Seawater is one of the most abundant natural resources on our planet. Electrolysis of seawater is not only a promising approach to produce clean hydrogen energy, but also of great significance to seawater desalination. The implementation of seawater electrolysis requires robust and efficient electrocatalysts that can sustain seawater splitting without chloride corrosion, especially for the anode. Here we report a three-dimensional core-shell metal-nitride catalyst consisting of NiFeN nanoparticles uniformly decorated on NiMoN nanorods supported on Ni foam, which serves as an eminently active and durable oxygen evolution reaction catalyst for alkaline seawater electrolysis. Combined with an efficient hydrogen evolution reaction catalyst of NiMoN nanorods, we have achieved the industrially required current densities of 500 and 1000 mA cm−2 at record low voltages of 1.608 and 1.709 V, respectively, for overall alkaline seawater splitting at 60 °C. This discovery significantly advances the development of seawater electrolysis for large-scale hydrogen production. Seawater electrolysis is a promising approach to produce hydrogen fuel and is also of great significance to seawater desalination. Here, the authors prepare 3D core-shell metal-nitride catalysts from earth-abundant elements for high-performance alkaline seawater electrolysis.

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Non-noble metal-nitride based electrocatalysts for high-performance alkaline seawater electrolysis

Hydrogen economy has emerged as a very promising alternative to the current hydrocarbon economy, which involves the process of harvesting renewable energy to split water into hydrogen and oxygen and then further utilization of clean hydrogen fuel. The production of hydrogen by water electrolysis is an essential prerequisite of the hydrogen economy with zero carbon emission. Among various water electrolysis technologies, alkaline water splitting has been commercialized for more than 100 years, representing the most mature and economic technology. Here, the historic development of water electrolysis is overviewed, and several critical electrochemical parameters are discussed. After that, advanced nonprecious metal electrocatalysts that emerged recently for negotiating the alkaline oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are discussed, including transition metal oxides, (oxy)hydroxides, chalcogenides, phosphides, and nitrides for the OER, as well as transition metal alloys, chalcogenides, phosphides, and carbides for the HER. In this section, particular attention is paid to the catalyst synthesis, activity and stability challenges, performance improvement, and industry-relevant developments. Some recent works about scaled-up catalyst synthesis, novel electrode designs, and alkaline seawater electrolysis are also spotlighted. Finally, an outlook on future challenges and opportunities for alkaline water splitting is offered, and potential future directions are speculated.

Clean and Affordable Hydrogen Fuel from Alkaline Water Splitting: Past, Recent Progress, and Future Prospects.

Developing energy- and time-saving methods to synthesize active and stable oxygen evolving catalysts is of great significance to hydrogen production from water electrolysis, which however remains a grand challenge. Here we report a one-step approach to grow highly porous S-doped Ni/Fe (oxy)hydroxide catalysts on Ni foam in several minutes under room temperature. This ultrafast method effectively engineers the surface of Ni foam into a rough S-doped Ni/Fe (oxy)hydroxide layer, which has multiple levels of porosity and good hydrophilic features and exhibits extraordinary oxygen evolution reaction (OER) performance in both alkaline salty water and seawater electrolytes. Specifically, the S-doped Ni/Fe (oxy)hydroxide catalyst requires low overpotentials of 300 and 398 mV to deliver current densities of 100 and 500 mA cm−2, respectively, when directly used as an OER catalyst in alkaline natural seawater electrolyte. Using this OER catalyst together with an efficient hydrogen evolution reaction catalyst, we have achieved the commercially demanded current densities of 500 and 1000 mA cm−2 at low voltages of 1.837 and 1.951 V, respectively, for overall alkaline seawater electrolysis at room temperature with very good durability. This work affords a cost-efficient surface engineering method to steer commercial Ni foam into robust OER catalysts for seawater electrolysis, which has important implications for both the hydrogen economy and environmental remediation.

Ultrafast room-temperature synthesis of porous S-doped Ni/Fe (oxy)hydroxide electrodes for oxygen evolution catalysis in seawater splitting

Heterogeneous Bimetallic Phosphide Ni2P-Fe2P as an Efficient Bifunctional Catalyst for Water/Seawater Splitting

Electrocatalytic oxygen evolution reaction (OER) is a core reaction responsible for converting renewable electricity into storable fuels; yet, it is kinetically challenging, because of the complex ...

Fe-Based Electrocatalysts for Oxygen Evolution Reaction: Progress and Perspectives

Electrolysis of water to generate hydrogen fuel is an attractive renewable energy storage technology. However, grid-scale freshwater electrolysis would put a heavy strain on vital water resources. Developing cheap electrocatalysts and electrodes that can sustain seawater splitting without chloride corrosion could address the water scarcity issue. Here we present a multilayer anode consisting of a nickel–iron hydroxide (NiFe) electrocatalyst layer uniformly coated on a nickel sulfide (NiSx) layer formed on porous Ni foam (NiFe/NiSx-Ni), affording superior catalytic activity and corrosion resistance in solar-driven alkaline seawater electrolysis operating at industrially required current densities (0.4 to 1 A/cm2) over 1,000 h. A continuous, highly oxygen evolution reaction-active NiFe electrocatalyst layer drawing anodic currents toward water oxidation and an in situ-generated polyatomic sulfate and carbonate-rich passivating layers formed in the anode are responsible for chloride repelling and superior corrosion resistance of the salty-water-splitting anode.

https://www.pnas.org/content/pnas/116/14/6624.full.pdf

Lei Wang

Papers

Solar-driven, highly sustained splitting of seawater into hydrogen and oxygen fuels