Micro-pyrolysis perturbation promotes electrocatalytic activity of tetranuclear nickel clusters

As for the preparation of efficient and stable electrocatalysts containing transition metal heteroatoms by high-temperature pyrolysis is intriguing. However, studies on the pyrolysis of complexes in low-temperature range to obtain efficient catalytic transport platforms are rare. Herein, we propose a micro-pyrolysis perturbation strategy in constructing nickel molecular cluster-based bifunctional electrocatalysts, derived from a case of the tetranuclear Schiff-based nickel molecular cluster Ni 4 (Ni 4 (II)C 46 H 68 N 4 O 18 ) with N, O coordination mode. The crystal structure undergoes mild decomposition of peripheral ligands during the pyrolysis process are revealed by in situ Thermogravimetry-mass spectrometry (TG-MS) and ex-situ synchrotron-based X-ray absorption spectroscopy (XAS) technology. Besides, nickel molecular clusters transform into amorphous materials with metal-centered active Ni-O exposed on the surface under micro-pyrolysis perturbation providing additional active sites. The bifunctional catalyst Ni 4 -350 displays a low overpotential of 247 mV for the OER, and 1.366 V for the UOR at 10 mA·cm −2, which is also stable in the alkaline medium for 10 h of continuous running. This model study highlights that the micro-pyrolysis perturbation strategy can provide stable highly active centres while retaining the host structural framework in Ni-based clusters with promising potential application in low-potential OER/UOR electrocatalysts.