Aqueous Glycerol to Glyceric Acid and Green Hydrogen by Visible-Light-Driven Photocatalysis with Ni/Co(PO<sub>4</sub>)<sub>2</sub>-TiO<sub>2</sub>: Parallel Utilization of Holes and Electrons
Thazhath R. Nivedhitha, Himanshu Bajpai, Jiffin Varghese Oommen, Athira Abraham, Inderjeet Chauhan, Chinnakonda S. Gopinath
Abstract
Replacing the kinetically sluggish oxygen evolution reaction (OER) with the oxidation of an abundantly available organic molecule to value-added product(s) (VAPs) at low voltage along with the hydrogen evolution reaction (HER) is a big challenge in water splitting, either by electrolysis or sunlight-driven photocatalysis. Glycerol oxidation to a VAP is kinetically fast, compared to an OER, and offers hope to enhance sunlight-driven water splitting to hydrogen by the concurrent utilization of holes and electrons. Mixed bimetal phosphates of Co and Ni (Co x Ni y (PO 4 ) 2 (CoNiP)) with different Co:Ni ratios (10:0, 7:3, 5:5, 3:7, and 0:10) were integrated with TiO 2 to generate final photocatalyst composites ( x wt % CoNiP with TiO 2 ) and employed for concurrent photocatalytic HER and glycerol oxidation. Irrespective of the weight ratios of CoNiP and TiO 2, any TiO 2 –CoNiP composite showed better photocatalytic activity for the HER and glycerol oxidation compared to virgin TiO 2 . The highest HER as well as selectively generated glyceric acid yield was observed to be 54 and 67 mmol/g, respectively, after 25 h of reaction under 1 sun conditions with TiO 2 –CoNiP-5:5. An increase in catalytic activity can be attributed to the formation of p–n heterojunctions of the constituent component along with uniform distribution of CoNiP to effectively utilize the charge carriers for redox reactions. Highly selective oxidation of glycerol to glyceric acid (85%), along with other minor products, is also demonstrated, which offers further scope to use solar light to generate VAPs in a sustainable manner. A simple comparison of H 2 yield and all oxidized products together indicates the better utilization of holes for the latter, and hence, there is scope to increase HER and possibly the whole photocatalytic activity.