Complete Photooxidation of Formaldehyde to CO(2) via Ni-Dual-Atom Decorated Crystalline Triazine Frameworks: A DFT Study

通过镍双原子修饰的结晶三嗪骨架将甲醛完全光氧化为CO₂:DFT研究

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Abstract

Formaldehyde (CH(2)O) emerges as a significant air pollutant, necessitating effective strategies for its oxidation to mitigate adverse impacts on human health and the environment. Among various technologies, the photooxidation of CH(2)O stands out owing to its affordability, safety, and effectiveness. Nitrogen-rich crystalline triazine-based organic frameworks (CTFs) exhibit considerable potential in this domain. Nevertheless, the weak and unstable CH(2)O adsorption hinders the overall oxidation efficiency of CTF. To address this limitation, we incorporate single and dual Ni atoms into nitrogen-rich CTFs by density functional theory (DFT) calculations, resulting in CTF-Ni and CTF-2Ni. This strategic modification significantly enhances the adsorption capability of CH(2)O. Notably, this synergy between Ni dual atoms activates CH(2)O by strong chemical adsorption, thereby reducing the energy barrier of CH(2)O oxidation and achieving the complete oxidation of CH(2)O to CO(2). Moreover, the introduction of dual-atom Ni over CTF ameliorates visible and near-infrared light absorption and facilitates photoexcited charge transfer and separation. Finally, the underlying mechanisms of complete CH(2)O oxidation over CTF-2Ni are proposed. This work offers novel insights into the rational design of photocatalysts for CH(2)O oxidation through the integration of Ni dual atoms into CTFs.

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