Optimized hierarchical nickel sulfide as a highly active bifunctional catalyst for overall water splitting

Rational design of non-noble metal electrocatalysts with high intrinsic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is extremely impressive for sustainable electrocatalytic water splitting systems. However, it still remains a major challenge to engineer bifunctional performance. Here, we put forward a highly efficient water electrolyzer based on Ni3S2-based materials. The hierarchical structure of Ni3S2 can be well regulated for optimizing the HER catalytic activity. The best c-Ni3S2/NF electrode exhibits a much smaller overpotential of 220 mV to reach the current density of 100 mA cm(-2). Upon introducing Fe species onto the Ni3S2/NF electrode by a simple dipping/drying method, the intrinsic OER activity can be extremely improved. As a result, the Fe-c-Ni3S2/NF catalyst showed excellent catalytic activity for the OER, including an overpotential of 193 mV at 10 mA cm(-2), high specific current density and excellent stability. Post-characterization studies proved that the remaining S anions have an effective influence on improving the OER intrinsic activity. The assembled water electrolyzer also presented superior performance, such as a very low cell voltage of 1.50 V at 10 mA cm(-2) and excellent durability for 120 h in alkaline medium. This strategy provides a promising way to design highly active and low-cost materials for overall water electrolysis.

Amorphous Cobalt Vanadium Oxide as a Highly Active Electrocatalyst for Oxygen Evolution

Xile Hu, Laurent Liardet

The water-splitting reaction provides a promising mechanism to store renewable energies in the form of hydrogen fuel. The oxidation half-reaction, the oxygen evolution reaction (OER), is a complex four-electron process that constitutes an efficiency bottleneck in water splitting. Here we report a highly active OER catalyst, cobalt vanadium oxide. The catalyst is designed on the basis of a volcano plot of metal–OH bond strength and activity. The catalyst can be synthesized by a facile hydrothermal route. The most active pure-phase material (a-CoVOx) is X-ray amorphous and provides a 10 mA cm–2 current density at an overpotential of 347 mV in 1 M KOH electrolyte when immobilized on a flat substrate. The synthetic method can also be applied to coat a high-surface-area substrate such as nickel foam. On this three-dimensional substrate, the a-CoVOx catalyst is highly active, reaching 10 mA cm–2 at 254 mV overpotential, with a Tafel slope of only 35 mV dec–1. This work demonstrates a-CoVOx as a promising electrocatalyst for oxygen evolution and validates M–OH bond strength as a practical descriptor in OER catalysis.

2018

Nanostructured Electrocatalysts for Water Splitting Reactions

Lucas-Alexandre Stern

At the dawn of the 21st century, mankind is facing an important energy challenge. Future energy demand can only be met by large scale exploitation of renewable energy resources. Solar energy is abundant, with a sufficient capacity for the growing energy demand. However, it is necessary to implement renewable energy storage means. Hydrogen is considered as the energy carrier of the future. An energy economy based on hydrogen is viable only if hydrogen is produced from sustainable means. Water electrolysis is the most promising technique to produce hydrogen directly from water. Yet, the efficiency is limited and electrocatalysts are required to drive both the hydrogen evolution reaction and oxygen evolution reaction. Scarce and expensive materials are currently used to drive these reactions. It is, thus, imperative that efficient Earth-abundant catalysts are developed. Nanostructuring enhances the performance of inexpensive materials for water splitting and several catalysts were studied for this goal. Chapter 2 describes the application of nanostructuring technique to the archetypical catalysts that are nickel oxides for oxygen evolution. The prepared nanoparticles show superior activity towards oxygen evolution than that of their bulk counterpart. The ultrafine size of nanoparticles synthesized allowed the exposure of a higher number of active sites. The activity for oxygen evolution was, thus, significantly enhanced. We also detailed that short conditioning of the electrode improved the performance of the evaluated materials. In chapter 3 we carefully studied nanoparticles and nanowires of nickel phosphide. The catalysts is known to be really active for hydrogen evolution. Our group suspected that this material was, also, a potential oxygen evolution catalyst. We proved, for the first time, that nickel phosphide is a remarkable oxygen evolution catalyst. Under alkaline conditions, used for oxygen evolution, we observed an in-situ formation of a core-shell heterostructure, a typical nanostructure architecture. The surface oxidation of this material allowed high oxygen evolution capabilities. We concluded that careful oxidation of nanostructured materials, as observed for nickel phosphide, is essential for the preparation of future outstanding oxygen evolution catalysts. Chapter 4 details the fabrication of direct solar-to-fuel electrode using cobalt phosphide as hydrogen evolving catalyst. Instead of using the electrical energy provided by solar energy, solar irradiation on the developed assembly allows direct hydrogen production. The careful design of the light-sensitive electrode (photocathode) is detailed. Simple incorporation of cobalt phosphide by means of photodeposition alleviates the cost of the electrode fabrication. The assembled electrode is active for hydrogen evolution under visible light irradiation. In the chapter 5 we sought to fabricate a 3-dimensional hydrogen evolving catalyst. This nanostructure is based on polymer brushes on a flat conducting substrate. Once the brushes are grown on the substrate, a molybdenum sulfide catalyst is then incorporated by simple soaking technique. We were able to tune the loading of the catalyst and the corresponding activity by changing the polymer properties. The height of the polymer was modified as well as its packing density. The resulting activity proved superior to similar approaches and to previous reports on carefully engineered molybdenum sulfide catalysts.

EPFL2017

Ni2P as a Janus catalyst for water splitting: the oxygen evolution activity of Ni2P nanoparticles

Ligang Feng, Xile Hu, Fang Song, Lucas-Alexandre Stern

Electrochemical water splitting into hydrogen and oxygen is a promising method for solar energy storage. The development of efficient electrocatalysts for water splitting has drawn much attention. However, catalysts that are active for both the hydrogen evolution and oxygen evolution reactions are rare. Herein, we show for the first time that nickel phosphide (Ni2P), an excellent hydrogen evolving catalyst, is also highly active for oxygen evolution. A current density of 10 mA cm(-2) is generated at an overpotential of only 290mV in 1M KOH. The high activity is attributed to the core-shell (Ni2P/NiOx) structure that the material adopts under catalytic conditions. The Ni2P nanoparticles can serve as both cathode and anode catalysts for an alkaline electrolyzer, which generates 10 mA cm(-2) at 1.63 V.

Royal Society of Chemistry2015

Nanostructured Electrocatalysts for Water Splitting Reactions

Lucas-Alexandre Stern

EPFL2017