Observation of O₂ Molecules Inserting intoFe–H Bonds in a Ferrous Metal–Organic Framework

Exploring the interactions between oxygen molecules and metal sites has been a significant topic. Most previous studies concentrated on enzyme-mimicking metal sites interacting with O₂ to form M–OO species, leaving the development of new types of O₂-activating metal sites and novel adsorption mechanisms largely overlooked. In this study, we reported an Fe(II)-doped metal–organic framework (MOF) [Fe₃Zn₂H₄(bibtz)₃] (<b>MAF-203</b>, H₂bibtz = 1<i>H</i>,1’<i>H</i>-5,5′-bibenzo[<i>d</i>][1,2,3]triazole), featuring an unprecedented tetrahedral Fe(II)HN₃ site. This MOF exhibits selective adsorption behavior for O₂ from air, achieving an O₂/N₂ separation selectivity of up to 67.1. Breakthrough experiments confirmed that <b>MAF-203</b> can effectively capture O₂ from the air even under a high relative humidity of 60%. X-ray absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectra, and ab initio molecular dynamics simulations were utilized to monitor the O₂ loading process on the Fe(II)HN₃ site. Interestingly, O₂ molecules could insert into the Fe–H bonds of the tetrahedral Fe^IIHN₃ sites, forming Fe^III–OOH species (instead of the commonly observed Fe–OO species) with an ultrahigh adsorption enthalpy of −99.2 kJ mol^–1. Consequently, the O₂ capture behavior of <b>MAF-203</b> enables efficient electrochemical 2e^– oxygen reduction for the production of H₂O₂ with air as the feedstock. Specifically, in a solid-state electrolyte electrolyzer without any liquid electrolyte, <b>MAF-203</b> achieved selective O₂ capture and continuous production of medical-grade H₂O₂ (3.2 wt %) solution without salts for 70 h, with performance comparable to that under pure O₂ conditions. The O₂ adsorption and activation mechanisms inaugurate a fresh chapter in grasping the interaction between O₂ molecules and metal sites.