Highly Efficient Metal-Free Nitrogen-Doped Nanocarbons with Unexpected Active Sites for Aerobic Catalytic Reactions

doi:10.1021/acsnano.9b05856

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	Highly Efficient Metal-Free Nitrogen-Doped Nanocarbons with Unexpected Active Sites for Aerobic Catalytic Reactions
	Lin, Yangming 2,3; Liu, Zigeng 3; Niu, Yiming 2; Zhang, Bingsen 2; Lu, Qing 3; Wu, Shuchang 2; Centi, Gabriele 4; Perathoner, Siglinda 4; Heumann, Saskia 3; Yu, Linhui 1,3
刊名	ACS NANO
	2019-12-01
卷号	13 期号:12 页码:13995-14004
关键词	nanodiamond carbon materials metal-free nitrogen-doped catalysis model catalyst kinetic isotope effect
ISSN号	1936-0851
DOI	10.1021/acsnano.9b05856
通讯作者	Lin, Yangming(yang-ming.lin@cec.mpg.de) ; Yu, Linhui(linhui.yu@cec.mpg.de)
英文摘要	Nitrogen (N)-doped nanocarbons (NDN) as metal-free catalysts have elicited considerable attention toward selective oxidation of alcohols with easily oxidizable groups to aldehydes in the past few years. However, finding a new NDN catalytic material that can meet the requirement of the feasibility on the aerobic catalytics for other complicated alcohols is a big challenge. The real active sites and the corresponding mechanisms on NDN are still unambiguous because of inevitable coexistence of diverse edge sites and N species based on recently reported doping methods. Here, four NDN catalysts with enriched pyridinic N species and without any graphitic N species are simply fabricated via a chemical-vapor-deposition-like method. The results of X-ray photoelectron spectroscopy and X-ray absorption near-edge structure spectra suggest that the dominating N species on NDN are pyridinic N. It is demonstrated that NDN catalysts perform impressive reactivity for aerobic oxidation of complicated alcohols at an atmospheric pressure. Eleven kinds of aromatic molecules with single N species and tunable pi conjugation systems are used as model catalysts to experimentally identify the actual role of each N species at a real molecular level. It is suggested that pyridinic N species play an unexpected role in catalytic reactions. Neighboring carbon atoms in pyridinic N species are responsible for facilitating the rate-determining step process clarified by kinetic isotope effects, in situ nuclear magnetic resonance, in situ attenuated total reflectance infrared, and theoretical calculation. Moreover, NDN catalysts exhibit a good catalytic feasibility on the synthesis of important natural products (e.g., intermediates of vitamin E and K3) from phenol oxidation.
资助项目	Strategic Priority Research Program of the Chinese Academy of Sciences[XDA09030103] ; National Natural Science Foundation of China[91545119] ; Max Planck Society
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Materials Science
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000505633300038
资助机构	Strategic Priority Research Program of the Chinese Academy of Sciences ; National Natural Science Foundation of China ; Max Planck Society
内容类型	期刊论文
源URL	[http://ir.imr.ac.cn/handle/321006/136367]
专题	金属研究所_中国科学院金属研究所
通讯作者	Lin, Yangming; Yu, Linhui
作者单位	1.Fuzhou Univ, Fuzhou 350002, Peoples R China 2.Chinese Acad Sci, Inst Met Res, 72 Wenhua Rd, Shenyang 110016, Peoples R China 3.Max Planck Inst Chem Energy Convers, Stiftstr 34-36, D-45470 Mulheim, Germany 4.Univ Messina, Vle F Stagno DAlcontres 31, I-98166 Messina, Italy 5.Max Planck Gesell, Fritz Haber Inst, Dept Inorgan Chem, Faradayweg 4-6, D-14195 Berlin, Germany
推荐引用方式 GB/T 7714	Lin, Yangming,Liu, Zigeng,Niu, Yiming,et al. Highly Efficient Metal-Free Nitrogen-Doped Nanocarbons with Unexpected Active Sites for Aerobic Catalytic Reactions[J]. ACS NANO,2019,13(12):13995-14004.
APA	Lin, Yangming.,Liu, Zigeng.,Niu, Yiming.,Zhang, Bingsen.,Lu, Qing.,...&Su, Dang Sheng.(2019).Highly Efficient Metal-Free Nitrogen-Doped Nanocarbons with Unexpected Active Sites for Aerobic Catalytic Reactions.ACS NANO,13(12),13995-14004.
MLA	Lin, Yangming,et al."Highly Efficient Metal-Free Nitrogen-Doped Nanocarbons with Unexpected Active Sites for Aerobic Catalytic Reactions".ACS NANO 13.12(2019):13995-14004.