Differences in the Electrochemical Performance of Pt-Based Catalysts Used for Polymer Electrolyte Membrane Fuel Cells in Liquid Half- and Full-Cells.

A substantial amount of research effort has been directed toward the development of Pt-based catalysts with higher performance and durability than conventional polycrystalline Pt nanoparticles to achieve high-power and innovative energy conversion systems. Currently, attention has been paid toward expanding the electrochemically active surface area (ECSA) of catalysts and increase their intrinsic activity in the oxygen reduction reaction (ORR). However, despite innumerable efforts having been carried out to explore this possibility, most of these achievements have focused on the rotating disk electrode (RDE) in half-cells, and relatively few results have been adaptable to membrane electrode assemblies (MEAs) in full-cells, which is the actual operating condition of fuel cells. Thus, it is uncertain whether these advanced catalysts can be used as a substitute in practical fuel cell applications, and an improvement in the catalytic performance in real-life fuel cells is still necessary. Therefore, from a more practical and industrial point of view, the goal of this review is to compare the ORR catalyst performance and durability in half- and full-cells, providing a differentiated approach to the durability concerns in half- and full-cells, and share new perspectives for strategic designs used to induce additional performance in full-cell devices.

Copper-Halide Polymer Nanowires as Versatile Supports for Single-Atom Catalysts.

Single-atom catalysts are heterogeneous catalysts with atomistically dispersed atoms acting as a catalytically active center, and have recently attracted much attention owing to the minimal use of noble metals. However, a scalable and inexpensive support that can stably anchor isolated atoms remains a challenge due to high surface energy. Here, copper-halide polymer nanowires with sub-nanometer pores are proposed as a versatile support for single-atom catalysts. The synthesis of the nanowires is straightforward and completed in a few minutes. Well-defined sub-nanometer pores and a large free volume of the nanowires are advantageous over any other support material. The nanowires can anchor various atomistically dispersed metal atoms into the sub-nanometer pores up to ≈3 at% via a simple solution process, and this value is at least twice as big as previously reported data. The hydrogen evolution reaction activity of -18.0 A mgPt -1 at -0.2 V overpotential shows its potential for single-atom catalysts support.

Advanced and In Situ Analytical Methods for Solar Fuel Materials.

In situ and operando techniques can play important roles in the development of better performing photoelectrodes, photocatalysts, and electrocatalysts by helping to elucidate crucial intermediates and mechanistic steps. The development of high throughput screening methods has also accelerated the evaluation of relevant photoelectrochemical and electrochemical properties for new solar fuel materials. In this chapter, several in situ and high throughput characterization tools are discussed in detail along with their impact on our understanding of solar fuel materials.

Photoelectrochemical H2 Evolution with a Hydrogenase Immobilized on a TiO2 -Protected Silicon Electrode.

The combination of enzymes with semiconductors enables the photoelectrochemical characterization of electron-transfer processes at highly active and well-defined catalytic sites on a light-harvesting electrode surface. Herein, we report the integration of a hydrogenase on a TiO2 -coated p-Si photocathode for the photo-reduction of protons to H2 . The immobilized hydrogenase exhibits activity on Si attributable to a bifunctional TiO2 layer, which protects the Si electrode from oxidation and acts as a biocompatible support layer for the productive adsorption of the enzyme. The p-Si|TiO2 |hydrogenase photocathode displays visible-light driven production of H2 at an energy-storing, positive electrochemical potential and an essentially quantitative faradaic efficiency. We have thus established a widely applicable platform to wire redox enzymes in an active configuration on a p-type semiconductor photocathode through the engineering of the enzyme-materials interface.

A Si photocathode protected and activated with a Ti and Ni composite film for solar hydrogen production.

An efficient, stable and scalable hybrid photoelectrode for visible-light-driven H2 generation in an aqueous pH 9.2 electrolyte solution is reported. The photocathode consists of a p-type Si substrate layered with a Ti and Ni-containing composite film, which acts as both a protection and electrocatalyst layer on the Si substrate. The film is prepared by the simple drop casting of the molecular single-source precursor, [{Ti2(OEt)9(NiCl)}2] (TiNipre), onto the p-Si surface at room temperature, followed by cathodic in situ activation to form the catalytically active TiNi film (TiNicat). The p-Si|TiNicat photocathode exhibits prolonged hydrogen generation with a stable photocurrent of approximately -5 mA cm(-2) at 0 V vs. RHE in an aqueous pH 9.2 borate solution for several hours, and serves as a benchmark non-noble photocathode for solar H2 evolution that operates efficiently under neutral-alkaline conditions.

Photoelectrochemical reduction of aqueous protons with a CuO|CuBi2O4 heterojunction under visible light irradiation.

A p-type heterojunction photoelectrode consisting of platinized CuBi2O4 layered on a CuO film was prepared. The CuO|CuBi2O4|Pt electrode photo-generates H2 in pH neutral aqueous solution during visible light irradiation and exhibits a substantially enhanced photocurrent compared to CuO|Pt and CuBi2O4|Pt electrodes. Reduced electron-hole recombination by the band offsets in the heterostructure is responsible for the improved photoelectrochemical performance of CuO|CuBi2O4 with a small band-gap of approximately 1.5 eV.

Unbiased photoelectrochemical water splitting in Z-scheme device using W/Mo-doped BiVO4 and Zn(x)Cd(1-x)Se.

Photoelectrochemical water splitting to generate H2 and O2 using only photon energy (with no added electrical energy) has been demonstrated with dual n-type-semiconductor (or Z-scheme) systems. Here we investigated two different Z-scheme systems; one is comprised of two cells with the same metal-oxide semiconductor (W- and Mo-doped bismuth vanadate), that is, Pt-W/Mo-BiVO4, and the other is comprised of the metal oxide and a chalcogenide semiconductor, that is, Pt-W/Mo-BiVO4 and Zn(0.2)Cd(0.8)Se. The redox couples utilized in these Z-scheme configurations were I(-)/IO3(-) or S(2-)/S(n)(2-), respectively. An electrochemical analysis of the system in terms of cell components is shown to illustrate the behavior of the complete photoelectrochemical Z-scheme water-splitting system. H2 gas from the unbiased photolysis of water was detected using gas chromatography-mass spectroscopy and using a membrane-electrode assembly. The electrode configuration to achieve the maximum conversion efficiency from solar energy to chemical energy with the given materials and the Z-scheme is discussed. Here, the possibilities and challenges of Z-scheme unbiased photoelectrochemical water-splitting devices and the materials to achieve practical solar-fuel generation are discussed.

Properties of Anion Exchange Membranes with a Focus on Water Electrolysis.

Recently, alkaline membrane water electrolysis, in which membranes are in direct contact with water or alkaline solutions, has gained attention. This necessitates new approaches to membrane characterization. We show how the mechanical properties of FAA3, PiperION, Nafion 212 and reinforced FAA3-PK-75 and PiperION PI-15 change when stress−strain curves are measured in temperature-controlled water. Since membranes show dimensional changes when the temperature changes and, therefore, may experience stresses in the application, we investigated seven different membrane types to determine if they follow the expected spring-like behavior or show hysteresis. By using a very simple setup which can be implemented in most laboratories, we measured the "true hydroxide conductivity" of membranes in temperature-controlled water and found that PI-15 and mTPN had higher conductivity at 60 °C than Nafion 212. The same setup was used to monitor the alkaline stability of membranes, and it was found that stability decreased in the order mTPN > PiperION > FAA3. XPS analysis showed that FAA3 was degraded by the attack of hydroxide ions on the benzylic position. Water permeability was analyzed, and mTPN had approximately two times higher permeability than PiperION and 50% higher permeability than FAA3.

Understanding potential-dependent competition between electrocatalytic dinitrogen and proton reduction reactions.

A key challenge to realizing practical electrochemical N2 reduction reaction (NRR) is the decrease in the NRR activity before reaching the mass-transfer limit as overpotential increases. While the hydrogen evolution reaction (HER) has been suggested to be responsible for this phenomenon, the mechanistic origin has not been clearly explained. Herein, we investigate the potential-dependent competition between NRR and HER using the constant electrode potential model and microkinetic modeling. We find that the H coverage and N2 coverage crossover leads to the premature decrease of NRR activity. The coverage crossover originates from the larger charge transfer in H+ adsorption than N2 adsorption. The larger charge transfer in H+ adsorption, which potentially leads to the coverage crossover, is a general phenomenon seen in various heterogeneous catalysts, posing a fundamental challenge to realize practical electrochemical NRR. We suggest several strategies to overcome the challenge based on the present understandings.

Electrochemical Nitrogen Reduction Kinetics on a Copper Sulfide Catalyst for NH3 Synthesis at Low Temperature and Atmospheric Pressure.

We studied the electrochemical synthesis of NH3 on Fe-CuS/C catalysts in an alkaline aqueous solution under ambient conditions. The metal chalcogenide catalyst is active in the nitrogen reduction reaction (NRR) for approximately 45 min with an NH3 production yield of 16 µg h-1 cm-2 at -0.4 VRHE, while it decomposes to CuO. The rapid degradation of the catalyst hinders the precise investigation of the NH3 production activity in longer time measurements. Herein, the electrochemical NH3 production rate is enhanced with increased overpotentials when the degradation effect is mitigated in the measurement, which was difficult to observe in the NRR reports. In the Tafel analysis, the exchange current density, heterogeneous rate constant, and transfer coefficient of the Fe-CuS/C catalyst on the NRR were estimated. When the electrode degradation is mitigated, one of the best NH3 production activities among the reported metal sulfide electrochemical NRR catalysts is obtained, which is 42 µg h-1 cm-2 at -0.6 VRHE.

Self-supported mesoscopic tin oxide nanofilms for electrocatalytic reduction of carbon dioxide to formate.

Here we report a self-supported SnO2 nanofilm prepared by a robust electrochemical process as an electrocatalyst for the CO2 reduction reaction. The SnO2 film had a large surface area originating from its nano-architecture and manifested high selectivity toward formate (over 60%), which resulted in CO2-to-formate current density up to 33.66 mA cm-2 that is among the state-of-the-art. We unveiled that the high performance of the SnO2 nanofilm is attributable to the presence of a metastable oxide under reductive conditions in addition to the abovementioned advantages.

Amphiphilic Ti porous transport layer for highly effective PEM unitized regenerative fuel cells.

Polymer electrolyte membrane unitized regenerative fuel cells (PEM-URFCs) require bifunctional porous transport layers (PTLs) to play contradictory roles in a single unitized system: hydrophobicity for water drainage in the fuel cell (FC) mode and hydrophilicity for water supplement in the electrolysis cell (EC) mode. Here, we report a high-performance amphiphilic Ti PTL suitable for both FC and EC modes, thanks to alternating hydrophobic and hydrophilic channels. To fabricate the amphiphilic PTL, we used a shadow mask patterning process using ultrathin polydimethylsiloxane (PDMS) brush as a hydrophobic surface modifier, which can change the Ti PTL's surface polarity without decreasing its electrical conductivity. Consequently, performance improved by 4.3 times in FC (@ 0.6 V) and 1.9 times in EC (@ 1.8 V) from amphiphilic PTL. To elucidate reason for performance enhancement, discrete gas emission through the hydrophobic channels in amphiphilic PTL was verified under scanning electrochemical microscopy.

Hydrogen-Mediated Thin Pt Layer Formation on Ni3N Nanoparticles for the Oxygen Reduction Reaction.

A simple wet-chemical route for the preparation of core-shell-structured catalysts was developed to achieve high oxygen reduction reaction (ORR) activity with a low Pt loading amount. Nickel nitride (Ni3N) nanoparticles were used as earth-abundant metal-based cores to support thin Pt layers. To realize the site-selective formation of Pt layers on the Ni3N core, hydrogen molecules (H2) were used as a mild reducing agent. As H2 oxidation is catalyzed by the surface of Ni3N, the redox reaction between H2 and Pt(IV) in solution was facilitated on the Ni3N surface, which resulted in the selective deposition of Pt on Ni3N. The controlled Pt formation led to a subnanometer (0.5-1 nm)-thick Pt shell on the Ni3N core. By adopting the core-shell structure, higher ORR activity than the commercial Pt/C was achieved. Electrochemical measurements showed that the thin Pt layer on Ni3N nanoparticle exhibits 5 times higher mass activity and specific activity than that of commercial Pt/C. Furthermore, it is expected that the proposed simple wet-chemical method can be utilized to prepare various transition-metal-based core-shell nanocatalysts for a wide range of energy conversion reactions.

Hierarchically Assembled Cobalt Oxynitride Nanorods and N-Doped Carbon Nanofibers for Efficient Bifunctional Oxygen Electrocatalysis with Exceptional Regenerative Efficiency.

Oxygen-based electrocatalysis is an integral aspect of a clean and sustainable energy conversion/storage system. The development of economic bifunctional electrocatalysts with high activity and durability during reversible reactions remains a great challenge. The tailored porous structure and separately presented active sites for oxygen reduction and oxygen evolution reactions (ORR and OER) without mutual interference are most crucial for achieving desired bifunctional catalysts. Here, we report a hybrid composed of sheath-core cobalt oxynitride (CoOx@CoNy) nanorods grown perpendicularly on N-doped carbon nanofiber (NCNF). The brush-like CoOx@CoNy nanorods, composed of metallic Co4N cores and oxidized surfaces, exhibit excellent OER activity (E = 1.69 V at 10 mA cm-2) in an alkaline medium. Although pristine NCNF or CoOx@CoNy alone had poor catalytic activity in the ORR, the hybrid showed dramatically enhanced ORR performance (E = 0.78 V at -3 mA cm-2). The experimental results coupled with a density functional theory (DFT) simulation confirmed that the broad surface area of the CoOx@CoNy nanorods with an oxidized skin layer boosts the catalytic OER, while the facile adsorption of ORR intermediates and a rapid interfacial charge transfer occur at the interface between the CoOx@CoNy nanorods and the electrically conductive NCNF. Furthermore, it was found that the independent catalytic active sites in the CoOx@CoNy/NCNF catalyst are continuously regenerated and sustained without mutual interference during the round-trip ORR/OER, affording stable operation of Zn-air batteries.

Highly efficient oxygen evolution reaction via facile bubble transport realized by three-dimensionally stack-printed catalysts.

Despite highly promising characteristics of three-dimensionally (3D) nanostructured catalysts for the oxygen evolution reaction (OER) in polymer electrolyte membrane water electrolyzers (PEMWEs), universal design rules for maximizing their performance have not been explored. Here we show that woodpile (WP)-structured Ir, consisting of 3D-printed, highly-ordered Ir nanowire building blocks, improve OER mass activity markedly. The WP structure secures the electrochemically active surface area (ECSA) through enhanced utilization efficiency of the extended surface area of 3D WP catalysts. Moreover, systematic control of the 3D geometry combined with theoretical calculations and various electrochemical analyses reveals that facile transport of evolved O2 gas bubbles is an important contributor to the improved ECSA-specific activity. The 3D nanostructuring-based improvement of ECSA and ECSA-specific activity enables our well-controlled geometry to afford a 30-fold higher mass activity of the OER catalyst when used in a single-cell PEMWE than conventional nanoparticle-based catalysts.

Social determinants of health and their impact on postcolectomy surgery readmissions: a multistate analysis, 2009-2014.

Aim: To examine the effect of race/ethnicity, insurance status and median household income on postoperative readmissions following colectomy. Patients & methods: Multivariate analysis of hospital discharge data from California, Florida, Maryland and New York from 2009 to 2014. Primary outcomes included adjusted odds of 30- and 90-day readmissions following colectomy by race, insurance status and median income quartile. Results: Total 330,840 discharges included. All 30-day readmissions were higher for black patients (adjusted odds ratio [aOR]: 1.07). Both 30- and 90-day readmissions were higher for Medicaid (aOR: 1.30 and 1.26) and Medicare (aOR: 1.30 and 1.29). The 30- and 90-day readmissions were lower in the highest income quartiles. Conclusion: Race, insurance status and median household income are all independent predictors of disparity in readmissions following colectomy.

Versatile biomimetic conductive polypyrrole films doped with hyaluronic acid of different molecular weights.

Electrically conductive polypyrrole (PPy) is an intriguing biomaterial capable of efficient electrical interactions with biological systems. Especially, biomimetic PPy-based biomaterials incorporating biomolecules, such as hyaluronic acid (HA), can impart the characteristic biological interactions with living cells/tissues to the conductive biomaterials. Here we report the effects of the molecular weight (MW) of HA on PPy-based biomaterials. We utilized HA of a wide range of MW (35 × 103 Da-3 × 106 Da) as dopants during the electrochemical production of PPy/HA films and their characterization of materials and cellular interactions. With increases in the MWs of HA dopants, PPy/HA exhibited more hydrophilic, higher electrochemical activity and lower impedance. In vitro studies revealed that PPy films doped with low MW HA were supportive to cell adhesion and growth, while PPy films doped with high MW HA were resistant to cell attachment. Subcutaneous implantation of the PPy/HA films for 4 weeks revealed that all the PPy/HA films were tissue compatible. We successfully demonstrate the importance of HA dopant MWs in modulating the chemical and electrical properties of the materials and cellular responses to the materials. Such materials have potential for various biomedical applications, including as tissue engineering scaffolds and as electrodes for neural recording and neuromodulation. STATEMENT OF SIGNIFICANCE: Hyaluronic acid (HA)-doped polypyrrole (PPy) films were electrochemically synthesized as novel biomimetic conductive materials capable of efficient electrical signaling and preferential biological interactions. Molecular weights (MWs) of HA varied in a wide range (35 × 103-2 × 106 Da) and critically determine chemical, electrochemical, and biological properties of PPy/HA. Especially, PPy films with low MW HA markedly support cell adhesion and growth, while PPy films with high MW HA are resistant to cell attachment. Furthermore, PPy/HA exhibits greatly improved tissue compatibility and in vivo EMG signal recording ability. We for the first time demonstrate that biomimetic PPy/HA-based biomaterials can serve as versatile and effective platforms for various biomedical applications, such as tissue engineering scaffolds and bioelectrodes.

Electrochemically Synthesized Nanoporous Molybdenum Carbide as a Durable Electrocatalyst for Hydrogen Evolution Reaction.

Demands for sustainable production of hydrogen are rapidly increasing because of environmental considerations for fossil fuel consumption and development of fuel cell technologies. Thus, the development of high-performance and economical catalysts has been extensively investigated. In this study, a nanoporous Mo carbide electrode is prepared using a top-down electrochemical process and it is applied as an electrocatalyst for the hydrogen evolution reaction (HER). Anodic oxidation of Mo foil followed by heat treatment in a carbon monoxide (CO) atmosphere forms a nanostructured Mo carbide with excellent interconnections, and these structural characteristics lead to high activity and durability when applied to the HER. Additionally, characteristic behavior of Mo is observed; metallic Mo nanosheets form during electrochemical anodization by exfoliation along the (110) planes. These nanosheets are viable for chemical modification, indicating their feasibility in various applications. Moreover, the role of carbon shells is investigated on the surface of the electrocatalysts, whereby it is suggested that carbon shells serve as a mechanical barrier against the oxidative degradation of catalysts that accompanies unavoidable volume expansion.

Electrochemical synthesis of nanoporous tungsten carbide and its application as electrocatalysts for photoelectrochemical cells.

Photoelectrochemical (PEC) cells are promising tools for renewable and sustainable solar energy conversion. Currently, their inadequate performance and high cost of the noble metals used in the electrocatalytic counter electrode have postponed the practical use of PEC cells. In this study, we report the electrochemical synthesis of nanoporous tungsten carbide and its application as a reduction catalyst in PEC cells, namely, dye-sensitized solar cells (DSCs) and PEC water splitting cells, for the first time. The method employed in this study involves the anodization of tungsten foil followed by post heat treatment in a CO atmosphere to produce highly crystalline tungsten carbide film with an interconnected nanostructure. This exhibited high catalytic activity for the reduction of cobalt bipyridine species, which represent state-of-the-art redox couples for DSCs. The performance of tungsten carbide even surpassed that of Pt, and a substantial increase (∼25%) in energy conversion efficiency was achieved when Pt was substituted by tungsten carbide film as the counter electrode. In addition, tungsten carbide displayed decent activity as a catalyst for the hydrogen evolution reaction, suggesting the high feasibility for its utilization as a cathode material for PEC water splitting cells, which was also verified in a two-electrode water photoelectrolyzer.

Reliable Multistate Data Storage with Low Power Consumption by Selective Oxidation of Pyramid-Structured Resistive Memory.

Multilevel data storage using resistive random access memory (RRAM) has attracted significant attention for addressing the challenges associated with the rapid advances in information technologies. However, it is still difficult to secure reliable multilevel resistive switching of RRAM due to the stochastic and multiple formation of conductive filaments (CFs). Herein, we demonstrate that a single CF, derived from selective oxidation by a structured Cu active electrode, can solve the reliability issue. High-quality pyramidal Cu electrodes with a sharp tip are prepared via the template-stripping method. Morphology-dependent surface energy facilitates the oxidation of Cu atoms at the tip rather than in other regions, and the tip-enhanced electric fields can accelerate the transport of the generated Cu ions. As a result, CF growth occurs mainly at the tip of the pyramidal electrode, which is confirmed by high-resolution electron microscopy and elemental analysis. The RRAM exhibits highly uniform and low forming voltages (the average forming voltage and its standard deviation for 20 pyramid-based RRAMs are 0.645 and 0.072 V, respectively). Moreover, all multilevel resistance states for the RRAMs are clearly distinguished and show narrow distributions within 1 order of magnitude, leading to reliable cell-to-cell performance for MLC operation.