Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.

Noble metal-free hydrogen evolution catalysts for water splitting

A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.

Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions

Energy density is the main property of rechargeable batteries that has driven the entire technology forward in past decades. Lithium-ion batteries (LIBs) now surpass other, previously competitive battery types (for example, lead–acid and nickel metal hydride) but still require extensive further improvement to, in particular, extend the operation hours of mobile IT devices and the driving mileages of all-electric vehicles. In this Review, we present a critical overview of a wide range of post-LIB materials and systems that could have a pivotal role in meeting such demands. We divide battery systems into two categories: near-term and long-term technologies. To provide a realistic and balanced perspective, we describe the operating principles and remaining issues of each post-LIB technology, and also evaluate these materials under commercial cell configurations. Post-lithium-ion batteries are reviewed with a focus on their operating principles, advantages and the challenges that they face. The volumetric energy density of each battery is examined using a commercial pouch-cell configuration to evaluate its practical significance and identify appropriate research directions.

Promise and reality of post-lithium-ion batteries with high energy densities

A co-doped carbon material, methods of making such materials, and electrochemical cells and devices comprising such materials are provided. The co-doped carbon material comprises a mesoporous carbon material doped with nitrogen and phoshporous (NPMC). The present NPMC exhibit catalytic activity for both oxygen reduction reaction and oxygen evolution reaction and may be useful as an electrode in an electrochemical cell and particularly as part of a battery. The present NPMC materials may be used as electrodes in primary zinc-air batteries and in rechargeable zinc-air batteries and many other energy systems.

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Metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions

Fe plays a critical, but not yet understood, role in enhancing the activity of the Ni-based oxygen evolution reaction (OER) electrocatalysts. We report electrochemical, in situ electrical, photoelectron spectroscopy, and X-ray diffraction measurements on Ni1–xFex(OH)2/Ni1–xFexOOH thin films to investigate the changes in electronic properties, OER activity, and structure as a result of Fe inclusion. We developed a simple method for purification of KOH electrolyte that uses precipitated bulk Ni(OH)2 to absorb Fe impurities. Cyclic voltammetry on rigorously Fe-free Ni(OH)2/NiOOH reveals new Ni redox features and no significant OER current until >400 mV overpotential, different from previous reports which were likely affected by Fe impurities. We show through controlled crystallization that β-NiOOH is less active for OER than the disordered γ-NiOOH starting material and that previous reports of increased activity for β-NiOOH are due to incorporation of Fe-impurities during the crystallization process. Through...

Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation

Metal-air batteries are promising for energy storage because of their high theoretical energy density, but their realization is hampered by the lack of efficient and robust air catalysts. Li et al. construct stable zinc-air batteries using novel catalysts for oxygen reduction and evolution reactions.

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Advanced zinc-air batteries based on high-performance hybrid electrocatalysts

Silicon’s sensitivity to corrosion has hindered its use in photoanode applications. We found that deposition of a ~2-nanometer nickel film on n-type silicon (n-Si) with its native oxide affords a high-performance metal-insulator-semiconductor photoanode for photoelectrochemical (PEC) water oxidation in both aqueous potassium hydroxide (KOH, pH = 14) and aqueous borate buffer (pH = 9.5) solutions. The Ni film acted as a surface protection layer against corrosion and as a nonprecious metal electrocatalyst for oxygen evolution. In 1 M aqueous KOH, the Ni/n-Si photoanodes exhibited high PEC activity with a low onset potential (~1.07 volts versus reversible hydrogen electrode), high photocurrent density, and durability. The electrode showed no sign of decay after ~80 hours of continuous PEC water oxidation in a mixed lithium borate–potassium borate electrolyte. The high photovoltage was attributed to a high built-in potential in a metal-insulator-semiconductor–like device with an ultrathin, incomplete screening Ni/NiO x layer from the electrolyte.

http://science.sciencemag.org/content/sci/342/6160/836.full.pdf

High-Performance Silicon Photoanodes Passivated with Ultrathin Nickel Films for Water Oxidation

High-performance, low-cost, safe and environmentally friendly batteries are important for portable electronics and electric vehicles. Here, we synthesized NiAlCo-layered double hydroxide (LDH) nanoplates attached to few-walled carbon nanotubes (NiAlCo LDH/CNT) as the cathode material of a rechargeable NiZn battery in aqueous alkaline electrolytes. The α-phase nickel hydroxide with ultrathin morphology and strong coupling to nanotubes afforded a cathode with a high capacity of ∼354 mA h g−1 and ∼278 mA h g−1 at current densities of 6.7 A g−1 and 66.7 A g−1, respectively. Al and Co co-doping is unique for stabilizing α-phase nickel hydroxide with only a small capacity loss of ∼6% over 2000 charge and discharge cycles at 66.7 A g−1. Rechargeable ultrafast NiZn batteries with NiAlCo LDH/CNT cathode and a zinc anode can deliver a cell voltage of ∼1.75 V, energy density of ∼274 W h kg−1 and power density of ∼16 kW kg−1 (based on active materials) with a charging time of <1 minute. The results open the possibility of ultrafast and safe batteries with high energy density.

Ultrafast high-capacity NiZn battery with NiAlCo-layered double hydroxide

Manganese oxides are cost-effective and green materials with rich electrochemical properties. Continuous research efforts have been undertaken to obtain MnO
 x
 materials with improved activity and stability for catalyzing the oxygen reduction reaction (ORR). Here, we have developed a novel ORR catalyst by nucleation and growth of Mn3O4 nanoparticles on graphene oxide (GO) sheets interconnected by electrically conducting multi-walled carbon nanotubes (MWCNTs). X-ray near edge absorption structure (XANES) spectroscopy revealed the partially reduced nature of GO and strong chemical coupling between the nanoparticles and the GO sheets. Incorporation of MWCNTs was found to improve the activity and stability of the hybrid by imparting higher conductivity to the hybrid material. Furthermore, surface oxidation of the manganese oxide nanoparticles through a calcination step was found to increase the density of ORR active sites. The strongly coupled and electrically interconnected Mn3O4/nanocarbon (Mn3O4/Nano-C) hybrid is one of the most active and stable manganese oxide-based ORR catalysts and shows promise for electrochemical energy conversion applications.

Engineering manganese oxide/nanocarbon hybrid materials for oxygen reduction electrocatalysis

Next-generation catalysts for water splitting are crucial towards a renewable hydrogen economy. MoS2 and WS2 represent earth-abundant, noble metal cathode alternatives with high catalytic activity at edge sites. One challenge in their development is to nanostructure these materials in order to achieve increased performance through the creation of additional edge sites. In this work, we demonstrate a simple route to form nanostructured-WS2 using sonochemical exfoliation to break interlayer and intralayer bonds in WS2 nanotubes. The resulting few-layer nanoflakes are ∼100 nm wide with a high density of edge sites. WS2 nanoflakes are utilized as cathodes for the hydrogen evolution reaction (HER) and exhibit superior performance to WS2 nanotubes and bulk particles, with a lower onset potential, shallower Tafel slope and increased current density. Future work may employ ultra-small nanoflakes, dopant atoms, or graphene hybrids to further improve electrocatalytic activity. 
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Ju Feng

Papers

Advanced zinc-air batteries based on high-performance hybrid electrocatalysts

High-Performance Silicon Photoanodes Passivated with Ultrathin Nickel Films for Water Oxidation

Ultrafast high-capacity NiZn battery with NiAlCo-layered double hydroxide

Engineering manganese oxide/nanocarbon hybrid materials for oxygen reduction electrocatalysis

WS2 nanoflakes from nanotubes for electrocatalysis