Tailoring iridium-palladium nanoparticles with Ir-rich skin: a highly durable anode electrocatalyst for acidic water electrolysis via a facile microwave-assisted chemical reduction method.

Electrochemical water splitting under acidic conditions is a clean way towards producing hydrogen fuels. The slow kinetics of the oxygen evolution reaction (OER) at the anode is currently a bottleneck for commercial acceptance of this technology. Therefore, arriving at more efficient and sustainable OER electrocatalysts is highly desirable. We here demonstrate the synthesis of iridium-palladium (IrPd) alloy nanoparticles (2-5 nm) with variable average composition (Ir : Pd = 1 : 0, 1 : 1, 1 : 3, 1 : 6, 1 : 9 and 0 : 1) using a facile one-pot microwave-assisted chemical reduction method. The IrPd nanoparticles show structure- and composition-dependent OER performance in acidic media. Utilizing different reduction strengths and precursor ratios, successful alloy catalysts were prepared with Ir-rich skin and sublayers of different Pd compositions. Their structures were revealed using high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and hydrogen underpotential deposition (Hupd) studies. It turned out that (1) the alloy OER catalyst also has a high electrochemically active surface area for hydrogen adsorption/desorption, (2) the OER performance is strongly dependent on the surface Ir contribution and (3) the intact Ir skin is essential for electrocatalyst stability.

Recovery, Regeneration, and Reapplication of PFSA Polymer from End-of-Life PEMFC MEAs.

We have developed a recovery, regeneration, and reapplication process for Nafion, a perfluorinated sulfonic acid (PFSA) ionomer, from end-of-life (EoL) low-temperature proton-exchange membrane (PEM) fuel cells (FCs). Samples of PFSA PEM recovered from EoL membrane-electrode assemblies (MEAs) with a history of close to 19,000 h of operation were recycled by dissolving the polymeric material in ethanol and applying the dissolved PFSA ionomer for producing the ionomer phase of the catalyst layer of new PEMFC cathodes. Structural characterizations show a marginally lower abundance of sulfonic groups for the EoL PEM compared to a fresh sample. Sulfonation of the former was employed to regenerate sulfonic groups to compensate for the lost ones. New gas-diffusion electrodes (GDEs) were prepared with the recycled PFSA ionomer both with and without sulfonation, and MEAs with these GDEs as cathodes were assembled through a state-of-the-art procedure. Electrochemical characterizations of the GDEs and single-cell studies of the MEAs showed that the electrochemical performances of catalyst layers containing recycled PFSA ionomer were at least similar to those containing fresh. Durability studies of the GDEs and MEAs, performed through a three-electrode liquid cell and a single cell, respectively, show the highest durability for the GDE/MEA with PFSA ionomer recycled without applying the sulfonation step. However, the GDE with PFSA ionomer obtained from recycling a re-sulfonated PEM shows a durability comparable to that of the GDE with fresh PFSA ionomer. Hence, PFSA material aged during PEMFC operation may be employed to produce highly functional and durable regenerated PFSA ionomer for PEMFC catalyst layers. The studied process of PFSA ionomer recycling is highly attractive for industrial adoption.

Multiple Bubble Removal Strategies to Promote Oxygen Evolution Reaction: Mechanistic Understandings from Orientation, Rotation, and Sonication Perspectives.

Bubble coverage of catalytically active sites is one of the well-known bottlenecks to the kinetics of the oxygen evolution reaction (OER). Herein, various bubble removal approaches (electrode orientation, rotating, and sonication) were considered for the OER performance evaluation of a state-of-the-art Ir-based electrocatalyst. Key parameters, such as catalyst mass loss, activity, overpotential, and charge- and mass-transfer mechanisms, were analyzed. First, it was suggested that a suitable orientation of the working electrode facilitates coalescence and sliding bubble effects on the catalyst surface, leading to better electrochemical performance than those of the traditional rotating disk electrode (RDE) configuration. Then, the convection and secondary Bjerknes force were explained as the responsible phenomena in improving the OER activity in the RDE and sonication methods. Finally, simultaneous implementation of the methods enhanced the catalyst mass activity up to 164% and provided fast charge-transfer kinetics and low double-layer capacitance, which eventually led to a 22% reduction in overpotential, while the catalyst loss slightly increased from 1.93 to 3.88%.

Insights into Degradation of the Membrane-Electrode Assembly Performance in Low-Temperature PEMFC: the Catalyst, the Ionomer, or the Interface?

Here, we report a study on the structural characteristics of membrane electrode assembly (MEA) samples obtained from a low-temperature (LT) polymer electrolyte membrane (PEM) fuel cell (FC) stack subjected to long-term durability testing for ∼18,500 h of nominal operation along with ∼900 on/off cycles accumulated over the operation time, with the total power production being 3.39 kW h/cm2 of MEA and the overall degradation being 87% based on performance loss. The chemical and physical states of the degraded MEAs were investigated through structural characterizations aiming to probe their different components, namely the cathode and anode electrocatalysts, the Nafion ionomer in the catalyst layers (CLs), the gas diffusion layers (GDLs), and the PEM. Surprisingly, X-ray diffraction and electron microscopy studies suggested no significant degradation of the electrocatalysts. Similarly, the cathode and anode GDLs exhibited no significant change in porosity and structure as indicated by BET analysis and helium ion microscopy. Nevertheless, X-ray fluorescence spectroscopy, elemental analysis through a CHNS analyzer, and comprehensive investigations by X-ray photoelectron spectroscopy suggested significant degradation of the Nafion, especially in terms of sulfur content, that is, the abundance of the -SO3- groups responsible for H+ conduction. Hence, the degradation of the Nafion, in both of the CLs and in the PEM, was found to be the principal mechanism for performance degradation, while the Pt/C catalyst degradation in terms of particle size enlargement or mass loss was minimal. The study suggests that under real-life operating conditions, ionomer degradation plays a more significant role than electrocatalyst degradation in LT-PEMFCs, in contrast to many scientific studies under artificial stress conditions. Mitigation of the ionomer degradation must be emphasized as a strategy to improve the PEMFC's durability.

Platinum recycling through electroless dissolution under mild conditions using a surface activation assisted Pt-complexing approach.

High industrial demand and limited global abundance of precious metals (PMs) make their recycling essential for industrial and societal sustainability. Owing to their high surface-to-volume ratio, recycling of nanoparticulate precious metals through dissolution in dilute acids at room temperature is quite relevant. However, their dissolution by approaches such as the cyclic oxidation-reduction of metal surfaces through surface potential manipulation may not be suitable for large-scale production. Here, we demonstrate fast dissolution of Pt-nanoparticles under mild conditions (normal temperature and pressure) in Cl- containing dilute acidic/neutral baths without using cyclic oxidation-reduction. We demonstrate that the dissolution of Pt nanoparticles through [PtClx]2- complexing is hindered by blockage of the Pt surface due to adsorption of non-oxide species (impurities), a phenomenon termed herein as non-oxide passivation (NOP). The nanoparticles can be kept active for the [PtClx]2- complexing through removal of the adsorbed species by surface activation, a process to remove the NOP layer by application of cyclic/continuous perturbation. As an example, average % dissolution rate (calculated on initial Pt loading) increases from ∼10% per h (∼30% dissolution in 3 h) for dissolution without NOP removal to ∼19% per h (∼55% dissolution in 3 h) for dissolution through cyclic activation of the Pt surface by HCl-water cycling. The approach may be implemented with a range of cost-efficient and non-toxic reagents for industrial-scale and environmentally friendly recycling of Pt.

Highly Stable Monocrystalline Silver Clusters for Plasmonic Applications.

Plasmonic sensor configurations utilizing localized plasmon resonances in silver nanostructures typically suffer from the rapid degradation of silver under ambient atmospheric conditions. In this work, we report on the fabrication and detailed characterization of ensembles of monocrystalline silver nanoparticles (NPs), which exhibit a long-term stability of optical properties under ambient conditions without any protective treatments. Ensembles with different densities (surface coverages) of size-selected NPs (mean diameters of 12.5 and 24 nm) on quartz substrates are fabricated using the cluster-beam technique and characterized by linear spectroscopy, two-photon-excited photoluminescence, surface-enhanced Raman scattering microscopy, and transmission electron, helium ion, and atomic force microscopies. It is found that the fabricated ensembles of monocrystalline silver NPs preserve their plasmonic properties (monitored with optical spectroscopy) and strong field enhancements (revealed by surface-enhanced Raman spectroscopy) at least 5 times longer as compared to chemically synthesized silver NPs with similar sizes. The obtained results are of high practical relevance for the further development of sensors, resonators, and metamaterials utilizing the plasmonic properties of silver NPs.

Tuning surface plasmons in interconnected hemispherical Au shells.

We present a new approach for making interconnected hemispherical shells by stripping Au from templates of anodized aluminum, where the metal thickness can be adjusted without affecting the outer radius of curvature, film roughness and the sharpness of the hemisphere contact areas. This provides increased understanding of the surface plasmon resonances (SPRs) observed for Film-On-Nanospheres (FONs) by decoupling these parameters, which are coupled in the case of FONs. Investigating the influence of the shell thicknesses on the spectral positions of SPRs for FONs involves a dielectric core with a fixed radius encased by a metal film with adjustable thickness. By performing linear reflection spectroscopy, we demonstrate a wide tunability of the SPR by tailoring the inner hemisphere diameter, while keeping the outer diameter fixed. Deposition of extra Au on top of thick, previously stripped hemispherical shells isolates optical response contributions from Au grain- and island-mediated roughness, and unsharpening contact areas in form of decreasing LSPR quality factor. Two-photon luminescence scanning optical microscopy of shells with different thicknesses, applying several different laser wavelengths, is exploited to map local electromagnetic hot spots and correlate the high field enhancements with the linear reflection spectroscopy measurements.

Two-photon luminescence microscopy oflarge-area gold nanostructures on templates of anodized aluminum.

Using linear reflection spectroscopy and far-field two-photon luminescence (TPL) scanning optical microscopy, we characterize highly enhancing, large-area gold nanostructures formed on porous templates made by anodization of aluminum with either oxalic acid or phosphoric acid. These templates are formed by a newly developed, stepwise technique making use of protective top oxide layers facilitating continuously tunable interpore distances. The upper, porous alumina layers are subsequently removed and the remaining embossed barrier layer is used as template for the sputtered gold, where the density of gold particles covering the sample is adjusted by regulating the sputtering conditions. We observe spatially averaged field intensity enhancement (FE) factors of up to ~5.210(2) and bright spots in the TPL-images exhibiting maximum FE factors of up to approximately 1410(2) which is the largest estimated FE from any hitherto examined structures with our setup. We relate this large-area massive FE to constructive interference of surface plasmon (SP) polaritons scattered from the densely packed, randomly distributed gold particles and directly correlate this particle density with the strong and broad SP resonances as well as the magnitude of the FE factors. The average FE and the position of high enhancements in the TPL-images are dictated by the excitation wavelength, and the structures could evidently serve as versatile structures facilitating practical molecular sensing.