Controlled crystal growth orientation and surface charge effects in self-assembled nickel oxide nanoflakes and their activity for the oxygen evolution reaction

Abstract

Although sustainable hydrogen production from solar energy is a promising route for the future, the cost of the necessary photovoltaic and photoelectrochemical devices as well as a lack of detailed understanding and control of catalyst interfaces in nanomaterials with high catalytic activity are the largest impediments to commercial implementation. Here, we report how a higher catalytic efficiency can be achieved by utilizing an earth-abundant Nickel oxide (NiO) catalyst via an improved control of the crystalline growth orientation and self-assembly. The relationship between the surface charge and the morphology of the nano-catalysts is investigated using a hydrothermal method where the pH is utilized to control both the crystal growth direction and crystallization of Ni(OH)2 and eventually in NiO, where the self-assembly properties of nanoflakes (NFs) into hierarchical flower-like nickel oxide NFs depend on balancing of forces during synthesis. The surface charge of the NiO at different pH values was measured with electrophoretic dynamic light scattering (EDLS) and is known to be closely related to that of Ni(OH)2 and is here utilized to control the relative change in the surface charge in the precursor solution. By preparing NiO NFs under variation of the pH conditions of the precursor Ni(OH)2 system, the surface energies of exposed lattice planes of the growing nanostructures can be altered and an enhanced crystal growth orientation in a different direction can be controlled. Specifically, the [111] and [220] growth orientation in cubic NiO can be favored or suppressed with respect to the [200] direction.Benefiting from the large surface area provided by the mesoporous NiO NFs, the catalyst electrode exhibits high activity toward the oxygen evolution reactions in alkaline electrolyte. The NiO nanostructure synthesized at pH 10 displays oxygen evolution reaction (OER) overpotential of 0.29 V and 0.35 V versus the reversible hydrogen electrode (RHE) at 1 mA cm−2 and 10 mA cm−2 current density, respectively. This is compared to commercial NiO with more than 0.15 V additional overpotential and the same or lower overpotential compared to RuO2 and IrO2 at alkaline conditions. The results show that the OER catalytic activity can be drastically increased by a detailed control of the crystal growth orientation and the self-assembly behavior where the active surface charge around the point of zero charge during synthesis of the metal hydroxides/oxides is introduced as an important design principle for producing efficient electrocatalysts.