期刊
ADVANCED ENERGY MATERIALS
卷 9, 期 30, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/aenm.201901505
关键词
carbon nitride; OER kinetics; photocatalysis; spin state; water splitting
类别
资金
- National Natural Science Foundation of China [21676193, 51661145026]
Solar-driven water splitting is in urgent need for sustainable energy research, for which accelerating oxygen evolution kinetics along with charge migration is the key issue. Herein, Mn3+ within pi-conjugated carbon nitride (C3N4) in form of Mn-N-C motifs is coordinated. The spin state (e(g) orbital filling) of Mn centers is regulated by controlling the bond strength of Mn-N. It is demonstrated that Mn serves as intrinsic oxygen evolution reaction (OER) site and the kinetics is dependent on its spin state with an optimized e(g) occupancy of approximate to 0.95. Specifically, the governing role of e(g) occupancy originates from the varied binding strength between Mn and OER intermediates. Benefiting from the rapid spin state-mediated OER kinetics, as well as extended optical absorption (to 600 nm) and accelerated charge separation by intercalated metal-to-ligand state, Mn-C3N4 stoichiometrically splits pure water with H-2 production rate up to 695.1 mu mol g(-1) h(-1) under simulated sunlight irradiation (AM1.5), and achieves an apparent quantum efficiency of 4.0% at 420 nm, superior to most solid-state based photocatalysts to date. This work for the first time correlates photocatalytic redox kinetics with the spin state of active sites, and suggests a nexus between photocatalysis and spin theory.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据