Cathodic Activation of Titania-Fly Ash Cenospheres for Efficient Electrochemical Hydrogen Production: A Proposed Solution to Treat Fly Ash Waste

Abstract

Fly ash (FA) is a waste product generated in huge amounts by coal-fired electric and steam-generating plants. As a result, the use of FA alone or in conjunction with other materials is an intriguing study topic worth exploring. Herein, we used FA waste in conjunction with titanium oxide (TiO2 ) to create (FA-TiO2 ) nanocomposites. For the first time, a cathodic polarization pre-treatment regime was applied to such nanocomposites to efficiently produce hydrogen from an alkaline solution. The FA-TiO2 hybrid nanocomposites were prepared by a straightforward solvothermal approach in which the FA raw material was mixed with titanium precursor in dimethyl sulfoxide (DMSO) and refluxed during a given time. The obtained FA-TiO2 hybrid nanocomposites were fully characterized using various tools and displayed a cenosphere-like shape. The synthesized materials were tested as electrocatalysts for the hydrogen evolution reaction (HER) in 0.1 M KOH solution in the dark, employing various electrochemical techniques. The as-prepared (unactivated) FA-TiO2 exhibited a considerable HER electrocatalytic activity, with an onset potential (EHER) value of −144 mV vs. RHE, a Tafel slope (−bc ) value of 124 mV dec−1 and an exchange current density (jo) of ~0.07 mA cm−2 . The FA-TiO2′s HER catalytic performance was significantly enhanced upon cathodic activation (24 h of chronoamperometry measurements performed at a high cathodic potential of −1.0 V vs. RHE). The cathodically activated FA-TiO2 recorded HER electrochemical kinetic parameters of EHER = −28 mV, −bc = 115 mV dec−1, jo = 0.65 mA cm−2, and an overpotential η10 = 125 mV to yield a current density of 10 mA cm−2 . Such parameters were comparable to those measured here for the commercial Pt/C under the same experimental conditions (EHER = −10 mV, −bc = 113 mV dec−1, jo = 0.88 mA cm−2, η10 = 110 mV), as well as to the most active electrocatalysts for H2 generation from aqueous alkaline electrolytes.