Tailored Electronic Structure of Ir in High Entropy Alloy for Highly Active and Durable Bifunctional Electrocatalyst for Water Splitting under an Acidic Environment.

Proton-exchange-membrane water electrolysis (PEMWE) requires an efficient and durable bifunctional electrocatalyst for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, Ir-based electrocatalyst is designed using the high entropy alloy (HEA) platform of ZnNiCoIrX with two elements (X: Fe and Mn). A facile dealloying in the vacuum system enables the construction of a nanoporous structure with high crystallinity using Zn as a sacrificial element. Especially, Mn incorporation into HEAs tailors the electronic structure of the Ir site, resulting in the d-band center being far away from the Fermi level. Downshifting of the d-band center weakens the adsorption energy with reaction intermediates, which is beneficial for catalytic reactions. Despite low Ir content, ZnNiCoIrMn delivers only 50 mV overpotential for HER at -50 mA cm-2 and 237 mV overpotential for the OER at 10 mA cm-2 . Furthermore, ZnNiCoIrMn shows almost constant voltage for the HER and OER for 100 h and a high stability number of 3.4 × 105 nhydrogen nIr -1 and 2.4 × 105 noxygen nIr -1 , demonstrating the exceptional durability of the HEA platform. The compositional engineering of ZnNiCoIrMn limits the diffusion of elements by high entropy effects and simultaneously tailors the electronic structure of active Ir sites, resulting in the modified cohesive and adsorption energies, all of which can suppress the dissolution of elements.

Mn-Dopant Differentiating the Ru and Ir Oxidation States in Catalytic Oxides Toward Durable Oxygen Evolution Reaction in Acidic Electrolyte.

Designing an efficient and durable electrocatalyst for the sluggish oxygen evolution reaction (OER) at the anode remains the foremost challenge in developing proton exchange membrane (PEM) electrolyzers. Here, a highly active and durable cactus-like nanoparticle with an exposed heterointerface between the IrO2 and the low oxidation state Ru by introducing a trace amount of Mn dopant is reported. The heterostructure fabrication relies on initial mixing of the Ru and Ir phases before electrochemical oxidation to produce a conjoined Ru/IrO2 heterointerface. Benefitting from electron transfer at the heterointerface, the low oxidation state Ru species shows excellent initial activity, which is maintained even after 180 h of continuous OER test. In a half-cell test, the Mn-doped RuIr nanocactus (Mn-RuIr NCT) achieves a mass activity of 1.85 A mgIr+Ru -1 at 1.48 VRHE , which is 139-fold higher than that of commercial IrO2 . Moreover, the superior electrocatalytic performance of Mn-RuIr NCT in the PEM electrolysis system ensures its viability in practical uses. The results of the excellent catalytic performance for acidic OER indicate that the heterostructuring robust rutile IrO2 and the highly active Ru species with a low oxidation state on the catalyst surface drive a synergistic effect.

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.

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.

Polystyrene-Based Hydroxide-Ion-Conducting Ionomer: Binder Characteristics and Performance in Anion-Exchange Membrane Fuel Cells.

Polystyrene-based polymers with variable molecular weights are prepared by radical polymerization of styrene. Polystyrene is grafted with bromo-alkyl chains of different lengths through Friedel-Crafts acylation and quaternized to afford a series of hydroxide-ion-conducting ionomers for the catalyst binder for the membrane electrode assembly in anion-exchange membrane fuel cells (AEMFCs). Structural analyses reveal that the molecular weight of the polystyrene backbone ranges from 10,000 to 63,000 g mol-1, while the ion exchange capacity of quaternary-ammonium-group-bearing ionomers ranges from 1.44 to 1.74 mmol g-1. The performance of AEMFCs constructed using the prepared electrode ionomers is affected by several ionomer properties, and a maximal power density of 407 mW cm-2 and a durability exceeding that of a reference cell with a commercially available ionomer are achieved under optimal conditions. Thus, the developed approach is concluded to be well suited for the fabrication of next-generation electrode ionomers for high-performance AEMFCs.

Interaction Mediator Assisted Synthesis of Mesoporous Molybdenum Carbide: Mo-Valence State Adjustment for Optimizing Hydrogen Evolution.

To overcome inherent limitations of molybdenum carbide (MoxC) for hydrogen evolution reaction (HER), i.e., low density of active site and nonideal hydrogen binding strength, we report the synthesis of valence-controlled mesoporous MoxC as a highly efficient HER electrocatalyst. The synthesis procedure uses an interaction mediator (IM), which significantly increases the density of active site by mediating interaction between PEO-b-PS template and Mo source. The valence state of Mo is tuned by systematic control of the environment around Mo by controlled heat treatment under air before thermal treatment at 1100 °C. Theoretical calculations reveal that the hydrogen binding is strongly influenced by Mo valence. Consequently, MoxC achieves a significant increase in HER activity (exceeding that of Pt/C at high current density ∼35 mA/cm2 in alkaline solution). In addition, a volcano-type correlation between HER activity and Mo valence is identified with various experimental indicators. The present strategies can be applied to various carbide and Mo-based catalysts, and the established Mo valence and HER relations can guide development of highly active HER electrocatalysts.

Investigation of the Support Effect in Atomically Dispersed Pt on WO3-x for Utilization of Pt in the Hydrogen Evolution Reaction.

Single-atom catalysts (SACs) have attracted growing attention because they maximize the number of active sites, with unpredictable catalytic activity. Despite numerous studies on SACs, there is little research on the support, which is essential to understanding SAC. Herein, we systematically investigated the influence of the support on the performance of the SAC by comparing with single-atom Pt supported on carbon (Pt SA/C) and Pt nanoparticles supported on WO3-x (Pt NP/WO3-x ). The results revealed that the support effect was maximized for atomically dispersed Pt supported on WO3-x (Pt SA/WO3-x ). The Pt SA/WO3-x exhibited a higher degree of hydrogen spillover from Pt atoms to WO3-x at the interface, compared with Pt NP/WO3-x , which drastically enhanced Pt mass activity for hydrogen evolution (up to 10 times). This strategy provides a new framework for enhancing catalytic activity for HER, by reducing noble metal usage in the field of SACs.

Bio-Derived Co2 P Nanoparticles Supported on Nitrogen-Doped Carbon as Promising Oxygen Reduction Reaction Electrocatalyst for Anion Exchange Membrane Fuel Cells.

Recently, nonnoble-metal catalysts such as a metal coordinated to nitrogen doped in a carbon matrix have been reported to exhibit superior oxygen reduction reaction (ORR) activity in alkaline media. In this work, Co2 P nanoparticles supported on heteroatom-doped carbon catalysts (NBSCP) are developed with an eco-friendly synthesis method using bean sprouts. NBSCP can be easily synthesized through metal precursor absorption and carbonization at a high temperature. It shows a very large specific surface area with various dopants such as nitrogen, phosphorus, and sulfur derived from small organic molecules. The catalyst can exhibit activity in various electrochemical reactions. In particular, excellent performance is noted for the ORR. Compared to the commercial Pt/C, NBSCP exhibits a lower onset potential, higher current density, and superior durability. This excellent ORR activity and durability is attributable to the synergistic effect between Co2 P nanoparticles and nitrogen-doped carbon. In addition, superior performance is noted on applying NBSCP to a practical anion exchange membrane fuel cell system. Through this work, the possibility of applying an easily obtained bio-derived material to energy conversion and storage systems is demonstrated.

An extremely low Pt loading cathode for a highly efficient proton exchange membrane water electrolyzer.

Direct self-terminated Pt electrodeposition on carbon paper enables precise control of loading Pt mass, from the sub-microgram to the sub-milligram scale. This can provide insight into the low limits of Pt use for reasonable performance of a proton exchange membrane water electrolyzer.

Transition metal alloying effect on the phosphoric acid adsorption strength of Pt nanoparticles: an experimental and density functional theory study.

The effect of alloying with transition metals (Ni, Co, Fe) on the adsorption strength of phosphoric acid on Pt alloy surfaces was investigated using electrochemical analysis and first-principles calculations. Cyclic voltammograms of carbon-supported Pt3M/C (M = Ni, Co, and Fe) electrocatalysts in 0.1 M HClO4 with and without 0.01 M H3PO4 revealed that the phosphoric acid adsorption charge density near the onset potential on the nanoparticle surfaces was decreased by alloying with transition metals in the order Co, Fe, Ni. First-principles calculations based on density functional theory confirmed that the adsorption strength of phosphoric acid was weakened by alloying with transition metals, in the same order as that observed in the electrochemical analysis. The simulation suggested that the weaker phosphoric acid adsorption can be attributed to a lowered density of states near the Fermi level due to alloying with transition metals.

Anomalous in situ Activation of Carbon-Supported Ni2P Nanoparticles for Oxygen Evolving Electrocatalysis in Alkaline Media.

Electrochemical water splitting is one of the most promising systems by which to store energy produced from sustainable sources, such as solar and wind energy. Designing robust and stable electrocatalysts is urgently needed because of the relatively sluggish kinetics of the anodic reaction, i.e. the oxygen evolution reaction (OER). In this study, we investigate the anomalous in situ activation behaviour of carbon-supported Ni2P nanoparticles (Ni2P/C) during OER catalysis in alkaline media. The activated Ni2P/C shows an exceptionally high activity and stability under OER conditions in which the overpotential needed to achieve 10 mA cm-2 was reduced from approximately 350 mV to approximately 300 mV after 8,000 cyclic voltammetric scans. In situ and ex situ characterizations indicate that the activity enhancement of Ni2P catalysts is due to a favourable phase transformation of the Ni centre to ß-NiOOH, including increases in the active area induced by structural deformation under the OER conditions. These findings provide new insights towards designing transition metal/phosphide-based materials for an efficient water splitting catalyst.

High-Performance Electroactive Polymer Actuators Based on Ultrathick Ionic Polymer-Metal Composites with Nanodispersed Metal Electrodes.

Ionic polymer-metal composites (IPMCs) have been proposed as biomimetic actuators that are operable at low applied voltages. However, the bending strain and generating force of the IPMC actuators have generally exhibited a trade-off relationship, whereas simultaneous enhancement of both the qualities is required for their practical applications. Herein, a significant improvement in both the strain and force of the IPMC actuators is achieved by a facile approach, exploiting thickness-controlled ion-exchange membranes and nanodispersed metal electrodes. To guarantee a large generating force of the IPMC actuators, ultrathick ion-exchange membranes are prepared by stacking pre-extruded Nafion films. Metal electrodes with a nanodispersed structure are formed on the membranes via alcohol-assisted electroless plating, which allows increased capacitance and facilitated ion transport. The resulting actuators exhibit greatly enhanced electromechanical properties, including an approximately four times larger strain and two times larger force compared to those of actuators having the conventional structure. Moreover, the ability to lift 16 coins (a weight of 124 g) has been successfully demonstrated using ultrathick IPMC actuators, which shows great promise in realizing artificial muscles.

Nickel Nanofoam/Different Phases of Ordered Mesoporous Carbon Composite Electrodes for Superior Capacitive Energy Storage.

Electrochemical energy storage devices based on electric double layer capacitors (EDLCs) have received considerable attention due to their high power density and potential for obtaining improved energy density in comparison to the lithium ion battery. Ordered mesoporous carbon (OMC) is a promising candidate for use as an EDLC electrode because it has a high specific surface area (SSA), providing a wider charge storage space and size-controllable mesopore structure with a long-range order, suppling high accessibility to the electrolyte ions. However, OMCs fabricated using conventional methods have several drawbacks including low electronic conductivity and long ionic diffusion paths in mesopores. We used nickel nanofoam, which has a relatively small pore (sub-100 nm to subµm) network structure, as a current collector. This provides a significantly shortened electronic/ionic current paths and plentiful surface area, enabling stable and close attachment of OMCs without the use of binders. Thus, we present hierarchical binder-free electrode structures based on OMC/Ni nanofoams. These structures give rise to enhanced specific capacitance and a superior rate capability. We also investigated the mesopore structural effect of OMCs on electrolyte transport by comparing the capacitive performances of collapsed lamellar, cylindrical, and spherical mesopore electrodes. The highly ordered and straightly aligned cylindrical OMCs exhibited the highest specific capacitance and the best rate capability.

Design of an Advanced Membrane Electrode Assembly Employing a Double-Layered Cathode for a PEM Fuel Cell.

The membrane electrolyte assembly (MEA) designed in this study utilizes a double-layered cathode: an inner catalyst layer prepared by a conventional decal transfer method and an outer catalyst layer directly coated on a gas diffusion layer. The double-layered structure was used to improve the interfacial contact between the catalyst layer and membrane, to increase catalyst utilization and to modify the removal of product water from the cathode. Based on a series of MEAs with double-layered cathodes with an overall Pt loading fixed at 0.4 mg cm(-2) and different ratios of inner-to-outer Pt loading, the MEA with an inner layer of 0.3 mg Pt cm(-2) and an outer layer of 0.1 mg Pt cm(-2) exhibited the best performance. This performance was better than that of the conventional single-layered electrode by 13.5% at a current density of 1.4 A cm(-2).

Highly efficient and durable TiN nanofiber electrocatalyst supports.

To date, carbon-based materials including various carbon nanostructured materials have been extensively used as an electrocatalyst support for proton exchange membrane fuel cell (PEMFC) applications due to their practical nature. However, carbon dissolution or corrosion caused by high electrode potential in the presence of O2 and/or water has been identified as one of the main failure modes for the device operation. Here, we report the first TiN nanofiber (TNF)-based nonwoven structured materials to be constructed via electrospinning and subsequent two-step thermal treatment processes as a support for the PEMFC catalyst. Pt catalyst nanoparticles (NPs) deposited on the TNFs (Pt/TNFs) were electrochemically characterized with respect to oxygen reduction reaction (ORR) activity and durability in an acidic medium. From the electrochemical tests, the TNF-supported Pt catalyst was better and more stable in terms of its catalytic performance compared to a commercially available carbon-supported Pt catalyst. For example, the initial oxygen reduction performance was comparable for both cases, while the Pt/TNF showed much higher durability from an accelerated degradation test (ADT) configuration. It is understood that the improved catalytic roles of TNFs on the supported Pt NPs for ORR are due to the high electrical conductivity arising from the extended connectivity, high inertness to the electrochemical environment and strong catalyst-support interactions.

Green synthesis of carbon-supported nanoparticle catalysts by physical vapor deposition on soluble powder substrates.

Metal and metal oxide nanoparticles (NPs) supported on high surface area carbon (NP/Cs) were prepared by the physical vapor deposition of bulk materials on an α-D-glucose (Glu) substrate, followed by the deposition of the NPs on carbon supports. Using Glu as a carrier for the transport of NPs from the bulk materials to the carbon support surfaces, ultrafine NPs were obtained, exhibiting a stabilizing effect through OH moieties on the Glu surfaces. This stabilizing effect was strong enough to stabilize the NPs, but weak enough to not significantly block the metal surfaces. As only the target materials and Glu are required in our procedure, it can be considered environmentally friendly, with the NPs being devoid of hazardous chemicals. Furthermore, the resulting NP/Cs exhibited an improvement in activity for various electrochemical reactions, mainly attributed to their high surface area.

A highly active and durable Co-N-C electrocatalyst synthesized using exfoliated graphitic carbon nitride nanosheets.

Exfoliated graphitic carbon nitride nanosheets (g-C3N4-NS) were applied for the first time for the preparation of an electrocatalyst for the oxygen reduction reaction (ORR). A less dense structure with increased surface area was observed for g-C3N4-NS compared to bulk g-C3N4 from detailed analyses including TEM, STEM, AFM with depth profiling, XRD, and UV-Vis spectroscopy. The pyrolysis of the prepared g-C3N4-NS with Co and carbon under an inert environment provided an enhanced accessibility to the N functionalities required for efficient interaction of Co and C with N for the formation of Co-N-C networks and produced a hollow and interconnected Co-N-C-NS structure responsible for high durability. The Co-N-C-NS electrocatalyst exhibited superior catalytic activity and durability and further displayed fast and selective four electron transfer kinetics for the ORR, as evidenced by various electrochemical experiments. The hollow, interconnected structure of Co-N-C-NS with increased pyridinic and graphitic N species has been proposed to play a key role in facilitating the desired ORR reaction.

Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles.

The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

Third-body effects of native surfactants on Pt nanoparticle electrocatalysts in proton exchange fuel cells.

The residual surfactant organic molecules on electrocatalysts are expected to enhance the tolerance to specific anion adsorption, whereas the surfactants have been generally regarded as contaminants that block active surfaces. In this study, the Pt nanoparticles with adsorbed surfactants were prepared, and their electrochemical characteristics at various phosphoric acid concentrations were studied by the half-cell test. The third-body effect was experimentally confirmed by the single-cell test with a phosphoric acid-doped polybenzimidazole membrane.