Enhanced Hydrogen Evolution Performance of Ni−Mo-Based Electrocatalysts in Seawater by Controlling Surface Wettability

Abstract

Environmental pollution and global warming have become enormous problems all over the world. At the United Nations Climate Change Conference, carbon neutrality was proposed as a way to solve this problem through the Paris Agreement in 2015. To achieve zero net carbon dioxide emissions, research on how to obtain energy from renewable energy resources has been intensively conducted. Among various candidates of renewable chemical fuels, green H2, produced by water electrolysis is considered as one of the promising, next generation chemical fuels.Almost 97% of earth’s water resources exist as seawater. Moreover, seawater has an advantage that it can be used as an electrolyte owing to the various ions, existing naturally. Therefore, one of the ultimate goals in green H2 generation is to directly utilize seawater as the electrolyte source.Although Pt-group materials (PGMs) are well known catalysts in hydrogen evolution reaction (HER) but one of the main challenges for wide commercialization with PGMs is its high cost and scarcity. In order to overcome this issue, research on HER catalysts using non-PGM (NPGM) has been intensively performed. Among various NPGM elements, Ni−Mo has great potential for electrocatalysts in HER owing to its cost effectiveness as well as their high electrocatalytic activities in wide pH range of electrolytes. It is well known that not only the electrocatalytic activity in HER, mainly originating from chemical compositions at the surface, but also the physical surface properties, especially the surface wettability, play an important role to regulate the electrocatalytic performance. The evolved bubbles by the HER form the solid−gas−liquid interfaces, which results in the turn-off of the active sites toward electrochemical reactions until the gas bubbles remove from the electrocatalytic surface. Previous studies reveal that this dynamic, evolutionary behavior of surface active sites by the bubble growth/departure significantly influence the electrocatalytic performance.Herein, we demonstrate the Ni−Mo-based material as the electrocatalyst toward HER in simulated seawater, which is 0.5 M phosphate buffer with 0.6 M NaCl. The electrocatalytic layers are deposited by simple electrodeposition with the aminated graphene oxide (aGO) to form composites (aGO/NiMo). The addition of aGO in Ni−Mo does not influence the electrocatalytic activity in HER, exhibiting nearly the same cyclic voltammograms with pure NiMo. Interestingly, the long-term performance of aGO/NiMo, however, is observed when compared to the pure NiMo. The enhanced durability by chronopotentiometric measurements in the aGO/NiMo is ascribed to the improved surface wettability, originating from added aGO. The images taken by high-speed camera clearly show that the H2 bubbles with smaller sizes at the surface of aGO/NiMo but much larger density than the ones at pure NiMo are observed. These phenomena denotes that the regeneration rate of active sites by bubbles departure from the surface is much higher in the aGO/NiMo than NiMo without aGO, indicating that the aGO is beneficial for improving the surface wettability. The longer residence of H2 bubbles at the pure NiMo increases the actual overpotential applied in the single active site under constant current density, leading to the faster degradation of electrocatalytic activity in HER. The physical properties of surface between aGO/NiMo and NiMo for surface wettability is also supported by surface roughness measurements in atomic force microscope and contact angles. Our study contributes to the fundamental design of the physical properties of electrocatalytic surfaces physical properties, thereby simply improving the electrochemical performance in HER.