ABSTRACT
Electrocatalytic water splitting is a promising and viable technology to produce clean, sustainable, and storable hydrogen as an energy carrier. However, to meet the ever-increasing global energy demand, it is imperative to develop high-performance non-precious metal-based electrocatalysts for the oxygen evolution reaction (OER), as the OER is considered the bottleneck for electrocatalytic water splitting. Spinels, in particular, are considered promising OER electrocatalysts due to their unique properties, precise structures, and compositions. Herein, the recent progress on the application of bimetallic-based spinels (AFe2 O4 , ACo2 O4 , and AMn2 O4 ; where A = Ni, Co, Cu, Mn, and Zn) as electrocatalysts for the OER is presented. The fundamental concepts of the OER are highlighted after which the family of spinels, their general formula, and classifications are introduced. This is followed by an overview of the various classifications of bimetallic-based spinels and their recent developments and applications as OER electrocatalysts, with special emphasis on enhancing strategies that have been formulated to improve the OER performance of these spinels. In conclusion, this review summarizes all studies mentioned therein and provides the challenges and future perspectives for bimetallic-based spinel OER electrocatalysts.
ABSTRACT
Sulphur dioxide (SO2), a known industrial pollutant and pulmonary irritant, is emitted to the atmosphere in excess of 120 Mt per annum. Great strides have been taken to reduce SO2 emissions, but with the growth of specifically China, and to a lesser extent India, it is on the rise again. The electrolysis of aqueous solutions of dissolved SO2 holds huge environmental potential in that SO2 is converted to sulphuric acid (H2SO4) and at the same time hydrogen gas is produced. A further benefit or incentive is that a sulphur depolarised electrolyser (SDE) operates at an applied potential that is about one volt lower than that of a regular water electrolyser. In taking this technology forward the greatest improvement to be made is in developing a suitable electrocatalyst, which is also the 'lowest hanging fruit' in that very limited research and development has been conducted on the electrocatalyst for this process. In this work, density functional theory is employed to model the electro-oxidation of SO2 on single crystal planes of the 4d and 5d transition metals. Two reaction mechanisms are considered, a HSO3 intermediate pathway and a SO3 intermediate pathway. The binding energies of all intermediates are found to scale with the surface reactivity (measured as the adsorption of OH). Irrespective of the pathway water needs to be activated and reduction of SO2 to elemental sulphur must be avoided. This requirement alone calls for an electrode potential of at least 0.7-0.8 V for all the investigated transition metals and thus challenges the proclaimed goal to operate the SDE at 0.6 V. A high chemical barrier is further found to severely limit the oxidation reaction on reactive metals. A much higher catalytic activity can be obtained on precious metals but at the cost of running the reaction at high overpotentials.
