Unleashing the room temperature boronization: Blooming of Ni-ZIF nanobuds for efficient photo/electro catalysis of water.

ABSTRACT

Water splitting provides an environmental-friendly and sustainable approach for generating hydrogen fuel. The inherent energetic barrier in two-core half reactions such as the Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) leads to undesired increased overpotential and constrained reaction kinetics. These challenges pose significant challenges that demand innovative solutions to overcome. One of the efficient ways to address this issue is tailoring the morphology and crystal structure of metal-organic frameworks (MOF). Nickel Zeolite Imidazolate Framework (Ni-ZIF) is a popular MOF and it can be tailored using facile chemical methods to unleash a remarkable bifunctional electro/photo catalyst. This innovative solution holds the capability to address prevailing obstacles such as inadequate electrical conductivity and limited access to active metal centers due to the influence of organic ligands. Thereby, applying boronization to the Ni-ZIF under different duration, one can induce blooming of nanobuds under room temperature and modify oxygen vacancies in order to achieve higher reaction kinetics in electro/photo catalysis. It can be evidenced by the 24-h boronized Ni-ZIF (BNZ), exhibiting lower overpotentials as electrocatalyst (OER-396 mV & HER-174 mV @ 20 mA/cm2) in 1 M KOH electrolyte and augmented gas evolution rates when employed as a photocatalyst (Hydrogen-14.37 µmol g-1min-1 & Oxygen-7.40 µmol g-1min-1). The 24-h boronization is identified as the optimum stage of crystalline to amorphous transformation which provided crystalline/amorphous boundaries as portrayed by X-Ray diffraction (XRD) and High Resolution-Transmission Electron Microscopy (HR-TEM) analysis. The flower-like transformation of 24-BNZ, characterized by crystalline-amorphous boundaries initiates with partial disruption of Ni-N bonds and formation of Ni-B bonds as evident from X-ray Photoelectron Spectroscopy (XPS). Further, the 24-h BNZ exhibit bifunctional catalytic activities with pre-longed stability. Overall, this work presents a comprehensive study of the electrocatalytic and photocatalytic water splitting properties of the tailored Ni-ZIF material.