PdAg/C Electrocatalysts Synthesized by Thermal Decomposition of Polymeric Precursors Improve Catalytic Activity for Ethanol Oxidation Reaction

An efficient ethanol oxidation reaction (EOR) is required to enhance energy production in alcohol-based fuel cells. The use of bimetallic catalysts promises decreasing reliance on platinum group metal (PGM) electrocatalysts by minimizing the use of these expensive materials in the overall electrocatalyst composition. In this article, an alternative method of bimetallic electrocatalyst synthesis based on the use of polymeric precursors is explored. PdAg/C electrocatalysts were synthesized by thermal decomposition of polymeric precursors and used as the anode electrocatalyst for EOR. Different compositions, including pristine Pd/C and Ag/C, as well as bimetallic Pd80Ag20/C, and Pd60Ag40/C electrocatalysts, were evaluated. Synthesized catalysts were characterized, and electrochemical activity evaluated. X-ray diffraction showed a notable change at diffraction peak values for Pd80Ag20/C and Pd60Ag40/C electrocatalysts, suggesting alloying (solid solution) and smaller crystallite sizes for Pd60Ag40/C. In a thermogravimetric analysis, the electrocatalyst Pd60Ag40/C presented changes in the profile of the curves compared to the other electrocatalysts. In the cyclic voltammetry results for EOR in alkaline medium, Pd60Ag40/C presented a more negative onset potential, a higher current density at the oxidation peak, and a larger electrically active area. Chronoamperometry tests indicated a lower poisoning rate for Pd60Ag40/C, a fact also observed in the CO-stripping voltammetry analysis due to its low onset potential. As the best performing electrocatalyst, Pd60Ag40/C has a lower mass of Pd (a noble and expensive metal) in its composition. It can be inferred that this bimetallic composition can contribute to decreasing the amount of Pd required while increasing the fuel cell performance and expected life. PdAg-type electrocatalysts can provide an economically feasible alternative to pure PGM-electrocatalysts for use as the anode in EOR in fuel cells.

Low-Pt NiNC-supported PtNi nanoalloy oxygen reduction reaction electrocatalysts—In situ tracking of the atomic alloying process

Carbon-supported platinum-nickel (Pt-Ni) alloy nanoparticles (NPs) emerge as the electrocatalysts of choice for deployment in polymer electrolyte membrane fuel cell (PEMFC) cathodes. To date, viable PtNi nanoalloy catalysts are characterized by large Pt weight loading of up to 50 wt%. To a large extent, their preparation processes often involve the use of expensive or even hazardous organometallic metal precursors, solvents and capping agents, substantially limiting their synthetic scalability and sustainability. Here, we report a novel synthetic strategy toward highly active low-Pt loaded PtNi nanoalloy Oxygen Reduction Reaction (ORR) catalysts. The synthesis involves the Pyrolysis and Leaching of Ni-organic polymers, subsequent Pt nanoparticle Deposition followed by thermal Alloying (referred to as PLDA) to prepare single Ni atom site (NiNC)-supported bimetallic PtNi nanoalloy electrocatalysts with very low Pt weight contents of 3–5 wt% Pt loading. We demonstrate that despite this low Pt weight loading, the catalysts exhibit more favorable Pt-mass activities compared to conventional, carbon-supported 20–30 wt%Pt Pt-loaded benchmark PtNi alloy catalysts. Using in situ transmission electron microscopy, cyclic voltammetry, and surface CO stripping techniques, we track and unravel the key stages of the formation process of the PtNi nanoparticle catalysts directly at the atomic scale. By carefully chosen reference experiments, we find that carbon-encapsulated Ni NPs, rather than NiNx single sites, serve exclusively as the Ni atom source for PtNi alloy formation during thermal treatments. Our materials concepts offer a pathway to further decrease the overall Pt content of PEM fuel cell devices.

The CO Tolerance of Pt/C and Pt-Ru/C Electrocatalysts in a High-Temperature Electrochemical Cell Used for Hydrogen Separation

This paper describes an experimental evaluation and comparison of Pt/C and Pt-Ru/C electrocatalysts for high-temperature (100–160 °C) electrochemical hydrogen separators, for the purpose of mitigating CO poisoning. The performances of both Pt/C and Pt-Ru/C (Pt:Ru atomic ratio 1:1) were investigated and compared under pure hydrogen and a H2/CO gas mixture at various temperatures. The electrochemically active surface area (ECSA), determined from cyclic voltammetry, was used as the basis for a method to evaluate the performances of the two catalysts. Both CO stripping and the underpotential deposition of hydrogen were used to evaluate the electrochemical surface area. When the H2/CO gas mixture was used, there was a complex overlap of mechanisms, and therefore CO peak could not be used to evaluate the ECSA. Hence, the hydrogen peaks that resulted after the CO was removed from the Pt surface were used to evaluate the active surface area instead of the CO peaks. Results revealed that Pt-Ru/C was more tolerant to CO, since the overlapping reaction mechanism between H2 and CO was suppressed when Ru was introduced to the catalyst. SEM images of the catalysts before and after heat treatment indicated that particle agglomeration occurs upon exposure to high temperatures (>100 °C)

Carbon-supported Platinum Electrocatalysts probed in a Gas Diffusion Setup with Alkaline Environment: how Particle Size and Mesoscopic Environment influence the Degradation Mechanism

In this work, we investigate the stability of four different types of Pt/C fuel cell catalysts upon applying accelerated degradation tests (ADTs) in a gas diffusion electrode (GDE) setup equipped with an anion exchange membrane (AEM). In contrast to previous investigations exposing the catalysts to liquid electrolyte, the GDE setup provides a realistic three-phase boundary of the reactant gas, catalyst and ionomer which enables reactant transport rates close to real fuel cells. Therefore, the GDE setup mimics the degradation of the catalyst under more realistic reaction conditions as compared to conventional electrochemical cells. Combining the determination of the loss in electrochemically active surface area (ECSA) of the Pt/C catalysts via CO stripping measurements with the change in particle size distribution determined by small-angle X-ray scattering (SAXS) measurements, we demonstrate that i) the degradation mechanism depends on the investigated Pt/C catalyst and might indeed be different to the one observed in conventional electrochemical cells, ii) degradation is increased in an oxygen gas atmosphere (as compared to an inert atmosphere), and iii) the observed degradation mechanism depends on the mesoscopic environment of the active phase. The measurements indicate an increased particle growth if small and large particles are immobilized next to each other on the same carbon support flakes as compared to a simple mix of two catalysts with small and large particles, respectively.

Carbon-supported Platinum Electrocatalysts probed in a Gas Diffusion Setup with Alkaline Environment: how Particle Size and Mesoscopic Environment influence the Degradation Mechanism

In this work, we investigate the stability of four different types of Pt/C fuel cell catalysts upon applying accelerated degradation tests (ADTs) in a gas diffusion electrode (GDE) setup equipped with an anion exchange membrane (AEM). In contrast to previous investigations exposing the catalysts to liquid electrolyte, the GDE setup provides a realistic three-phase boundary of the reactant gas, catalyst and ionomer which enables reactant transport rates close to real fuel cells. Therefore, the GDE setup mimics the degradation of the catalyst under more realistic reaction conditions as compared to conventional electrochemical cells. Combining the determination of the loss in electrochemically active surface area (ECSA) of the Pt/C catalysts via CO stripping measurements with the change in particle size distribution determined by small-angle X-ray scattering (SAXS) measurements, we demonstrate that i) the degradation mechanism depends on the investigated Pt/C catalyst and might indeed be different to the one observed in conventional electrochemical cells, ii) degradation is increased in an oxygen gas atmosphere (as compared to an inert atmosphere), and iii) the observed degradation mechanism depends on the mesoscopic environment of the active phase. The measurements indicate an increased particle growth if small and large particles are immobilized next to each other on the same carbon support flakes as compared to a simple mix of two catalysts with small and large particles, respectively.

Carbon-supported Platinum Electrocatalysts probed in a Gas Diffusion Setup with Alkaline Environment: how Particle Size and Mesoscopic Environment influence the Degradation Mechanism

In this work, we investigate the stability of four different types of Pt/C fuel cell catalysts upon applying accelerated degradation tests (ADTs) in a gas diffusion electrode (GDE) setup equipped with an anion exchange membrane (AEM). In contrast to previous investigations exposing the catalysts to liquid electrolyte, the GDE setup provides a realistic three-phase boundary of the reactant gas, catalyst and ionomer which enables reactant transport rates close to real fuel cells. Therefore, the GDE setup mimics the degradation of the catalyst under more realistic reaction conditions as compared to conventional electrochemical cells. Combining the determination of the loss in electrochemically active surface area (ECSA) of the Pt/C catalysts via CO stripping measurements with the change in particle size distribution determined by small-angle X-ray scattering (SAXS) measurements, we demonstrate that i) the degradation mechanism depends on the investigated Pt/C catalyst and might indeed be different to the one observed in conventional electrochemical cells, ii) degradation is increased in an oxygen gas atmosphere (as compared to an inert atmosphere), and iii) the observed degradation mechanism depends on the mesoscopic environment of the active phase. The measurements indicate an increased particle growth if small and large particles are immobilized next to each other on the same carbon support flakes as compared to a simple mix of two catalysts with small and large particles, respectively.

PAC Synthesis and Comparison of Catalysts for Direct Ethanol Fuel Cells

Pt/C, PtMOn/C (M = Ni, Sn, Ti, and PtX/C (X = Rh, Ir) catalyst systems were prepared by using the pulse alternating current (PAC) technique. Physical and electrochemical parameters of samples were carried out by x-ray powder diffraction (XRD), transmission electron microscopy (TEM), and CO stripping. The catalytic activity of the synthesized samples for the ethanol electrooxidation reaction (EOR) was investigated. The XRD patterns of the samples showed the presence of diffraction peaks characteristic for Pt, NiO, SnO2, TiO2, Rh, and Ir. The TEM images indicate that the Pt, Rh, and PtIr (alloys) particles had a uniform distribution over the carbon surface in the Pt/C, PtRh/C, PtIr/C, and PtMOn/C (M = Ni, Sn, Ti) catalysts. The electrochemically active surface area of catalysts was determined by the CO-stripping method. The addition of a second element to Pt or the use of hybrid supported catalysts can evidently improve the EOR activity. A remarkable positive affecting shift of the onset potential for the EOR was observed as follows: PtSnO2/C > PtTiO2/C ≈ PtIr/C ≈ PtNiO/C > PtRh/C ≈ Pt/C. The addition of SnO2 to Pt/C catalyst led to the decrease of the onset potential and to significantly facilitate the EOR. The long-term cyclic stability of the synthesized catalysts was investigated. Thereby, the PtSnO2/C catalyst prepared by the PAC technique can be considered as a promising anode catalyst for direct ethanol fuel cells.

Size dependent oxygen reduction and methanol oxidation reactions: catalytic activities of PtCu octahedral nanocrystals

Synthesis of PtCu octahedral nanocatalysts with controlled size and strain exhibit excellent oxygen reduction reaction, but leads to higher onset over-potentials in methanol oxidation reaction and CO-stripping.