Nanodiamonds in sp2/sp3 configuration for radical to nonradical oxidation: Core-shell layer dependence
Nanodiamonds in sp2/sp3 configuration for radical to nonradical oxidation: Core-shell layer dependence
复制标题
sp(2)/sp(3)构型的纳米金刚石用于自由基至非自由基氧化：核-壳层依赖性
DOI：
10.1016/j.apcatb.2017.10.007
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发表时间：
2018-03-01
影响因子：
22.1
通讯作者：
Wang, Shaobin
中科院分区：
文献类型：
--
作者：
Duan, Xiaoguang;Ao, Zhimin;Wang, Shaobin
sp(2)/sp(3)分子构型的纳米碳具有多种结构和电子性质，在结构-活性化学中表现出复杂性。在这项工作中，我们采用sp(2)/sp(3)构型的爆轰纳米金刚石作为特征核/壳结构来证明结构与催化之间的内在相关性。经退火的爆轰纳米金刚石在过氧单硫酸盐活化和有机氧化方面表现出优异的催化活性。在界面处发现了电荷输运的协同效应，构建了一个富电子的碳表面，进一步提高了催化活性，密度泛函理论（DFT）计算证明了这一点。更重要的是，实验结果和理论预测都表明，通过过氧单硫酸盐（PMS）活化的催化氧化与sp(2)/sp(3)构型中石墨碳层的比例密切相关。纳米金刚石上石墨层的增加将使PMS的活化从基于自由基的反应转变为非自由基的催化氧化途径。碳催化氧化电位可调的新催化特性在环境催化和有机合成领域具有广阔的应用前景。
Nanocarbons in molecular configurations of sp(2)/sp(3) present versatile structural and electronic properties, exhibiting a complexity in the structure-activity chemistry. In this work, we employed detonation nanodiamonds constructed as a characteristic core/shell structure in the sp(2)/sp(3) configuration to demonstrate the intrinsic correlation between the structure and catalysis. Annealed detonation nanodiamonds were found to show a superb activity for catalytic peroxymonosulfate activation and organic oxidation. A synergistic effect of charge transport was discovered at the interface to construct an electron-enriched carbon surface that further promoted the catalytic activity evidenced by the density functional theory (DFT) calculations. More importantly, both experimental results and theoretical predictions revealed that the catalytic oxidation via peroxymonosulfate (PMS) activation was intimately dependent on the proportion of graphitic carbon layer in the sp(2)/sp(3) configurations. The increase of graphitic layers on nanodiamonds would alter the PMS activation from a radical-based reaction to a nonradical pathway for catalytic oxidation. The novel catalytic properties of tunable oxidative potentials from carbocatalysiS may simulate fascinating prospects for environmental catalysis and organic synthesis.