On–Off Switching of a Photocatalytic Overall Reaction through Dynamic Spin-State Transition in a Hofmann Clathrate System

笼状水合物 化学 光催化 催化作用 光化学 自旋(空气动力学) 化学物理 凝聚态物理 热力学 有机化学 水合物 物理
作者
Guo‐Zhang Huang,Yuan‐Sheng Xia,Feng Yang,Wei‐Jian Long,Jingjing Liu,Jia‐Peng Liao,Mi Zhang,Jiang Liu,Ya‐Qian Lan
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:145 (49): 26863-26870 被引量:25
标识
DOI:10.1021/jacs.3c09513
摘要

Spin-state transition is a vital factor that dominates catalytic processes, but unveiling its mechanism still faces the great challenge of the lack of catalyst model systems. Herein, we propose that the {Fe-Pt} Hofmann clathrates, whose dynamic spin-state transition of metal centers can be chemically manipulated through iodine treatment, can serve as model systems in the spin-related structural–catalytic relationship study. Taking the photocatalytic synthesis of H2O2 as the basic catalytic reaction, when the spin state of Fe(II) in the clathrate is high spin (HS), sacrificial agents are indispensable to the photosynthesis of H2O2 because only the photocatalytic oxygen reduction reaction (ORR) occurs; when it is low spin (LS), both the ORR and water oxidation reaction (WOR) can take place, enabling a high H2O2 photosynthesis rate of 66 000 μM g–1 h–1 under visible-light irradiation. In situ characterizations combined with density functional theory calculations confirmed that, compared with the HS-state counterpart, the LS state can induce strong charge transfer between the LS Fe(II) and the iodide-coordinating Pt(IV) in the polymer and reduce the energy barriers for both the ORR and WOR processes, dominating the on–off switching upon the photosynthesis of H2O2 in O2-saturated water. What's more, the one-pot tandem reactions were conducted to utilize the synthesized H2O2 for transforming the low-value-added sodium alkenesulfonates into value-added bromohydrin products with decent conversion rates. This work provides a pioneering investigation into on–off switching the photocatalytic overall reaction through manipulating the metallic spin-state transition in spin-crossover systems.
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