Bifunctional Ni Foam Supported TiO2@Ni3S2 core@shell Nanorod Arrays for Boosting Electrocatalytic Biomass Upgrading and H2 Production Reactions

Abstract Replacing traditional oxygen evoltion reaction (OER) with biomass oxidation reaction (BOR) is an advantageous alternative choice to obtain green hydrogen energy from electrocatalytic water splitting. Herein, a novel of extremely homogeneous Ni 3 S 2 nanosheets covered TiO 2 nanorod arrays are in situ growth on conductive Ni foam (Ni/TiO 2 @Ni 3 S 2 ). The Ni/TiO 2 @Ni 3 S 2 electrode exhibits excellent electrocatalytic activity and long‐term stability for both BOR and hydrogen evolution reaction (HER). Especially, taking glucose as a typical biomass, the average hydrogen production rate of the HER‐glucose oxidation reaction (GOR) two‐electrode system reached 984.74 µmol h −1 , about 2.7 times higher than that of in a common HER//OER two‐electrode water splitting system (365.50 µmol h −1 ). The calculated power energy saving efficiency of the GOR//HER system is about 13% less than that of the OER//HER system. Meanwhile, the corresponding selectivity of the value‐added formic acid produced by GOR reaches about 80%. Moreover, the Ni/TiO 2 @Ni 3 S 2 electrode also exhibits excellent electrocatalytic activity on a diverse range of typical biomass intermediates, such as urea, sucrose, fructose, furfuryl alcohol (FFA), 5‐hydroxymethylfurfural (HMF), and alcohol (EtOH). These results show that Ni/TiO 2 @Ni 3 S 2 has great potential in electrocatalysis, especially in replacing OER reaction with BOR reaction and promoting the sustainable development of hydrogen production.