Hydrogen Oxidation Reaction Research Articles

Comparative Study of Anion Exchange Membranes for Application in Advanced AEM Water Electrolysers

The chemical nature of hydrogen combined with its capability to be an energy carrier for energy conversion devices with zero- emission and its higher energy density than any other commercial fossil fuel-based energy source, make it unique [1]. The International Renewable Energy Agency has identified three of the most viable technologies for producing hydrogen in large volume, namely: alkaline water electrolyzers (AWEs), proton exchange membrane water electrolyzers (PEMWEs), and anion exchange membrane water electrolyzers (AEMWEs) [2]. Among the three types of electrochemical devices the AEMWEs are the newest and most promising, because they (i) have the same slim design of the PEMWEs, (ii) can operate at high current densities, and (iii) can use non-precious catalysts [3]. The durability and efficiency of the AEMWEs systems are significantly influenced by the anion exchange membranes (AEMs), which are currently under development. In addition, the used catalysts, as well as the methods for fabrication of the membrane electrode assemblies (MEAs) also impact substantially the electrolyzer’s performance. Catalyst-coated substrate (CCS) is one of the methods for fabrication of MEAs [4], while the other used method is known as catalyst coated membranes (CCMs). The Reactive Spray Deposition Technology (RSDT) is an innovative flame-assisted method that can be used for fabrication MEAs from both types [5].In this work, CCS are fabricated by the ultrasonic spray deposition method and 5 MEAs are assembled with various AEM membranes. This approach involves the application of Platinum Group Metal (PGM) catalysts, Pt/C and as cathode and anode catalyst layers, onto a Gas Diffusion Layer (C-GDL) and a porous transport layer (Ti-PTL). As fabricated CCSs are assembled with the three state-of-the-art commercially available AEMs, namely: FAA-3, Sustainion X-37, and TM1, and their performance is evaluated. In addition, CCSs with ultra-low PGM loadings in their catalyst layers are fabricated with the RSDT method and better performance in comparison to the baseline MEAs with high PGM loadings, is achieved. This comparative study provides valuable insights into the strengths and weaknesses of each membrane type for application in AEM water electrolysers. Reference: [1] M. G. Rasul, M. A. Hazrat, M. A. Sattar, M. I. Jahirul, and M. J. Shearer, “The future of hydrogen: Challenges on production, storage and applications,” Energy Conversion and Management, vol. 272, p. 116326, Nov. 2022, doi: 10.1016/j.enconman.2022.116326.[2] D. Yang et al., “Patent analysis on green hydrogen technology for future promising technologies,” International Journal of Hydrogen Energy, vol. 48, no. 83, pp. 32241–32260, Oct. 2023, doi: 10.1016/j.ijhydene.2023.04.317.[3] D. S. Falcão, “Green Hydrogen Production by Anion Exchange Membrane Water Electrolysis: Status and Future Perspectives,” Energies, vol. 16, no. 2, p. 943, Jan. 2023, doi: 10.3390/en16020943.[4] J. E. Park et al., “High-performance anion-exchange membrane water electrolysis,” Electrochimica Acta, vol. 295, pp. 99–106, Feb. 2019, doi: 10.1016/j.electacta.2018.10.143.[5] Z. Zeng, J. Xing, L. Bonville, D. R. Dekel, R. Maric, and S. Bliznakov, “Advanced nickel-based catalysts for the hydrogen oxidation reaction in alkaline media synthesized by reactive spray deposition technology: Study of the effect of particle size,” International Journal of Hydrogen Energy, p. S0360319923013721, Apr. 2023, doi: 10.1016/j.ijhydene.2023.03.249.

Boosting electrochemical performance of Ni/YSZ electrode through simultaneous injection of nickel and ceria

Nickel/oxygen ion conducting ceramic composite powders (Ni/YSZ) are commonly used materials for fuel electrodes of solid oxide fuel cells and electrolyzers. One of the ways for increasing the activity of Ni/YSZ is infiltration/impregnation, where a formed porous electrode is impregnated with solutions of active elements, followed by thermolysis. In this study, Ni/YSZ electrodes simultaneously impregnated with nickel and ceria particles in different ratios are investigated. It is shown that the introduction of highly dispersed nickel only slightly increases the activity of the Ni/YSZ electrode and does not affect the pathway of the hydrogen oxidation reaction. If a minor amount of ceria particles is introduced into the electrode, it significantly increases its activity and partially changes the reaction mechanism. The best performance is obtained for the electrode impregnated with an equal volume solution of nickel and cerium nitrates. The polarization resistance of such an electrode in wet hydrogen is about 0.05 and 0.17 Ohm cm2 at 850 and 600 °C, respectively, which is about 10 and 65 times lower compared to initial Ni/YSZ. Long-term tests of more than 1100 h in a wet hydrogen atmosphere at 700 °C showed satisfactory stability of polarization resistance of all investigated electrodes.

Hydrogen Electrode Reactions in Energy-Related Electrocatalysis Systems.

Hydrogen electrode reactions, including hydrogen evolution reactions and hydrogen oxidation reactions, are fundamental and crucial within aqueous electrochemistry. Particularly in energy-related electrocatalysis processes, there is a consistent involvement of hydrogen-related electrochemical processes, underscoring the need for in-depth study. This review encompasses significant reports, delving into elementary steps and reaction mechanisms of hydrogen electrode reactions, as well as catalyst design strategies. In addition, we focus on the application of hydrogen electrode reaction mechanism in different energy-related electrocatalytic reactions, and the significance of the promotion and suppression of reaction kinetics in different reaction systems. It thoroughly elucidated the significance of these reactions and the need for a deeper understanding, offering a novel perspective for the future development of this field.

Quantum confinement-induced anti-electrooxidation of metallic nickel electrocatalysts for hydrogen oxidation

AbstractThe anion-exchange-membrane fuel cell (AEMFC) is an attractive and cost-effective energy-conversion technology because it can use Earth-abundant and low-cost non-precious metal catalysts. However, non-precious metals used in AEMFCs to catalyse the hydrogen oxidation reaction are prone to self-oxidation, resulting in irreversible failure. Here we show a quantum well-like catalytic structure (QWCS), constructed by atomically confining Ni nanoparticles within a carbon-doped-MoOx/MoOx heterojunction (C-MoOx/MoOx) that can selectively transfer external electrons from the hydrogen oxidation reaction while remaining itself metallic. Electrons of Ni nanoparticles gain a barrier of 1.11 eV provided by the QWCS leading to Ni stability up to 1.2 V versus the reversible hydrogen electrode (VRHE) whereas electrons released from the hydrogen oxidation reaction easily cross the barrier by a gating operation of QWCS upon hydrogen adsorption. The QWCS-catalysed AEMFC achieved a high-power density of 486 mW mgNi−1 and withstood hydrogen starvation operations during shutdown–start cycles, whereas a counterpart AEMFC without QWCS failed in a single cycle.

Recent Advances in Revealing the Electrocatalytic Mechanism for Hydrogen Energy Conversion System.

In light of the intensifying global energy crisis and the mounting demand for environmental protection, it is of vital importance to develop advanced hydrogen energy conversion systems. Electrolysis cells for hydrogen production and fuel cell devices for hydrogen utilization are indispensable in hydrogen energy conversion. As one of the electrolysis cells, water splitting involves two electrochemical reactions, hydrogen evolution reaction and oxygen evolution reaction. And oxygen reduction reaction coupled with hydrogen oxidation reaction, represent the core electrocatalytic reactions in fuel cell devices. However, the inherent complexity and the lack of a clear understanding of the structure-performance relationship of these electrocatalytic reactions, have posed significant challenges to the advancement of research in this field. In this work, the recent development in revealing the mechanism of electrocatalytic reactions in hydrogen energy conversion systems is reviewed, including in situ characterization and theoretical calculation. First, the working principles and applications of operando measurements in unveiling the reaction mechanism are systematically introduced. Then the application of theoretical calculations in the design of catalysts and the investigation of the reaction mechanism are discussed. Furthermore, the challenges and opportunities are also summarized and discussed for paving the development of hydrogen energy conversion systems.

A catalyst family of high-entropy alloy atomic layers with square atomic arrangements comprising iron- and platinum-group metals.

We report a catalyst family of high-entropy alloy (HEA) atomic layers having three elements from iron-group metals (IGMs) and two elements from platinum-group metals (PGMs). Ten distinct quinary compositions of IGM-PGM-HEA with precisely controlled square atomic arrangements are used to explore their impact on hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). The PtRuFeCoNi atomic layers perform enhanced catalytic activity and durability toward HER and HOR when benchmarked against the other IGM-PGM-HEA and commercial Pt/C catalysts. Operando synchrotron x-ray absorption spectroscopy and density functional theory simulations confirm the cocktail effect arising from the multielement composition. This effect optimizes hydrogen-adsorption free energy and contributes to the remarkable catalytic activity observed in PtRuFeCoNi. In situ electron microscopy captures the phase transformation of metastable PtRuFeCoNi during the annealing process. They transform from random atomic mixing (25°C), to ordered L10 (300°C) and L12 (400°C) intermetallic, and finally phase-separated states (500°C).

Dual-Intermetallic Heterostructure on Hierarchical Nanoporous Metal for Highly Efficient Alkaline Hydrogen Electrocatalysis.

Constructing well-defined active multisites is an effective strategy to break linear scaling relationships to develop high-efficiency catalysts toward multiple-intermediate reactions. Here, dual-intermetallic heterostructure composed of tungsten-bridged Co3W and WNi4 intermetallic compounds seamlessly integrated on hierarchical nanoporous nickel skeleton is reported as a high-performance nonprecious electrocatalyst for alkaline hydrogen evolution and oxidation reactions. By virtue of interfacial tungsten atoms configuring contiguous multisites with proper adsorptions of hydrogen and hydroxyl intermediates to accelerate water dissociation/combination and column-nanostructured nickel skeleton facilitating electron and ion/molecule transportations, nanoporous nickel-supported Co3W-WNi4 heterostructure exhibits exceptional hydrogen electrocatalysis in alkaline media, with outstanding durability and impressive catalytic activities for hydrogen oxidation reaction (geometric exchange current density of ≈6.62 mA cm-2) and hydrogen evolution reaction (current density of ≈1.45 A cm-2 at overpotential of 200 mV). Such atom-ordered intermetallic heterostructure alternative to platinum group metals shows genuine potential for hydrogen production and utilization in hydroxide-exchange-membrane water electrolyzers and fuel cells.

Tailored Design of Mesoporous Nanospheres with High Entropic Alloy Sites for Efficient Redox Electrocatalysis.

High Entropy Alloys (HEAs) are a versatile material with unique properties, tailored for various applications. They enable pH-sensitive electrocatalytic transformations like hydrogen evolution reaction (HER) and hydrogen oxidation reactions (HOR) in alkaline media. Mesoporous nanostructures with high surface area are preferred for these electrochemical reactions, but designing mesoporous HEA sis challenging. To overcome this challenge, a low-temperature triblock copolymer-assisted wet-chemical approach is developed to produce mesoporous HEA nanospheres composed of PtPdRuMoNi systems with sufficient entropic mixing. Owing to active sites with inherent entropic effect, mesoporous features, and increased accessibility, optimized HEA nanospheres promote strong HER/HOR performance in alkaline medium. At 30 mV nominal overpotential, it exhibits a mass activity of ≈167 (HER) and 151 A gPt -1 (HOR), far exceeding commercial Pt-C electrocatalysts (34 and 48 A gPt -1) and many recently reportedvarious alloys. The Mott-Schottky analysis reveals HEA nanospheres inherit high charge carrier density, positive flat band potential, and smaller charge transfer barrier, resulting in better activity and faster kinetics. This micelle-assisted synthetic enable the exploration of the compositional and configurational spaces of HEAs at relatively low temperature, while simultaneously facilitating the introduction of mesoporous nanostructures for a wide range of catalytic applications.

The Role of Phosphorus on Alkaline Hydrogen Oxidation Electrocatalysis for Ruthenium Phosphides.

Transition metal/p-block compounds are regarded as the most essential materials for electrochemical energy converting systems involving various electrocatalysis. Understanding the role of p-block element on the interaction of key intermediates and interfacial water molecule orientation at the polarized catalyst-electrolyte interface during the electrocatalysis is important for rational designing advanced p-block modified metal electrocatalysts. Herein, taking a sequence of ruthenium phosphides (including Ru2P, RuP and RuP2) as model catalysts, we establish a volcanic-relation between P-proportion and alkaline hydrogen oxidation reaction (HOR) activity. The dominant role of P for regulating hydroxyl binding energy is validated by active sites poisoning experiments, pH-dependent infection-point behavior, in situ surface enhanced infrared absorption spectroscopy, and density functional theory calculations, in which P could tailor the d-band structure of Ru, optimize the hydroxyl adsorption sites across the Ru-P moieties, thereby leading to improved proportion of strongly hydrogen-bonded water and facilitated proton-coupled electron transfer process, which are responsible for the enhanced alkaline HOR performance.

The Role of Phosphorus on Alkaline Hydrogen Oxidation Electrocatalysis for Ruthenium Phosphides

Transition metal/p‐block compounds are regarded as the most essential materials for electrochemical energy converting systems involving various electrocatalysis. Understanding the role of p‐block element on the interaction of key intermediates and interfacial water molecule orientation at the polarized catalyst‐electrolyte interface during the electrocatalysis is important for rational designing advanced p‐block modified metal electrocatalysts. Herein, taking a sequence of ruthenium phosphides (including Ru2P, RuP and RuP2) as model catalysts, we establish a volcanic‐relation between P‐proportion and alkaline hydrogen oxidation reaction (HOR) activity. The dominant role of P for regulating hydroxyl binding energy is validated by active sites poisoning experiments, pH‐dependent infection‐point behavior, in situ surface enhanced absorption spectroscopy, and density functional theory calculations, in which P could tailor the d‐band structure of Ru, optimize the hydroxyl adsorption sites across the Ru‐P moieties, thereby leading to improved proportion of strongly hydrogen‐bonded water and facilitated proton‐coupled electron transfer process, which are responsible for the enhanced alkaline HOR performance.

Immobilizing Ordered Oxophilic Indium Sites on Platinum Enabling Efficient Hydrogen Oxidation in Alkaline Electrolyte.

Addressing the sluggish kinetics in the alkaline hydrogen oxidation reaction (HOR) is a pivotal yet challenging step toward the commercialization of anion-exchange membrane fuel cells (AEMFCs). Here, we have successfully immobilized indium (In) atoms in an orderly fashion into platinum (Pt) nanoparticles supported by reduced graphene oxide (denoted as O-Pt3In/rGO), significantly enhancing alkaline HOR kinetics. We have revealed that the ordered atomic matrix enables uniform and optimized hydrogen binding energy (HBE), hydroxyl binding energy (OHBE), and carbon monoxide binding energy (COBE) across the catalyst. With a mass activity of 2.3066 A mg-1 at an overpotential of 50 mV, over 10 times greater than that of Pt/C, the catalyst also demonstrates admirable CO resistance and stability. Importantly, the AEMFC implementing this catalyst as the anode catalyst has achieved an impressive power output compared to Pt/C. This work not only highlights the significance of constructing ordered oxophilic sites for alkaline HOR but also sheds light on the design of well-structured catalysts for energy conversion.

Behaviour of Pt10-xRux/C catalysts towards the hydrogen oxidation reaction in acidic medium in the presence of adsorbed CO

Pt10-xRux/C materials are synthesised using a classical polyol method and comprehensively characterised by thermogravimetric analysis, inductively coupled plasma – optical emission spectroscopy, electron transmission microscopy and x-ray diffraction. In N2-saturated electrolyte, the PtRu/C catalysts display lower onset potentials for adsorbed CO (COads) removal than the pure Pt/C one. Although the surface coverages of Pt by Ru are high, the PtRu/C catalysts display higher activity than the Pt/C one towards the hydrogen oxidation reaction (HOR), but the same mechanism occurs on all the catalysts. However, when the surface of the catalysts is saturated by COads, the HOR starts at a lower potential on Pt/C than on PtRu/C; Pt/C displays higher activity toward the HOR in the presence of COads between 0.40 and 0.55 V vs RHE. On Pt/C, a small part of COads desorbs into CO2 from 0.40 V through an Eley-Rideal mechanism, freeing very active Pt sites for the HOR. For potentials higher than 0.55 V vs RHE, the PtRu/C catalysts display higher activity for COads removal through the bifunctional mechanism. Ru atoms also block the most active Pt sites for the COads removal and the HOR.

Unconventional hcp/fcc Nickel Heteronanocrystal with Asymmetric Convex Sites Boosts Hydrogen Oxidation

Developing non‐platinum group metal catalysts for the sluggish hydrogen oxidation reaction (HOR) is critical for alkaline fuel cells. To date, Ni‐based materials are the most promising candidates but still suffer from insufficient performance. Herein, we report an unconventional hcp/fcc Ni (u‐hcp/fcc Ni) heteronanocrystal with multiple epitaxial hcp/fcc heterointerfaces and coherent twin boundaries, generating rugged surfaces with plenty of asymmetric convex sites. Systematic analyses discover that such convex sites enable the adsorption of *H in unusual bridge positions with weakened binding energy, circumventing the over‐strong *H adsorption on traditional hollow positions, and simultaneously stabilizing interfacial *H2O. It thus synergistically optimizes the HOR thermodynamic process as well as reduces the kinetic barrier of the rate‐determining Volmer step. Consequently, the developed u‐hcp/fcc Ni exhibits the top‐rank alkaline HOR activity with a mass activity of 40.6 mA mgNi‐1 (6.3 times higher than fcc Ni control) together with superior stability and high CO‐tolerance. These results provide a paradigm for designing high‐performance catalysts by shifting the adsorption state of intermediates through configuring surface sites.

Fuel starvation in automotive PEMFC stacks: hydrogen stoichiometry and electric cell-to-cell interaction

Fuel gross starvation (FGS) in a polymer electrolyte membrane fuel cell is an error state, during which the supplied amount of fuel is insufficient to sustain the requested electrical current. A novel experimental technique was developed to intentionally provoke well-controlled fuel starvation situations of one single cell in a multi-cell fuel cell stack. This modification was implemented in a 20 cell stack of automotive-sized cell geometry and carbon composite bipolar plates (BP). The intentional fuel starvation situation was analyzed using a printed circuit board to measure the current density distribution (CDD) in addition to a multipoint cell voltage monitoring (CVM) to measure local cell voltages. The provoked detrimental subsidiary reactions of the anode were found to take place spatially separated from the normal hydrogen oxidation reaction. It was therefore possible to determine and intentionally vary the hydrogen stoichiometry of the fuel starved cell. This error state caused intense distortions of the starved cells CDD and local cell voltages. The maximum difference obtained between outlet and inlet voltage of the modified cell was 1.4 V. Compared to the average current density, a more than 4-times higher maximum local current density was measured in the affected cell. Adjacent cells were also affected via electric cell-to-cell interaction. Characteristic patterns therefore became visible in the cell voltage distribution, measured by the inlet and outlet CVM. The use of carbon composite BP is favoring the occurrence of these patterns due to their relatively high electric sheet resistance. Using the new hardware setup, we could investigate the relation between the hydrogen stoichiometry of the affected cell during FGS and the observed irregular redistribution of current density and local cell voltages.

Synergistic coupling of defective Ru nanoclusters with oxygen-ligand-steered Ru single-atoms modifying interfacial water structure and key intermediates bonding toward efficient hydrogen energy conversion

Constructing highly efficient ruthenium (Ru)-based electrocatalysts and understanding their reaction mechanisms for hydrogen energy conversion are highly desirable, but extremely challenge. Herein, we integrate the well-dispersed defective Ru nanoclusters and oxygen-coordinated Ru single atoms into one electrocatalyst (RuSA-O4/RuNC) toward alkaline hydrogen oxidation and evolution reactions (HOR/HER). Synergistic catalytic mechanism of dual-sites has been revealed by in situ ATR-SEIRAS characterization, EDTA/SCN– poisoning experiments and DFT calculations. Benefiting from the electronic redistribution between RuSA-O4 and RuNC sites, the single-atom RuSA-O4 species can act as Lewis acid sites that display strong affinity toward interfacial water via an O-down (H2O↓) conformation and subsequently promote water dissociation/formation as well as hydroxide adsorption. Meanwhile, adjacent defective Ru sites have around thermoneutral value of H adsorption free energy. RuNC works with RuSA-O4 species, collaboratively reducing reaction barriers. As expected, the RuSA-O4/RuNC achieves 20.3 times mass activity of commercial Pt/C for alkaline HOR at 10 mV overpotential and excellent alkaline HER activity with a low overpotential of 22 mV to deliver 10 mA cm−2, as well as considerable HER mass activity of 17.0-times compared to commercial Pt/C at 50 mV overpotential. Besides, the synergistic dual-sites strategy can also be extended to prepare efficient PtSA-O4/PtNC and IrSA-O4/IrNC electrocatalysts.

Electrochemical behaviour of redox-robust electrode in contact with protonic electrolyte: Case of double-layered Sr2Fe1.5Mo0.5O6-δ - Ce0.8Sm0.2O2-δ composite

Electrochemical devices based on proton-conducting oxides offer a significant potential for implementation in a variety of high-temperature electrochemical applications. It is a well-known fact that electrochemical devices require active electrodes to function optimally. Over the last few years, Sr2Fe1.5Mo0.5O6-δ has received much attention as an effective redox-robust electrode for oxygen conducting electrolytes. This study presents, for the first time, the results of investigations on a double-layered composite electrode based on Sr2Fe1.5Mo0.5O6-δ in contact with a barium-free proton-conducting electrolyte La0.9Sr0.1ScO3-δ. It was found that the investigated electrode exhibits low polarization resistance about 0.15 and 0.22 Ohm cm2 in wet air and wet hydrogen at 600 °C, respectively. In addition, the electrode exhibits acceptable redox stability and CO2 tolerance. Also, the results of electrochemical impedance spectra analysis and a discussion on the parallel pathways of hydrogen oxidation and oxygen reduction reactions and the nature of rate-determining steps are presented in the manuscript. The obtained results show the high prospects for a Sr2Fe1.5Mo0.5O6-δ - based composite electrode for protonic ceramic electrochemical cells.

Unraveling Stoichiometry Effect in Nickel‐Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes

AbstractAnion‐exchange membrane fuel cells provide the possibility to use platinum group metal‐free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel‐tungsten (Ni−W) alloy catalysts, we show that the Ni : W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen‐bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state‐of‐the‐art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next‐generation catalysts for fuel cells.

Unraveling Stoichiometry Effect in Nickel-Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes.

Anion-exchange membrane fuel cells provide the possibility to use platinum group metal-free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel-tungsten (Ni-W) alloy catalysts, we show that the Ni : W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen-bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state-of-the-art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next-generation catalysts for fuel cells.

Phase manipulating toward Ni catalysts via lattice nitrogen endows high energy density hydrogen gas battery

Metastable structures commonly generate unique catalytic effects. However, it is challenging to prepare due to thermodynamic limitations. Here, we first propose a nitrogen insertion strategy for Ni phase manipulating in alkaline hydrogen oxidation reaction (HOR). With the incremental lattice nitrogen, face centered cubic (fcc), bi-mixed fcc and N-induced an unconventional hexagonal close packed (N-u-hcp), tri-mixed fcc-Ni/N-u-hcp-Ni/Ni3N and Ni3N phase evolves successively, with corresponding volcanic HOR activities. Specifically, the biphasic fcc-Ni/N-u-hcp-Ni shows highest activity of 67 A g−1. Theoretical calculations show that lattice nitrogen reduce the formation energy of biphasic Ni, and this biphasic structure could provide electron rich interface to optimize the adsorption of H* and OH*. As a proof-of-concept for Ni-H2 battery, the gas diffusion electrode prepared with this biphasic Ni catalyst achieves an 8 Ah Ni-H2 battery with 163 Wh kg−1. This study provides an inspiration for the controllable synthesis of metastable nano-catalysts and demonstrates the efficient catalysis in practical hydrogen energy applications.

Iridium-Based Alkaline Hydrogen Oxidation Reaction Electrocatalysts.

The hydroxide exchange membrane fuel cells (HEMFCs) are promising but lack of high-performance anode hydrogen oxidation reaction (HOR) electrocatalysts. The platinum group metals (PGMs) have the HOR activity in alkaline medium two to three orders of magnitude lower than those in acid, leading to the high required PGMs amount on anode to achieve high HEMFC performance. The mechanism study demonstrates the hydrogen binding energy of the catalyst determines the alkaline HOR kinetics, and the adsorbed OH and water on the catalyst surface promotes HOR. Iridium (Ir) has a unique advantage for alkaline HOR due to its similar hydrogen binding energy to Pt and enhanced adsorption of OH. However, the HOR activity of Ir/C is still unsatisfied in practical HEMFC applications. Further fine tuning the adsorption of the intermediate on Ir-based catalysts is of great significance to improve their alkaline HOR activity, which can be reasonably realized by structure design and composition regulation. In this concept, we address the current understanding about the alkaline HOR mechanism and summarize recent advances of Ir-based electrocatalysts with enhanced alkaline HOR activity. We also discuss the perspectives and challenges on Ir-based electrocatalysts in the future.