Construction of Concave PdAg Nanoshells with Limited Thickness for Efficient Electroxidation of Ethanol

Noble metal nanocrystals enclosed with curved surfaces are of great benefit for applications in electrocatalysis since the atomic steps and kinks on these facets have higher chemical activity. Herein, we report the fabrication of PdAg nanoshells with tunable thickness in the range of 5–13 nm and a unique concave cubic morphology, as well as the exploration of their applications for ethanol oxidation reaction (EOR) in alkaline media. The success of current work relies on the conformal deposition of PdAg on concave Au nanocubes, where the controlled reaction kinetics and proper chosen capping agent are both crucial for the growth mode. When loaded on carbon black and working as electrocatalysts, they exhibited superb electrochemical activity (e.g., 600.21 mA mg−1 in mass activity and 19.57 A m−2 in specific activity), together with improved EOR kinetics and long-term durability, as compared to Au@Pd nanoparticles and commercial Pd/C. The current work offers a feasible strategy to produce PdAg bimetallic nanocrystals with concave surface and validates their promising application as fuel cell catalysts, which could be extended to morphology engineering of other noble-metal nanocrystals for a broad range of applications.

Recent Studies on Bimetallic Pt–M Catalyst for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells

Due to environmental pollution and global warming, research on new energy sources that can replace fossil fuels is important. A fuel cell is an eco-friendly energy conversion system that discharges water, and uses hydrogen as fuel. Although platinum is a widely used catalyst in PEMFCs, it has commercial limitations because of its low stability and high cost. Pt-based bimetal catalysts are being studied to improve performance and reduce the cost of fuel cell catalysts. Pt-M is excellent in terms of performance, stability, and cost, avoiding the disadvantages of the Pt catalyst. Studies on various bimetallic catalysts have been conducted, and among them, studies on Pt-Ni, Pt-Co, and Pt-Fe have been the most active. This review summarizes reports of fuel cell catalysts using Pt-M from 2014 to 2020. In recent studies, in order to improve the Pt-M performance, there have been attempts to change the pretreatment, the type of support, and the composition of Pt and M. There have also been studies that have applied new synthetic methods, which are different from traditional synthetic methods. Many Pt-M catalysts have shown better performance than commercial Pt/C, and exhibited stable performance in durability tests.

Recent Studies on Bimetallic Pt–M Catalyst for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells

Due to environmental pollution and global warming, research on new energy sources that can replace fossil fuels is important. A fuel cell is an eco-friendly energy conversion system that discharges water, and uses hydrogen as fuel. Although platinum is a widely used catalyst in PEMFCs, it has commercial limitations because of its low stability and high cost. Pt-based bimetal catalysts are being studied to improve performance and reduce the cost of fuel cell catalysts. Pt-M is excellent in terms of performance, stability, and cost, avoiding the disadvantages of the Pt catalyst. Studies on various bimetallic catalysts have been conducted, and among them, studies on Pt-Ni, Pt-Co, and Pt-Fe have been the most active. This review summarizes reports of fuel cell catalysts using Pt-M from 2014 to 2020. In recent studies, in order to improve the Pt-M performance, there have been attempts to change the pretreatment, the type of support, and the composition of Pt and M. There have also been studies that have applied new synthetic methods, which are different from traditional synthetic methods. Many Pt-M catalysts have shown better performance than commercial Pt/C, and exhibited stable performance in durability tests.

The Gas diffusion electrode setup as a testing platform for evaluating fuel cell catalysts: a comparative RDE-GDE study

Gas diffusion electrode (GDE) setups have been recently introduced as a new experimental approach to test the performance of fuel cell catalysts. As compared to the state-of-the-art in fundamental research, i.e., rotating disk electrode (RDE) measurements, GDE measurements offer several advantages. Most importantly mass transport limitations, inherent to RDE measurements are avoided. In a GDE setup the reactant, e.g., oxygen gas, is not dissolved into a liquid electrolyte but distributed through a gas diffusion layer (GDL), as it is actually the case in fuel cells. Consequently, much higher current densities can be achieved, and the catalysts can be studied in a wider and more relevant potential range. Furthermore, direct contact to a liquid electrolyte can be avoided and elevated temperatures can be employed in a straight-forward manner. However, the use of GDE setups also comes with some challenges. The determined performance is not strictly related to the catalyst itself (intrinsic activity), but also to the quality of the catalyst film preparation. Therefore, it might be even more important than in RDE testing to develop standardized procedures to prepare catalysts inks and films that can be reproduced effortlessly in research laboratories for fundamental and applied experimentation. To develop such standardized testing protocols, we present a comparative RDE – GDE study, where we investigate several commercial standard Pt/C fuel cell catalysts with respect to the oxygen reduction reaction (ORR). The study highlights the strengths of the GDE approach as an intermediate “testing step” between RDE and membrane electrode assembly (MEA) tests when developing new fuel catalysts.

Operando SAXS Study of a Pt/C Fuel Cell Catalyst with an X-ray Laboratory Source

Small angle X-ray scattering (SAXS) is a powerful technique to investigate the degradation of catalyst materials. Ideally such investigations are performed <i>operando</i>, i.e., during a catalytic reaction. An example of <i>operando </i>measurements is to observe the degradation of fuel cell catalysts during an accelerated stress test (AST). Fuel cell catalysts consist of Pt or Pt alloy nanoparticles (NPs) supported on a high surface area carbon. A key challenge of operando SAXS measurements is a proper background subtraction of the carbon support to extract the information of the size distribution of the Pt NPs as a function of the AST treatment. Typically, such operando studies require the use of synchrotron facilities. The background measurement can then be performed by anomalous SAXS (aSAXS) or in a grazing incidence con-figuration. In this work we present a proof-of-concept study demonstrating the use of a laboratory X-ray diffractometer for <i>operando </i>SAXS. Data acquisition of <i>operando </i>SAXS with a laboratory X-ray diffractometer is desirable due to the general challenging and limited accessibility of synchrotron facilities. They become even more crucial under the ongoing and foreseen restrictions related to the COVID-19 pandemic. Although, it is not the aim to completely replace synchrotron-based studies, it is shown that the background subtraction can be achieved by a simple experimental consideration in the setup that can ultimately facilitate <i>operando </i>SAXS measurements at a synchrotron facility. <br>

Operando SAXS Study of a Pt/C Fuel Cell Catalyst with an X-ray Laboratory Source

Small angle X-ray scattering (SAXS) is a powerful technique to investigate the degradation of catalyst materials. Ideally such investigations are performed <i>operando</i>, i.e., during a catalytic reaction. An example of <i>operando </i>measurements is to observe the degradation of fuel cell catalysts during an accelerated stress test (AST). Fuel cell catalysts consist of Pt or Pt alloy nanoparticles (NPs) supported on a high surface area carbon. A key challenge of operando SAXS measurements is a proper background subtraction of the carbon support to extract the information of the size distribution of the Pt NPs as a function of the AST treatment. Typically, such operando studies require the use of synchrotron facilities. The background measurement can then be performed by anomalous SAXS (aSAXS) or in a grazing incidence con-figuration. In this work we present a proof-of-concept study demonstrating the use of a laboratory X-ray diffractometer for <i>operando </i>SAXS. Data acquisition of <i>operando </i>SAXS with a laboratory X-ray diffractometer is desirable due to the general challenging and limited accessibility of synchrotron facilities. They become even more crucial under the ongoing and foreseen restrictions related to the COVID-19 pandemic. Although, it is not the aim to completely replace synchrotron-based studies, it is shown that the background subtraction can be achieved by a simple experimental consideration in the setup that can ultimately facilitate <i>operando </i>SAXS measurements at a synchrotron facility. <br>