Metastable hexagonal close-packed palladium hydride in liquid cell TEM.

Metastable phases-kinetically favoured structures-are ubiquitous in nature1,2. Rather than forming thermodynamically stable ground-state structures, crystals grown from high-energy precursors often initially adopt metastable structures depending on the initial conditions, such as temperature, pressure or crystal size1,3,4. As the crystals grow further, they typically undergo a series of transformations from metastable phases to lower-energy and ultimately energetically stable phases1,3,4. Metastable phases sometimes exhibit superior physicochemical properties and, hence, the discovery and synthesis of new metastable phases are promising avenues for innovations in materials science1,5. However, the search for metastable materials has mainly been heuristic, performed on the basis of experiences, intuition or even speculative predictions, namely 'rules of thumb'. This limitation necessitates the advent of a new paradigm to discover new metastable phases based on rational design. Such a design rule is embodied in the discovery of a metastable hexagonal close-packed (hcp) palladium hydride (PdHx) synthesized in a liquid cell transmission electron microscope. The metastable hcp structure is stabilized through a unique interplay between the precursor concentrations in the solution: a sufficient supply of hydrogen (H) favours the hcp structure on the subnanometre scale, and an insufficient supply of Pd inhibits further growth and subsequent transition towards the thermodynamically stable face-centred cubic structure. These findings provide thermodynamic insights into metastability engineering strategies that can be deployed to discover new metastable phases.

Triptycene Branched Poly(aryl-co-aryl piperidinium) Electrolytes for Alkaline Anion Exchange Membrane Fuel Cells and Water Electrolyzers.

Alkaline polymer electrolytes (APEs) are essential materials for alkaline energy conversion devices such as anion exchange membrane fuel cells (AEMFCs) and water electrolyzers (AEMWEs). Here, we report a series of branched poly(aryl-co-aryl piperidinium) with different branching agents (triptycene: highly-rigid, three-dimensional structure; triphenylbenzene: planar, two-dimensional structure) for high-performance APEs. Among them, triptycene branched APEs showed excellent hydroxide conductivity (193.5 mS cm-1 @80 °C), alkaline stability, mechanical properties, and dimensional stability due to the formation of branched network structures, and increased free volume. AEMFCs based on triptycene-branched APEs reached promising peak power densities of 2.503 and 1.705 W cm-2 at 75/100 % and 30/30 % (anode/cathode) relative humidity, respectively. In addition, the fuel cells can run stably at a current density of 0.6 A cm-2 for 500 h with a low voltage decay rate of 46 µV h-1 . Importantly, the related AEMWE achieved unprecedented current densities of 16 A cm-2 and 14.17 A cm-2 (@2 V, 80 °C, 1 M NaOH) using precious and non-precious metal catalysts, respectively. Moreover, the AEMWE can be stably operated under 1.5 A cm-2 at 60 °C for 2000 h. The excellent results suggest that the triptycene-branched APEs are promising candidates for future AEMFC and AEMWE applications.

Surface Electrochemistry of Carbon Electrodes and Faradaic Reactions in Capacitive Deionization.

Recent advances in electrochemical desalination techniques have paved way for utilization of saline water. In particular, capacitive deionization (CDI) enables removal of salts with high energy efficiency and economic feasibility, while its applicability has been challenged by degradation of carbon electrodes in long-term operations. Herein, we report a thorough investigation on the surface electrochemistry of carbon electrodes and Faradaic reactions that are responsible for stability issues of CDI systems. By using bare and membrane CDI (MCDI) as model systems, we identified various electrochemical reactions of carbon electrodes with water or oxygen, with thermodynamics and kinetics governed by the electrode potential and pH. As a result, a complete overview of the Faradaic reactions taking place in CDI was constructed by tracing the physicochemical changes occurring in CDI and MCDI systems.

Direct Synthesis of Intermetallic Platinum-Alloy Nanoparticles Highly Loaded on Carbon Supports for Efficient Electrocatalysis.

Compared to nanostructured platinum (Pt) catalysts, ordered Pt-based intermetallic nanoparticles supported on a carbon substrate exhibit much enhanced catalytic performance, especially in fuel cell electrocatalysis. However, direct synthesis of homogeneous intermetallic alloy nanocatalysts on carbonaceous supports with high loading is still challenging. Herein, we report a novel synthetic strategy to directly produce highly dispersed MPt alloy nanoparticles (M = Fe, Co, or Ni) on various carbon supports with high catalyst loading. Importantly, a unique bimetallic compound, composed of [M(bpy)3]2+ cation (bpy = 2,2'-bipyridine) and [PtCl6]2- anion, evenly decomposes on carbon surface and forms uniformly sized intermetallic nanoparticles with a nitrogen-doped carbon protection layer. The excellent oxygen reduction reaction (ORR) activity and stability of the representative reduced graphene oxide (rGO)-supported L10-FePt catalyst (37 wt %-FePt/rGO), exhibiting 18.8 times higher specific activity than commercial Pt/C catalyst without degradation over 20 000 cycles, well demonstrate the effectiveness of our synthetic approach toward uniformly alloyed nanoparticles with high homogeneity.

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.

Epitaxial growth of a single-crystal hybridized boron nitride and graphene layer on a wide-band gap semiconductor.

Vertical and lateral heterogeneous structures of two-dimensional (2D) materials have paved the way for pioneering studies on the physics and applications of 2D materials. A hybridized hexagonal boron nitride (h-BN) and graphene lateral structure, a heterogeneous 2D structure, has been fabricated on single-crystal metals or metal foils by chemical vapor deposition (CVD). However, once fabricated on metals, the h-BN/graphene lateral structures require an additional transfer process for device applications, as reported for CVD graphene grown on metal foils. Here, we demonstrate that a single-crystal h-BN/graphene lateral structure can be epitaxially grown on a wide-gap semiconductor, SiC(0001). First, a single-crystal h-BN layer with the same orientation as bulk SiC was grown on a Si-terminated SiC substrate at 850 °C using borazine molecules. Second, when heated above 1150 °C in vacuum, the h-BN layer was partially removed and, subsequently, replaced with graphene domains. Interestingly, these graphene domains possess the same orientation as the h-BN layer, resulting in a single-crystal h-BN/graphene lateral structure on a whole sample area. For temperatures above 1600 °C, the single-crystal h-BN layer was completely replaced by the single-crystal graphene layer. The crystalline structure, electronic band structure, and atomic structure of the h-BN/graphene lateral structure were studied by using low energy electron diffraction, angle-resolved photoemission spectroscopy, and scanning tunneling microscopy, respectively. The h-BN/graphene lateral structure fabricated on a wide-gap semiconductor substrate can be directly applied to devices without a further transfer process, as reported for epitaxial graphene on a SiC substrate.

Highly Durable and Active PtFe Nanocatalyst for Electrochemical Oxygen Reduction Reaction.

Demand on the practical synthetic approach to the high performance electrocatalyst is rapidly increasing for fuel cell commercialization. Here we present a synthesis of highly durable and active intermetallic ordered face-centered tetragonal (fct)-PtFe nanoparticles (NPs) coated with a "dual purpose" N-doped carbon shell. Ordered fct-PtFe NPs with the size of only a few nanometers are obtained by thermal annealing of polydopamine-coated PtFe NPs, and the N-doped carbon shell that is in situ formed from dopamine coating could effectively prevent the coalescence of NPs. This carbon shell also protects the NPs from detachment and agglomeration as well as dissolution throughout the harsh fuel cell operating conditions. By controlling the thickness of the shell below 1 nm, we achieved excellent protection of the NPs as well as high catalytic activity, as the thin carbon shell is highly permeable for the reactant molecules. Our ordered fct-PtFe/C nanocatalyst coated with an N-doped carbon shell shows 11.4 times-higher mass activity and 10.5 times-higher specific activity than commercial Pt/C catalyst. Moreover, we accomplished the long-term stability in membrane electrode assembly (MEA) for 100 h without significant activity loss. From in situ XANES, EDS, and first-principles calculations, we confirmed that an ordered fct-PtFe structure is critical for the long-term stability of our nanocatalyst. This strategy utilizing an N-doped carbon shell for obtaining a small ordered-fct PtFe nanocatalyst as well as protecting the catalyst during fuel cell cycling is expected to open a new simple and effective route for the commercialization of fuel cells.

Remnant Copper Cation-Assisted Atom Mixing in Multicomponent Nanoparticles.

Nanostructured high-/medium-entropy compounds have emerged as important catalytic materials for energy conversion technologies, but complex thermodynamic relationships involved with the element mixing enthalpy have been a considerable roadblock to the formation of stable single-phase structures. Cation exchange reactions (CERs), in particular with copper sulfide templates, have been extensively investigated for the synthesis of multicomponent heteronanoparticles with unconventional structural features. Because copper cations within the host copper sulfide templates are stoichiometrically released with incoming foreign cations in CERs to maintain the overall charge balance, the complete absence of Cu cations in the nanocrystals after initial CERs would mean that further compositional variation would not be possible by subsequent CERs. Herin, we successfully retained a portion of Cu cations within the silver sulfide (Ag2S) and gold sulfide (Au2S) phases of Janus Cu2-xS-M2S (M = Ag, Au) nanocrystals after the CERs, by partially suppressing the transformation of the anion sublattice that inevitably occurs during the introduction of external cations. Interestingly, the subsequent CERs on Janus Cu1.81S-M2S (M = Ag, Au), by utilizing the remnant Cu cations, allowed the construction of Janus Cu1.81S-AgxAuyS, which preserved the initial heterointerface. The synthetic strategy described in this work to suppress the complete removal of the Cu cation from the template could fabricate the CER-driven heterostructures with greatly diversified compositions, which exhibit unusual optical and catalytic properties.

High Free Volume Polyelectrolytes for Anion Exchange Membrane Water Electrolyzers with a Current Density of 13.39 A cm-2 and a Durability of 1000 h.

The rational design of the current anion exchange polyelectrolytes (AEPs) is challenging to meet the requirements of both high performance and durability in anion exchange membrane water electrolyzers (AEMWEs). Herein, highly-rigid-twisted spirobisindane monomer is incorporated in poly(aryl-co-aryl piperidinium) backbone to construct continuous ionic channels and to maintain dimensional stability as promising materials for AEPs. The morphologies, physical, and electrochemical properties of the AEPs are investigated based on experimental data and molecular dynamics simulations. The present AEPs possess high free volumes, excellent dimensional stability, hydroxide conductivity (208.1 mS cm-1 at 80 °C), and mechanical properties. The AEMWE of the present AEPs achieves a new current density record of 13.39 and 10.7 A cm-2 at 80 °C by applying IrO2 and nonprecious anode catalyst, respectively, along with outstanding in situ durability under 1 A cm-2 for 1000 h with a low voltage decay rate of 53 µV h-1 . Moreover, the AEPs can be applied in fuel cells and reach a power density of 2.02 W cm-2 at 80 °C under fully humidified conditions, and 1.65 W cm-2 at 100 °C, 30% relative humidity. This study provides insights into the design of high-performance AEPs for energy conversion devices.

Instantaneous Thermal Energy for Swift Synthesis of Single-Atom Catalysts for Unparalleled Performance in Metal-Air Batteries and Fuel Cells.

Based on experimental and computational evidence, phthalocyanine (Pc) compounds in the form of quaternary-bound metal-nitrogen (N) atoms are the most effective catalysts for oxygen reduction reaction (ORR). However, the heat treatment process used in their synthesis may compromise the ideal structure, causing the agglomeration of transition metals. To overcome this issue, a novel method is developed for synthesizing iron (Fe) single-atom catalysts with ideal structures supported by thermally exfoliated graphene oxide (GO). This is achieved through a short heat treatment of only 2.5 min involving FePc and N, N-dimethylformamide in the presence of GO. According to the synthesis mechanism revealed by this study, carbon monoxide acts as a strong linker between the single Fe atoms and graphene. It facilitates the formation of a structure containing oxygen species between FeN4 and graphene, which provides high activity and stability for the ORR. These catalysts possess an enormous number of active sites and exhibit enhanced activity toward the alkaline ORR. They demonstrate excellent performance when applied to real electrochemical devices, such as zinc-air batteries and anion exchange membrane fuel cells. It is expected that the instantaneous heat treatment method developed in this study will aid in the development of high-performing single-atom catalysts.

Pd nanocrystals on WC as a synergistic electrocatalyst for hydrogen oxidation reactions.

Electrocatalysts for hydrogen oxidation reactions (HORs) are the key to renewable-energy technologies including fuel cells, hydrogen pumps, and water splitting. Despite the significant technological interest and tremendous efforts that have been made, development of hydrogen electrode catalysts with high activity at low cost remains a great challenge. Here, we report the preparation, characterization, and electrochemical properties of a hybrid material composed of Pd nanocrystals grown on spontaneously oxidized WC as a high-performance catalyst for the HOR. The Pd/WC hybrid exhibits enhanced catalytic activity compared to a carbon supported Pd (Pd/C) catalyst, making it a Pt-free, effective catalyst for the HOR. The remarkable catalytic activity arises from synergistic ligand effects between Pd and WC.

Chemical tuning of electrochemical properties of Pt-skin surfaces for highly active oxygen reduction reactions.

Pt-skin surfaces were successfully fabricated by the chemical deposition of additional Pt on corrugated Pt-Ni nanoparticles with Pt-skeleton surfaces. Compared to the Pt-skin formed by heat annealing, the chemically-tuned Pt-skin had a higher Pt coordination number and surface crystallinity, which resulted in superior ORR activity and durability.

Effect of particle size of PtRu nanoparticles embedded in WO3 on electrocatalysis.

Size-controlled PtRu nanoparticles embedded in WO3 were prepared by simultaneous multigun sputtering on pure targets of Pt, Ru, and WO3. The mean diameter of the PtRu nanoparticles, as confirmed by high-resolution transmission electron microscopy, can be varied from -2.3 to -3.6 nm by varying the RF power ratio of PtRu and WO3. On the basis of transmission electron diffraction results for the PtRu nanoparticles embedded in WO3, it was confirmed that PtRu exists as an alloy metal phase, whereas the WO3 matrix is present as an amorphous phase. Size-controlled PtRu/WO3 electrodes were found to exhibit unique electronic properties depending on their size, which affected the potential of zero total charge and the methanol oxidation reaction. The mass activity of PtRu/WO3 for methanol oxidation was determined by the interplay of the surface electronic factors at the metal-solution interface; the oxophilicity of the nanoparticles increased with decreasing particle size.

Multiscale Architectured Membranes, Electrodes, and Transport Layers for Next-Generation Polymer Electrolyte Membrane Fuel Cells.

Over the past few decades, considerable advances have been achieved in polymer electrolyte membrane fuel cells (PEMFCs) based on the development of material technology. Recently, an emerging multiscale architecturing technology covering nanometer, micrometer, and millimeter scales has been regarded as an alternative strategy to overcome the hindrance to achieving high-performance and reliable PEMFCs. This review summarizes the recent progress in the key components of PEMFCs based on a novel architecture strategy. In the first section, diverse architectural methods for patterning the membrane surface with random, single-scale, and multiscale structures as well as their efficacy for improving catalyst utilization, charge transport, and water management are discussed. In the subsequent section, the electrode structures designed with 1D and 3D multiscale structures to enable low Pt usage, improve oxygen transport, and achieve high electrode durability are elucidated. Finally, recent advances in the architectured transport layer for improving mass transportation including pore gradient, perforation, and patterned wettability for gas diffusion layer and 3D structured/engineered flow fields are described.

Role of electronic perturbation in stability and activity of Pt-based alloy nanocatalysts for oxygen reduction.

The design of electrocatalysts for polymer electrolyte membrane fuel cells must satsify two equally important fundamental principles: optimization of electrocatalytic activity and long-term stability in acid media (pH <1) at high potential (0.8 V). We report here a solution-based approach to the preparation of Pt-based alloy with early transition metals and realistic parameters for the stability and activity of Pt(3)M (M = Y, Zr, Ti, Ni, and Co) nanocatalysts for oxygen reduction reaction (ORR). The enhanced stability and activity of Pt-based alloy nanocatalysts in ORR and the relationship between electronic structure modification and stability were studied by experiment and DFT calculations. Stability correlates with the d-band fillings and the heat of alloy formation of Pt(3)M alloys, which in turn depends on the degree of the electronic perturbation due to alloying. This concept provides realistic parameters for rational catalyst design in Pt-based alloy systems.

Electrocatalytic effects of carbon dissolution in Pd nanoparticles.

Highly dispersed Pd nanoparticles were prepared by borohydride reduction of Pd(acac)(2) in 1,2-propanediol at an elevated temperature. They were uniformly dispersed on carbon black without significant aggregation. X-ray diffraction showed that carbons from the Pd precursor dissolved in Pd, increasing its lattice parameter. A modified reduction process was tested to remove the carbon impurities. Carbon removal greatly enhanced catalytic activity toward the oxygen reduction reaction. It also generated an inconsistency between the electronic modifications obtained from X-ray photoelectron spectroscopy and the electrochemical method. CO displacement measurements showed that the formation of Pd-C bonds decreased the work function of the surface Pd atoms.

Oxygen Plasma-Mediated Microstructured Hydrocarbon Membrane for Improving Interface Adhesion and Mass Transport in Polymer Electrolyte Fuel Cells.

Developing a method for fabricating high-efficient and low-cost fuel cells is imperative for commercializing polymer electrolyte membrane (PEM) fuel cells (FCs). This study introduces a mechanical and chemical modification technique using the oxygen plasma irradiation process for hydrocarbon-based (HC) PEM. The oxygen functional groups were introduced on the HC-PEM surface through the plasma process in the controlled area, and microsized structures were formed. The modified membrane was incorporated with plasma-treated electrodes, improving the adhesive force between the HC-PEM and the electrode. The decal transfer was enabled at low temperatures and pressures, and the interfacial resistance in the membrane-electrode assembly (MEA) was reduced. Furthermore, the micropillar structured electrode configuration significantly reduced the oxygen transport resistance in the MEA. Various diagnostic techniques were conducted to find out the effects of the membrane surface modification, interface adhesion, and mass transport, such as physical characterizations, mechanical stress tests, and diverse electrochemical measurements.

Surface structures and electrochemical activities of Pt overlayers on Ir nanoparticles.

Pt overlayers were deposited on carbon-supported Ir nanoparticles with various coverages. Structural and electrochemical characterizations were performed using transmission electron microscopy (TEM), X-ray diffraction, high-resolution powder diffraction (HRPD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), cyclic voltammetry (CV), CO stripping voltammetry, and N2O reduction. The surface of Ir nanoparticles was covered with Pt overlayers with thickness varying from the submonolayer scale to more than two monolayers. Surface analyses such as CV and CO stripping voltammetry indicated that the Pt overlayers were uniformly deposited on the Ir nanoparticles, and the resultant Pt overlayers exhibited gradual changes in surface characteristics toward the Pt surface as the surface coverage increased. The distinct CO stripping characteristics and the enhanced Pt utilization affected electrocatalytic activities for methanol oxidation. The electrochemical stability of the Pt overlayer was compared with a commercial carbon-supported Pt catalyst by conducting a potential cycling experiment.

Emerging carbon shell-encapsulated metal nanocatalysts for fuel cells and water electrolysis.

The development of low-cost, high-efficiency electrocatalysts is of primary importance for hydrogen energy technology. Noble metal-based catalysts have been extensively studied for decades; however, activity and durability issues still remain a challenge. In recent years, carbon shell-encapsulated metal (M@C) catalysts have drawn great attention as novel materials for water electrolysis and fuel cell applications. These electrochemical reactions are governed mainly by interfacial charge transfer between the core metal and the outer carbon shell, which alters the electronic structure of the catalyst surface. Furthermore, the rationally designed and fine-tuned carbon shell plays a very interesting role as a protective layer or molecular sieve layer to improve the performance and durability of energy conversion systems. Herein, we review recent advances in the use of M@C type nanocatalysts for extensive applications in fuel cells and water electrolysis with a focus on the structural design and electronic structure modulation of carbon shell-encapsulated metal/alloys. Finally, we highlight the current challenges and future perspectives of these catalytic materials and related technologies in this field.

Feasibility of a Spherical Hollow Carbon Framework as a Stable Host Material for Reversible Metallic Li Storage.

A spherical hollow carbon framework decorated with functional heteroatoms is designed and synthesized using ultrasonic spray pyrolysis as a potential anode material for lithium metal batteries (LMBs). The pore structure of the hollow carbon framework can be tailored by melamine, which is a functional additive for integrating abundant nanopores and the uniform decoration of heteroatoms in the structure. The large surface area and pore volume of the hollow carbon framework offer enhanced reversibility and capability for metallic Li storage. In addition, the dendritic growth of Li and volume changes induced by repeated Li plating and stripping can be effectively suppressed during cycling. More importantly, atomic-scale decorations of heteroatoms can effectively lower the overpotential for the nucleation and growth of metallic Li inside the hollow carbon framework. It is mainly responsible for improving the cycle performance and rate capability, even at a high current density. Finally, the hollow carbon framework anode shows stable behavior toward Li plating and stripping without significant capacity fading in the LMBs than conventional Li metal anodes.