown that the Pt/20%g–C₃N₄–CNS catalyst has the best catalytic performance and stability. These Pt/g–C₃N₄–CNS catalysts were analyzed by TEM, XRD, XPS, and BET characterization. It is discovered that the amount of g-C₃N₄ greatly influenced the structure and chemical properties of Pt/CNS precursor. As the content of g-C₃N₄ increases, the content of pyridine nitrogen and pyrrole nitrogen also increases, and N species can enhance the interaction between Pt nanoparticles and CNS, promote Pt dispersion, and increase the specific surface area of the catalyst. Similarly, an excessive addition of g-C₃N₄ will cause a sharp decline in the conductivity of the catalyst, and then led to the decline of MOR activity.     

Recent advances in two-dimensional Pt based electrocatalysts for methanol oxidation reaction

Direct methanol fuel cells (DMFCs) had been attracted considerable attention for its advantages of high energy density, simplified systems and readily transportation and storage of methanol. However, the notoriously sluggish kinetics of methanol oxidation reaction (MOR) of the anode reaction, had greatly affected the commercialization of DMFCs. On one hand, Pt based catalyst are still the most effective MOR catalysts, while the high cost caused by the high loadings of electrocatalyst to compensate the low MOR activity impedes the wide accessible of DMFCs. In addition, the occurrence of catalyst poisoning owing to the strong interaction between Pt and carbon monoxide (CO) generated during the MOR processing, further leading to the fast decay in the performance and stability of MOR electrocatalysts. Two-dimensional (2D) Pt based nanostructures is regarded to be one promising and effective class of MOR electrocatalysts, and attracted much attention due to the high electron mobility, highly exposed active sites, and extraordinary thermal conduction. In this review, the mechanism of MOR was firstly introduced, and then the synthesis conditions, structure characteristics and methanol oxidation performances both in acidic and alkaline dielectric of 2D Pt based nanocatalysts were introduced. Subsequently, we briefly analyzed the structural characteristics of 2D Pt based nanocatalysts and their advantages, including the low platinum loadings, high specific surface area and majority of atomic active sites exposed. Finally, the opportunities and challenges for designing of advanced 2D Pt based nanocatalysts was proposed and discussed.     

Anchoring single Pt atoms on hollow Ag3VO4 spheres for improved activity towards photocatalytic H2 evolution reaction

The high cost of noble metal catalysts has been a great bottleneck for the catalyst industry. Using the noble metal at a single-atom level for catalytic applications could dramatically decrease the cost. The impacts of single Pt atoms on the photocatalytic performance of Ag₃VO₄ have been investigated and reported. In this report, single Pt atoms were anchored on the surface of Ag₃VO₄ (AVO) as a cocatalyst, and the resultant composite photocatalyst has been studied for photocatalytic H₂ production from water driven by visible light. The as-prepared AVO particles are hollow nanospheres in the monoclinic phase with a bandgap of 2.20 eV. The light absorption edge of AVO/Pt is slightly red-shifted compared to that of the pristine AVO, indicating more visible light absorption of AVO/Pt. The XPS peaks of Ag, V, and Pt exhibit a significant shift after AVO and Pt get into contact, suggesting the strong interaction between the surface Ag and V atoms, and single Pt atoms. After 3-h illumination, the photocatalytic H₂ evolution amount from AVO/Pt is improved up to 1400 μmol, which is 2.8 times that on the bare AVO. Such efficient photocatalytic H₂ evolution on AVO/Pt is still maintained after five reaction cycles. The better photocatalytic performance of AVO/Pt has been attributed to the more efficient visible light utilization and the lower interfacial charge transfer resistance, as demonstrated in the DRS and EIS spectra. The presence of the surface Pt atoms also leads to a higher amount of reactive radicals, which could efficiently promote the surface redox reactions.     

Pore-scale study of effects of different Pt loading reduction schemes on reactive transport processes in catalyst layers of proton exchange membrane fuel cells

Reducing the Platinum (Pt) loading while maintaining the performance is highly desired for promoting the commercial use of proton exchange membrane fuel cells (PEMFCs). Different methods have been adopted to fabricate catalyst layers (CLs) with low Pt loading, including utilizing lower Pt/C catalysts (MA), mixing high Pt/C catalysts with bare carbon black particles (MB), and reducing CL thickness while maintaining high Pt/C ratio (MC). In this study, self-developed pore-scale model is adopted to investigate the performance of the three Pt reduction methods. It is found that MA shows the best performance while MB shows the worst. Then, effects of Pt dispersion are further explored. The results show that denser Pt sites will result in higher local oxygen flux and thus higher local transport resistance. Therefore, MA method, which shows the better Pt dispersion, leads to improved performance. Third, CLs with quasi-realistic structures are investigated. Higher tortuosity resulting from the random pores produces higher bulk resistance along the thickness direction, while MA still exhibits the best performance. Finally, improved CL structures are investigated by designing perforated CL structures. It is found that adding perforations can significantly reduce the bulk transport resistance and can improve the CL performance. It is demonstrated that CL structure plays important roles on performance, and there are still huge potentials to further improve CL performance by increasing Pt dispersion and optimizing CL structures.     

Preparation of PEDOT-modified double-layered hollow carbon spheres as Pt catalyst support for methanol oxidation

In this paper, Pt nanoparticles (Pt NPs) deposited hybrid carbon support is prepared by modifying double-layered hollow carbon spheres（DLHCs）with poly(3,4-ethylenedioxythiophene) (PEDOT) and used as anode catalyst of methanol oxidation. The structure of nanocomposites is characterized by SEM, TEM, FT-IR, XRD and XPS, confirming the greatly enhanced synergistic effect between the PEDOT and DLHCs, and illustrating the uniform distribution of Pt NPs on the PEDOT/DLHCs composite surface with a small particle size (~2.63 nm). Cyclic voltammetry, chronoamperometry and impedance spectroscopy applied to determine the electrocatalytic activity of catalysts, it is found that the synthesized PEDOT/DLHCs/Pt possesses excellent characteristics such as large electrochemically active surface area and high mass activity of 59.45 m² g⁻¹ and 807 mA mg⁻¹ in 0.5 M H₂SO₄ containing 1 M methanol solution, which is almost 1.24 and 2.8 times greater than those of commercial Pt/C, and the catalyst exhibits superior stability after 500 durability cycles. The enhanced electrocatalytic behavior can be ascribed to the excellent electronic conductivity of PEDOT-modified DLHCs and the strong binding of PEDOT/DLHCs to Pt NPs, suggesting that the PEDOT/DLHCs/Pt is a promising electrocatalyst for direct methanol fuel cell.