Electrochemical Stability and Degradation of Commercial Pd/C Catalyst in Acidic Media

Palladium has attracted significant attention as a catalyst or co-catalyst for many electrochemical reactions in energy conversion devices. We have studied electrochemical stability of a commercial Pd/C sample in an acidic electrolyte by exposing it to an accelerated stress test (AST) to mimic potential spikes in fuel cells and electrolyzers during start/stop events. AST consisted of extensive rapid potential cycling (5000 cycles, 1 V/s) in two potential regions, namely AST1 was performed between 0.4 and 1.4 VRHE, while AST2 was performed between 0.05 and 1.4 VRHE. Degradation of Pd/C was monitored by the changes in Pd electrochemical surface area, while the hydrogen evolution reaction (HER) was used as a test reaction to observe the corresponding impact of the degradation on the activity of Pd/C. Significant Pd/C degradation and HER activity loss were observed in both potential regions. Coupling of the electrochemical flow cell with an inductively coupled plasma mass spectrometry device showed substantial Pd dissolution during both ASTs. Identical location scanning electron microscopy revealed that Pd dissolution is followed by redeposition during both ASTs, resulting in particle size growth. Particle size growth was seen as especially dramatic in the case of AST2, when particularly large Pd nanostructures were obtained on top of the catalyst layer. According to the results presented in this work, (in)stability of Pd/C and other Pd-based nanocatalysts should be studied systematically as it may present a key factor limiting their application in energy conversion devices

Reduced graphene oxide as efficient carbon support for Pd-based ethanol oxidation catalysts in alkaline media

The sluggish kinetics of the ethanol oxidation reaction (EOR) and the related development of low-cost, highly active and stable anode catalysts still remains the major challenge in alkaline direct ethanol fuel cells (ADEFCs). In this respect, we synthesized a PdNiBi nanocatalyst on reduced graphene oxide (rGO) via a facile synthesis method. The prepared composite catalyst was physicochemically characterized by SEM, STEM, EDX, ICP-OES and XRD to analyze the morphology, particle distribution and size, elemental composition and structure. The electrochemical activity and stability towards EOR in alkaline media were examined using the thin-film rotating disk electrode technique. The results reveal well-dispersed and strongly anchored nanoparticles on the rGO support, providing abundant active sites. The PdNiBi/rGO presents a higher EOR activity and stability compared to a commercial Pd/C ascribed to a high ECSA and synergistic effects between Pd, Ni and Bi and the rGO material. These findings suggest PdNiBi/rGO as a promising anode catalyst in ADEFC applications

The Painters

ConspectusThe foreseeable worldwide energy and environmental challenges demand renewable alternative sources, energy conversion, and storage technologies. Therefore, electrochemical energy conversion devices like fuel cells, electrolyzes, and supercapacitors along with photoelectrochemical devices and batteries have high potential to become increasingly important in the near future. Catalytic performance in electrochemical energy conversion results from the tailored properties of complex nanometer-sized metal and metal oxide particles, as well as support nanostructures. Exposed facets, surface defects, and other structural and compositional features of the catalyst nanoparticles affect the electrocatalytic performance to varying degrees. The characterization of the nanometer-size and atomic regime of electrocatalysts and its evolution over time are therefore paramount for an improved understanding and significant optimization of such important technologies like electrolyzers or fuel cells. Transmission electron microscopy (TEM) and scanning transmission electron microscope (STEM) are to a great extent nondestructive characterization tools that provide structural, morphological, and compositional information with nanoscale or even atomic resolution. Due to recent marked advancement in electron microscopy equipment such as aberration corrections and monochromators, such insightful information is now accessible in many institutions around the world and provides huge benefit to everyone using electron microscopy characterization in general.Classical <i>ex situ</i> TEM characterization of random catalyst locations however suffers from two limitations regarding catalysis. First, the necessary low operation pressures in the range of 10^–6 to 10^–9 mbar for TEM are not in line with typical reaction conditions, especially considering electrocatalytic solid–liquid interfaces, so that the active state cannot be assessed. Second, and somewhat related, is the lack of time resolution for the evaluation of alterations of the usually highly heterogeneous nanomaterials. Two methods offer a solution to these shortcomings, namely, identical location TEM (IL-TEM) and electrochemical in situ liquid TEM. The former is already well established and has delivered novel insights particularly into degradation processes; however, characterization is still performed in vacuum. The latter circumvents this issue by using dedicated <i>in situ</i> TEM holders but introduces extremely demanding technical challenges. Although the introduction of revolutionizing thin SiN window cells, which elegantly confine the specimen from vacuum, has allowed demonstration of the potential of the <i>in situ</i> approach, the reproducibility and data interpretation is still limited predominately due to the strong interaction of the electron beam with the supporting electrolyte and electrode material. Because of the importance of understanding the nanoelectrochemical structure–function relationship, this Account aims to convey a timely perspective on the opportunities and particularly the challenges in electrochemical identical location TEM and <i>in situ</i> liquid cell TEM with a focus on electrochemical energy conversion

Robust SrTiO₃ Passivation of Silicon Photocathode by Reduced Graphene Oxide for Solar Water Splitting

Development of a robust photocathode using low-cost and high-performing materials, e.g., p-Si, to produce clean fuel hydrogen has remained challenging since the semiconductor substrate is easily susceptible to (photo)corrosion under photoelectrochemical (PEC) operational conditions. A protective layer over the substrate to simultaneously provide corrosion resistance and maintain efficient charge transfer across the device is therefore needed. To this end, in the present work, we utilized pulsed laser deposition (PLD) to prepare a high-quality SrTiO3 (STO) layer to passivate the p-Si substrate using a buffer layer of reduced graphene oxide (rGO). Specifically, a very thin (3.9 nm ∼10 unit cells) STO layer epitaxially overgrown on rGO-buffered Si showed the highest onset potential (0.326 V vs RHE) in comparison to the counterparts with thicker and/or nonepitaxial STO. The photovoltage, flat-band potential, and electrochemical impedance spectroscopy measurements revealed that the epitaxial photocathode was more beneficial for charge separation, charge transfer, and targeted redox reaction than the nonepitaxial one. The STO/rGO/Si with a smooth and highly epitaxial STO layer outperforming the directly contacted STO/Si with a textured and polycrystalline STO layer showed the importance of having a well-defined passivation layer. In addition, the numerous pinholes formed in the directly contacted STO/Si led to the rapid degradation of the photocathode during the PEC measurements. The stability tests demonstrated the soundness of the epitaxial STO layer in passivating Si against corrosion. This study provided a facile approach for preparing a robust protection layer over a photoelectrode substrate in realizing an efficient and, at the same time, durable PEC device.</p

Improving the HER Activity and Stability of Pt Nanoparticles by Titanium Oxynitride Support

Water electrolysis powered by renewables is regarded as the feasible route for the production of hydrogen, obtained at the cathode side through electrochemical hydrogen evolution reaction (HER). Herein, we present a rational strategy to improve the overall HER catalytic performance of Pt, which is known as the best monometallic catalyst for this reaction, by supporting it on a conductive titanium oxynitride (TiONx) dispersed over reduced graphene oxide nanoribbons. Characterization of the Pt/TiONx composite revealed the presence of small Pt particles with diameters between 2 and 3 nm, which are well dispersed over the TiONx support. The Pt/TiONx nanocomposite exhibited improved HER activity and stability with respect to the Pt/C benchmark in an acid electrolyte, which was ascribed to the strong metal–support interaction (SMSI) triggered between the TiONx support and grafted Pt nanoparticles. SMSI between TiONx and Pt was evidenced by X-ray photoelectron spectroscopy (XPS) through a shift of the binding energies of the characteristic Pt 4f photoelectron lines with respect to Pt/C. Density functional theory (DFT) calculations confirmed the strong interaction between Pt nanoparticles and the TiONx support. This strong interaction improves the stability of Pt nanoparticles and weakens the binding of chemisorbed H atoms thereon. Both of these effects may result in enhanced HER activity

Insights into electrochemical dealloying of Cu out of Au-doped Pt-alloy nanoparticles at the sub-nano-scale

Pt alloy nanoparticles present the most probable candidate to be used as the cathode cathodic oxygen reduction reaction electrocatalyst for achieving commercialization targets of the low-temperature fuel cells. It is therefore very important to understand its activation and degradation processes. Besides the ones known from the pure Pt electrocatalysts, the dealloying phenomena possess a great threat since the leached less-noble metal can interact with the polymer membrane or even poison the electrocatalyst. In this study, we present a solution, supported by in-depth advance electrochemical characterization, on how to suppress the removal of Cu from the Pt alloy nanoparticles

Robust SrTiO3 Passivation of Silicon Photocathode by Reduced Graphene Oxide for Solar Water Splitting

Development of a robust photocathode using lowcost and high-performing materials, e.g., p-Si, to produce clean fuel hydrogen has remained challenging since the semiconductor substrate is easily susceptible to (photo)corrosion under photoelectrochemical (PEC) operational conditions. A protective layer over the substrate to simultaneously provide corrosion resistance and maintain efficient charge transfer across the device is therefore needed. To this end, in the present work, we utilized pulsed laser deposition (PLD) to prepare a high-quality SrTiO3 (STO) layer to passivate the p-Si substrate using a buffer layer of reduced graphene oxide (rGO). Specifically, a very thin (3.9 nm ∼10 unit cells) STO layer epitaxially overgrown on rGO-buffered Si showed the highest onset potential (0.326 V vs RHE) in comparison to the counterparts with thicker and/or nonepitaxial STO. The photovoltage, flat-band potential, and electrochemical impedance spectroscopy measurements revealed that the epitaxial photocathode was more beneficial for charge separation, charge transfer, and targeted redox reaction than the nonepitaxial one. The STO/rGO/Si with a smooth and highly epitaxial STO layer outperforming the directly contacted STO/Si with a textured and polycrystalline STO layer showed the importance of having a well-defined passivation layer. In addition, the numerous pinholes formed in the directly contacted STO/Si led to the rapid degradation of the photocathode during the PEC measurements. The stability tests demonstrated the soundness of the epitaxial STO layer in passivating Si against corrosion. This study provided a facile approach for preparing a robust protection layer over a photoelectrode substrate in realizing an efficient and, at the same time, durable PEC device

Insights into electrochemical dealloying of Cu out of Au-doped Pt-alloy nanoparticles at the sub-nano-scale

Pt alloy nanoparticles present the most probable candidate to be used as the cathode cathodic oxygen reduction reaction electrocatalyst for achieving commercialization targets of the low-temperature fuel cells. It is therefore very important to understand its activation and degradation processes. Besides the ones known from the pure Pt electrocatalysts, the dealloying phenomena possess a great threat since the leached less-noble metal can interact with the polymer membrane or even poison the electrocatalyst. In this study, we present a solution, supported by in-depth advance electrochemical characterization, on how to suppress the removal of Cu from the Pt alloy nanoparticles

Multielectrode Teflon electrochemical nanocatalyst investigation system

The most common approach in the search for the optimal low temperature fuel cell catalyst remains “trial and error”. Therefore, large numbers of different potential catalytic materials need to be screened. The well-established and most commonly used method for testing catalytic electrochemical activity under well-defined hydrodynamics is still thin film rotating disc electrode (TF-RDE). Typically this method is very time consuming and is subjected to impurity problems. In order to avoid these issues a new multielectrode electrochemical cell design is presented, where 8 different electrocatalysts can be measured simultaneously at identical conditions. The major advantages over TF-RDE method are: • Faster catalyst screening times. • Greater impurity tolerance. • The option of internal standard

Miniature hydraulic nanotubes test rig

Kljub temu, da je v hidravliki večinoma prisotno hidravlično olje, ki prav tako pripomore k mazanju kontaktnih delov, je obraba še vedno eden izmed najbolj problematičnih pojavov, ki zmanjšujejo življenjsko dobo sestavin. Zaradi tega je na trgu veliko hidravličnih olj z dodatki, ki izboljšajo lastnosti olja. Izum nanocevk iz MoS2 z ugodnimi tribološkimi lastnostmi je pokazal možnost njihove uporabe kot dodatek hidravličnim mineralnim oljem. Za ugotovitev ustreznosti uporabe nanocevk v hidravličnih sistemih smo zasnovali in izdelali miniaturno hidravlično preizkuševališče. Da so se dobljeni rezultati lahko primerjali s standardnim oljem brez dodanih nanocevk, smo izdelali dve identični preizkuševališči, ki omogočata sočasno testiranje standardnega mineralnega olja, ter mineralnega olja z nanocevkami. Preizkuševališči vsebujeta zobniško črpalko s pogonskim motorjem, varnostni ventil, potni ventil, diferencialni hidravlični valj, filter, ter rezervoar. Preizkus smo izvajali neprekinjeno 6 dni, s frekvenco preklapljanja potnega ventila 2 Hz. Med preizkusom smo spremljali tlak med P vodom črpalke in potnega ventila. Prav tako smo s pomočjo infrardeče kamere spremljali temperaturo sestavin.Hydraulic oils are used in hydraulics also for lubrication, however the wear and tear on the components are still a major problem which affects the life of the parts. The invention of MoS2 nanotubes with beneficial tribolobical properties have shown the possibility of being very useful as additives to hydraulic oil. In order to test whether or not the additives are truly useful in hydraulic systems, we designed and built two identical miniature hydraulic test rigs so we could compare the results in which one was using regular mineral oil and the other using mineral oil with added nanotubes. The test rigs contained a gear pump with a drive motor, a safety valve, a spool valve, a differential hydraulic valve, a filter and a tank. The test was conducted for six days at a switching frequency of 2 Hz. During the test, we measured the pressure on the P line of the pump and on the A line of the spool valve. We also measured the temperature of the components with an infrared camera