Ozone Decomposition on Defective Graphene: Insights from Modeling

Abstract

We propose via first-principles calculations that graphene tailored with specific structural or foreign-atom defects can be used as catalysts for O3 decomposition. Compared to the pristine graphene, we show that introduction of thermodynamically stable surface defects, that is, Stone-Wales, 555–777 divacancy or nitrogen atoms to graphene, can drastically lower the chemisorption energy barrier of O3. The ozonides once formed can evolve into epoxide or ketone-like intermediate structures on graphene, which assist in the sustainable conversion of O3 to O2. The minimal energy needed to complete the O3 decomposition cycle on different graphene substrates has the order of E555–777 (0.22 eV) < E N‑doping (0.33 eV) < E Stone‑Wales (0.61 eV) < E pristine graphene (1.08 eV). As two most promising catalysts, 555–777 divacant and N-doped graphene shows a clear adsorption selectivity to O3 under the ambient conditions. N-doped graphene outperforms 555–777 divacant graphene at the stage of physisorption in that the former catalyst separates O3 from the ambient gases by a much larger adsorption energy. These results and conclusions are a pivotal and necessary step that should stimulate both the proof-of-principle experiments and the computational search of metal-free catalysts for O3 decomposition.

Graphitized Carbon-Supported Co@Co3O4 for Ozone Decomposition over the Entire Humidity Range

“…The O–O bond length in the O 3 molecule increases to 1.42 and 1.46 Å over the Co@Co 3 O 4 -C sample (Figure S22). This accelerated the O–O bond breaking, generating epoxy (C–O–C) groups that facilitate the subsequent decomposition of O 3 . Moreover, residual O 3 resulted in the destruction of the carbon support, generating traces of CO 2 , which were detected in the gas phase (Figure S20).…”

Controlling Moisture for Enhanced Ozone Decomposition: A Study of Water Effects on CeO2 Surfaces and Catalytic Activity

“…Moreover, a theoretical investigation of ozone decomposition on defective graphene revealed an activation barrier of 0.63 eV. Through nitrogen doping and defect formation, this barrier was subsequently reduced to 0.21 eV …”

Modulation of CO adsorption on 4,12,2-graphyne by Fe atom doping and applied electric field

“…The gapless property of 4,12,2-G also limits its application in electronic equipment. Encouragingly, the existing research indicates that the electronic properties of graphene can be changed or even the adsorption performance can be improved by introducing defects, [19,20] doping metal atoms, [21][22][23][24] modifying functional groups, [25,26] and other means. It is noteworthy that Fe is often selected as a doped atom to improve the adsorption capacity of carbon materials for CO gas.…”