Colloidal Ni<sub>2</sub>P Nanocrystals Encapsulated in Heteroatom-Doped Graphene Nanosheets: A Synergy of 0D@2D Heterostructure Toward Overall Water Splitting
Umesh P. Suryawanshi, Uma V. Ghorpade, Dong Min Lee, Mingrui He, Seung Wook Shin, Priyank V. Kumar, Jun Sung Jang, Hyo Rim Jung, Mahesh P. Suryawanshi, Jin Hyeok Kim
Abstract
Transition-metal phosphide (TMP) nanostructures have been extensively studied for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, phase-controlled synthesis of colloidal Ni2P nanocrystals (NCs) or related heterostructures remains challenging and their use as bifunctional electrocatalysts in overall water splitting (OWS) is not systematically studied. Herein, zero-dimensional (0D) colloidal Ni2P NCs are synthesized using a robust solution-phase method and encapsulated in two-dimensional (2D) N- and S-doped graphene (NSG) nanosheets via facile ex situ sonication to form a 0D@2D Ni2P@NSG heterostructure. The interaction between surface functionalities of Ni2P NCs and defective NSG via strong van der Waals force provides a robust sheath to Ni2P NCs when encapsulated in NSG nanosheets, further enhancing the specific surface area and active site exposure. Density functional theory calculations indicate that the dual interaction of N and S dopants with Ni2P benefits the synergistic effect of optimized water and hydrogen free energy adsorption. As a result, Ni2P@NSG electrocatalysts manifest high catalytic activity toward HER and OER, and a two-electrode alkaline electrolyzer assembled by Ni2P@NSG as both an anode and a cathode requires only 1.572 V to reach a current density of 10 mA/cm2.