The effect of pH on the hydrogen oxidation and evolution reaction (HOR/HER) rates is addressed for the first time for the three most active monometallic surfaces: Pt, Ir, and Pd carbon-supported catalysts. Kinetic data were obtained for a proton exchange membrane fuel cell (PEMFC; pH z 0) using the H 2 -pump mode and with a rotating disk electrode (RDE) in 0.1 M NaOH. Our findings point toward: (i) a similar z100-fold activity decrease on all these surfaces when going from low to high pH; (ii) a reaction rate controlled by the Volmer step on Pt/C; and (iii) the H-binding energy being the unique and sole descriptor for the HOR/HER in alkaline electrolytes. Based on a detailed discussion of our data, we propose a new mechanism for the HOR/HER on Pt-metals in alkaline electrolytes.Fuel cells and electrolyzers are important for renewable energy conversion and storage. They are currently based on protonexchange membranes (PEMs) operating at low pH (pH z 0), which offer high power densities, but require large amounts of platinum for the oxygen reduction reaction (ORR) in fuel cells 1 and of Ir for the oxygen evolution reaction (OER) in electrolyzers. 2 For the hydrogen oxidation/evolution reaction (HOR/HER) only very small amounts of Pt are required due to its extremely high activity for the HOR/HER. 3 The H 2 anode performance in PEMFCs suggested exchange current densities (i 0 ) in the order of 10 2 mA cm Pt À2 , 4 which was conrmed by mass-transport-free fuel cell measurements 3,5 and microelectrode data. 6 Until then, 100-fold lower i 0 -values for Pt in acid were reported erroneously, generally based on rotating disk electrode (RDE) measurements 7,8 from which, however, the kinetics of reactions with i 0 -values much above the diffusion limited RDE current density (z2-3 mA cm disk À2 ) cannot be quantied. 9In an alkaline electrolyte, non-noble metal catalysts are very active for the ORR 10,11 and for the OER, 12,13 so that in conjunction with alkaline membranes (OH À -exchange membranes 14,15 ) a replacement of the noble-metal intensive PEM technology by alkaline membrane technology seems promising. Unfortunately, for yet unclear reasons, the HOR/ HER kinetics on Pt are much slower in alkaline than in acid electrolytes, and large amounts of Pt are needed to catalyze the HOR/HER in an alkaline environment. 9 Therefore, it is critical to develop alternative HOR/HER catalysts for alkaline electrolytes and -to guide this search -to elucidate the reasons for the poor HOR/HER activity of Pt in alkaline electrolytes.Traditionally, the overall reactions have been written either with protons in acid or with hydroxide ions in alkaline media: 16 in acid:in base:The future of electromobility relies on the development of cost effective and durable energy conversion systems such as fuel cells and electrolyzers. These devices, based on proton-exchange membranes (PEMs), operating at pH 0, offer high power densities, but require large amounts of noble metal for the oxygen reduction reaction (ORR) in fuel cells and the oxygen evo...

In this study, the influence of catalyst loading on the performance of a proton exchange membrane (PEM) water electrolyzer is investigated (Nafion 212 membrane; IrO 2 /TiO 2 (anode) and Pt/C (cathode)). Due to the fast kinetics of the hydrogen evolution reaction (HER) on platinum (Pt), the Pt loading on the cathode can be reduced from 0.30 mg Pt cm −2 to 0.025 mg Pt cm −2 without any negative effect on performance. On the anode, the iridium (Ir) loading was varied between 0.20-5.41 mg Ir cm −2 and an optimum in performance at operational current densities (≥1 A cm −2 ) was found for 1-2 mg Ir cm −2 . At higher Ir loadings, the performance decreases at high current densities due to insufficient water transport through the catalyst layer whereas at Ir loadings <0.5 mg Ir cm −2 the catalyst layer becomes inhomogeneous, which leads to a lower electrochemically active area and catalyst utilization, resulting in a significant decrease of performance. To investigate the potential for a large-scale application of PEM water electrolysis, the Ir-specific power density (g Ir kW −1 ) for membrane electrode assemblies (MEAs) with different catalyst loadings is analyzed as a function of voltage efficiency, and the consequences regarding catalyst material requirements are discussed. PEM water electrolysis could provide electrolytic hydrogen for large-scale energy storage and mobility in a future energy scenario based on renewable energy sources. Currently, only a small share of the global hydrogen demand is served by PEM electrolysis due to the relatively high costs associated with this technology.

Operando X-ray absorption spectroscopy studies of transition metal dissolution in Li-ion batteries.

The aim of this study is to provide a better understanding of performance degrading mechanisms occurring when a proton exchange membrane water electrolyzer (PEM-WE) is coupled with renewable energies, where times of operation and idle periods alternate. An accelerated stress test (AST) is proposed, mimicking a fluctuating power supply by operating the electrolyzer cell between high (3 A cm −2 geo) and low current densities (0.1 A cm −2 geo), alternating with idle periods during which no current is supplied and the cell rests at open circuit voltage (OCV). Polarization curves, periodically recorded during the OCV-AST, reveal an initial increase in activity (≈50 mV after 10 cycles) followed by a significant decrease in performance during prolonged OCV cycling due to an increasing high frequency resistance (HFR) (≈1.6-fold after 718 cycles). These performance changes can clearly be related to the OCV periods, since they are not observed in a reference experiment where the OCV period is replaced by a potential hold at 1.3 V. The origin of the phenomena, which are responsible for the initial performance gain as well as the subsequent decay are analyzed via detailed electrochemical and physical characterization of the MEAs, and an operating strategy to prevent performance degradation is proposed.