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At least 1,513 records · Page 84

Ionomer-free and recyclable porous-transport electrode for high-performing proton-exchange-membrane water electrolysis

Abstract Clean hydrogen production requires large-scale deployment of water-electrolysis technologies, particularly proton-exchange-membrane water electrolyzers (PEMWEs). However, as iridium-based electrocatalysts remain the only practical option for PEMWEs, their low abundance will become a bottleneck for a sustainable hydrogen economy. Herein, we propose high-performing and durable ionomer-free porous transport electrodes (PTEs) with facile recycling features enabling Ir thrifting and reclamation. The ionomer-free porous transport electrodes offer a practical pathway to investigate the role of ionomer in the catalyst layer and, from microelectrode measurements, point to an ionomer poisoning effect for the oxygen evolution reaction. The ionomer-free porous transport electrodes demonstrate a voltage reduction of > 600 mV compared to conventional ionomer-coated porous transport electrodes at 1.8 A cm −2 and <0.1 mg Ir cm −2 , and a voltage degradation of 29 mV at average rate of 0.58 mV per 1000-cycles after 50k cycles of accelerated-stress tests at 4 A cm −2 . Moreover, the ionomer-free feature enables facile recycling of multiple components of PEMWEs, which is critical to a circular clean hydrogen economy.

08 HYDROGEN↗

Proton-controlled molecular ionic ferroelectrics

Abstract Molecular ferroelectric materials consist of organic and inorganic ions held together by hydrogen bonds, electrostatic forces, and van der Waals interactions. However, ionically tailored multifunctionality in molecular ferroelectrics has been a missing component despite of their peculiar stimuli-responsive structure and building blocks. Here we report molecular ionic ferroelectrics exhibiting the coexistence of room-temperature ionic conductivity (6.1 × 10 −5 S/cm) and ferroelectricity, which triggers the ionic-coupled ferroelectric properties. Such ionic ferroelectrics with the absorbed water molecules further present the controlled tunability in polarization from 0.68 to 1.39 μC/cm 2 , thermal conductivity by 13% and electrical resistivity by 86% due to the proton transfer in an ionic lattice under external stimuli. These findings enlighten the development of molecular ionic ferroelectrics towards multifunctionality.

42 ENGINEERING↗

Author Correction: Proton irradiation-decelerated intergranular corrosion of Ni-Cr alloys in molten salt

In the original version of this article, numbers for the beam current densities were incorrectly given as 1.5, 2.0, and 2.5 mA cm -2 in various locations, instead of the correct values 0.3, 0.4, and 0.5 mA cm -2 . This was owing to a measurement error coming from the indirect correspondence between the Faraday cup and the beam profile monitor (BPM) on the accelerator as the proton beam traveling along the beamline resulted in mismatching between calculated values and real beam currents, which were obtained by ex-situ calibration. The following changes have been made in the correct version. The eighth sentence of the Results, and the figure legend of Fig. 2j state '0.3, 0.4, 0.5 mA cm -2 ' in place of '1.5, 2.0, 2.5 mA cm -2 '. The figure legend of Fig. 1j–l states '0.5, 0.4, 0.3 mA cm -2 ' in place of '2.5, 2.0, 1.5 mA cm -2 '. Figure 1e states '0.5 mA cm -2 ' in place of '2.5 mA cm -2 ', Fig. 1h states '0.4 mA cm -2 ' in place of '2.0 mA cm -2 ', and Fig. 1k states ‘0.3 mA cm -2 ' in place of ‘1.5 mA cm -2 '. Figure 2c states '0.5 mA cm -2 ' in place of '2.5 mA cm -2 ', Fig. 2d states '0.4 mA cm -2 ' in place of '2.0 mA cm -2 ', and Fig. 2e states '0.3 mA cm -2 ' in place of '1.5 mA cm -2 '. Figure 2j and k states ‘0.3 mA cm -2 ', '0.4 mA cm -2 ', '0.5 mA cm -2 ' in place of '1.5 mA cm -2 ', '2.0 mA cm -2 ', and '2.5 mA cm -2 ', respectively. The figure legend of Fig. 3b states '0.4 mA cm -2 ' in place of '2.0 mA cm -2 '. The figure legend of Supplementary Fig. 1 states '0.5 mA cm -2 ' in place of '2.5 mA cm -2 '. This has been corrected in the PDF and HTML versions of the Article.

36 MATERIALS SCIENCE↗

Elliptic anisotropy measurement of the f 0 (980) hadron in proton-lead collisions and evidence for its quark-antiquark composition

Despite the f 0 (980) hadron having been discovered half a century ago, the question about its quark content has not been settled: it might be an ordinary quark-antiquark ($q\bar{q}$) meson, a tetraquark ($q\bar{q}$$q\bar{q}$) exotic state, a kaon-antikaon ($K\bar{K}$) molecule, or a quark-antiquark-gluon ($q\bar{q}$g) hybrid. This paper reports strong evidence that the f 0 (980) state is an ordinary $q\bar{q}$ meson, inferred from the scaling of elliptic anisotropies (v 2 ) with the number of constituent quarks (n q ), as empirically established using conventional hadrons in relativistic heavy ion collisions. The f 0 (980) state is reconstructed via its dominant decay channel f 0 (980) → π + π − , in proton-lead collisions recorded by the CMS experiment at the LHC, and its v 2 is measured as a function of transverse momentum (p T ). It is found that the n q = 2 ($q\bar{q}$ state) hypothesis is favored over n q = 4 ($q\bar{q}$$q\bar{q}$ or $K\bar{K}$ states) by 7.7, 6.3, or 3.1 standard deviations in the p T < 10, 8, or 6 GeV/c ranges, respectively, and over n q = 3 ($q\bar{q}$g hybrid state) by 3.5 standard deviations in the p T < 8 GeV/c range. This result represents the first determination of the quark content of the f 0 (980) state, made possible by using a novel approach, and paves the way for similar studies of other exotic hadron candidates.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis

Iridium-based electrocatalysts remain the only practical anode catalysts for proton exchange membrane (PEM) water electrolysis, due to their excellent stability under acidic oxygen evolution reaction (OER), but are greatly limited by their high cost and low reserves. Here, in this study, we report a nickel-stabilized, ruthenium dioxide (Ni-RuO 2 ) catalyst, a promising alternative to iridium, with high activity and durability in acidic OER for PEM water electrolysis. While pristine RuO 2 showed poor acidic OER stability and degraded within a short period of continuous operation, the incorporation of Ni greatly stabilized the RuO 2 lattice and extended its durability by more than one order of magnitude. When applied to the anode of a PEM water electrolyser, our Ni-RuO 2 catalyst demonstrated >1,000 h stability under a water-splitting current of 200 mA cm -2 , suggesting potential for practical applications. Density functional theory studies, coupled with operando differential electrochemical mass spectroscopy analysis, confirmed the adsorbate-evolving mechanism on Ni-RuO 2 , as well as the critical role of Ni dopants in stabilization of surface Ru and subsurface oxygen for improved OER durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sensitive proton-radiation detectors

In this study, halide perovskite nanocrystal scintillators detect high-energy protons with sensitivity suitable for clinical applications.

36 MATERIALS SCIENCE↗

Low-iridium stabilized ruthenium oxide anode catalyst for durable proton-exchange membrane water electrolysis

While mixing iridium (Ir) with ruthenium oxide (RuO 2 ) has proven to be an effective strategy for reducing Ir loading in anode catalysts for proton-exchange membrane (PEM) water electrolysers, achieving industrially relevant long-term stability typically requires an Ir-rich, Ru-lean combination. Here, in this study, by combining density functional theory with Metropolis Monte Carlo methods, we discovered that sufficient stabilization in the RuO 2 lattice could be achieved with less than 50 at.% of Ir, and that Ir in the first subsurface layer plays a critical role. By effectively dispersing Ir dopants within the RuO 2 lattice, we demonstrated an Ir:Ru atomic ratio of only 1:6 that exhibited exceptional stability for over 1,500 h of continuous water electrolysis at 2 A cm −2 . Our Ru 6 IrO x catalyst has the potential to reduce Ir loading by 80% compared with current commercial PEM water electrolysers, and its stability was further validated under industrial testing conditions in a 25-cm 2 PEM electrolyser.

36 MATERIALS SCIENCE↗

Protons on the line

Stable regions in four-dimensional phase space were observed by following the motion of accelerated proton beams subject to nonlinear forces. Here, this provides insights into the physics of dynamical systems and may lead to improved accelerator designs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Atomically dispersed Pt and Fe sites and Pt–Fe nanoparticles for durable proton exchange membrane fuel cells

Proton exchange membrane fuel cells convert hydrogen and oxygen into electricity without emissions. The high cost and low durability of Pt-based electrocatalysts for the oxygen reduction reaction hinder their wide application, and the development of non-precious metal electrocatalysts is limited by their low performance. Here we design a hybrid electrocatalyst that consists of atomically dispersed Pt and Fe single atoms and Pt–Fe alloy nanoparticles. Its Pt mass activity is 3.7 times higher than that of commercial Pt/C in a fuel cell. More importantly, the fuel cell with a low Pt loading in the cathode (0.015 mg Pt cm –2 ) shows an excellent durability, with a 97% activity retention after 100,000 cycles and no noticeable current drop at 0.6 V for over 200 hours. These results highlight the importance of the synergistic effects among active sites in hybrid electrocatalysts and provide an alternative way to design more active and durable low-Pt electrocatalysts for electrochemical devices.

25 ENERGY STORAGE↗

Advances and challenges for experiment and theory for multi-electron multi-proton transfer at electrified solid–liquid interfaces

Multi-electron, multi-proton transfer is important in a wide spectrum of processes spanning biological, chemical and physical systems. These reactions have attracted significant interest due to both fundamental curiosity and potential applications in energy technology. In this Perspective Review, we shed light on modern aspects of electrode processes in the 21st century, in particular on the recent advances and challenges in multistep electron/proton transfers at solid–liquid interfaces. Ongoing developments of analytical techniques and operando spectrometry at electrode/electrolyte interfaces and reliable computational approaches to simulate complicated interfacial electrochemical reactions enable us to obtain microscopic insights about these complex processes, such as the role of quantum effects in electrochemical reactions. Our motivation in this Perspective Review is to provide a comprehensive survey and discussion of state-of-the-art developments in experiments, materials, and theories for modern electrode process science, as well as to present an outlook for the future directions in this field.

Sakaushi, Ken↗

Understanding of A-site deficiency in layered perovskites: promotion of dual reaction kinetics for water oxidation and oxygen reduction in protonic ceramic electrochemical cells

Protonic ceramic electrochemical cells (PCECs) are promising solid-state energy conversion devices which enable the conversion of energy between electricity and hydrogen at intermediate temperatures. Rapid conversion between chemical and electrical energy via PCEC technology will assist in overcoming grand challenges in energy storage. To achieve highly efficient reversible operation between hydrogen production and electricity generation, boosting water-oxidation and oxygen reduction activities of the oxygen electrode while maintaining the durable operation is one of the early-stage technical opportunities. In this study, an A-site deficient layered perovskite (PrBa 0.8 Ca 0.2 ) 0.95 Co 2 O 6–δ has been developed as an oxygen electrode for a PCEC which presents superior electrochemical performances. The electrolysis current density reached as high as –0.72 A cm –2 at 1.3 V, and a peak power density of 0.540 W cm –2 was obtained at 600 °C in electrolysis and fuel cell mode, respectively. The PCEC with the new electrode shows good durability under practical operating conditions for 160 hours in both operating modes with no observable degradation. Here, the reversibility between the electrolysis and fuel cell mode is also successfully demonstrated.

30 DIRECT ENERGY CONVERSION↗

Inferring relative dose-dependent color center populations in proton irradiated thoria single crystals using optical spectroscopy

In this work, we have utilized photoluminescence spectroscopy and optical ellipsometry to characterize the dose-dependence of the photoluminescence emission intensity and changes in optical absorption of thoria single crystals subject to irradiation with energetic protons at room- and elevated-temperatures. The photoluminescence peaks and the optical absorption bands are attributed to creation of new electronic states emerging from defects resulting from displacement damage. These bands are most likely associated with electrons trapped at the oxygen vacancy sites similar to color centers formed in other irradiated oxides and halides. Our experimental observations are supported by a standard density functional theory calculation of the electronic structure in pristine and oxygen vacancy-bearing thoria crystals. The dose-dependence of the intensity of the photoluminescence peaks is used to parameterize a rate theory model that estimates the concentration of color centers in the irradiated crystals. This parameterization provides optimized migration barrier parameters for oxygen interstitials and vacancies that simultaneously capture the optical response of the crystals irradiated at room- and elevated-temperature. These optical spectroscopy techniques offer a promising pathway to characterize the population of color centers formed at the sites of oxygen anion vacancies, particularly in irradiated nuclear fuels, where atomic-level defects cannot be readily imaged using electron microscopy. When combined with other direct and indirect characterization tools, our approach can provide new insight into defect formation and accumulation in energy materials over single atomic to extended length scales.

36 MATERIALS SCIENCE↗

Chasing protons in lithium-ion batteries

Parasitic reactions between delithiated cathode materials and non-aqueous electrolytes have been a major barrier that limits the upper cutoff potential of cathode materials. It is of great importance to suppress such parasitic reactions to unleash the high-energy-density potential of high voltage cathode materials. Although major effort has been made to identify the chemical composition of the cathode electrolyte interface using various cutting edge characterization tools, the chemical nature of parasitic reactions remains a puzzle. This severely hinders the rational development of stable high voltage cathode/electrolyte pairs for high-energy density lithium-ion batteries. This report highlights our latest effort in understanding the chemical/electrochemical role of the cathode electrolyte interface using protons as a chemical tracer for parasitic reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗