期刊
NANO LETTERS
卷 21, 期 9, 页码 4122-4128出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.nanolett.1c01204
关键词
partial CH4 photooxidation; liquid oxygenates; atmospheric pressure; oxide semiconductors
类别
资金
- National Key R&D Program of China [2019YFA0210004, 2017YFA0207301]
- National Natural Science Foundation of China [21975242, U2032212, 21890754]
- Strategic Priority Research Program of Chinese Academy of Sciences [XDB36000000]
- Youth Innovation Promotion Association of CAS [CX2340007003]
- Key Research Program of Frontier Sciences of CAS [QYZDY-SSW-SLH011]
- Major Program of Development Foundation of Hefei Center for Physical Science and Technology [2020HSC-CIP003]
- Users with Excellence Program of Hefei Science Center CAS [2020HSC-UE001]
- University Synergy Innovation Program of Anhui Province [GXXT-2020-001]
- Fok Ying-Tong Education Foundation [161012]
By designing two-dimensional oxide semiconductors and utilizing active O- species on ZnO nanosheets to activate the C-H bond of CH4, the selective production of liquid oxygenates has been successfully achieved.
Direct CH4 photoconversion into liquid oxygenates under mild conditions still represents a huge challenge. Herein, two-dimensional oxide semiconductors are designed to generate abundant active O- species for activating C-H bond of methane. Taking the synthetic ZnO nanosheets as an example, in situ electron paramagnetic resonance spectra verified their lattice oxygen atoms could capture photoexcited holes and generate active O- species, which could efficiently abstract H from CH4 to generate center dot CH3 radicals. Gibbs free energy calculations and in situ Fourier-transform infrared spectroscopy corroborated the rate-limiting step was the first C-H bond activation process, whereas the exoergic oxidation of *CHO to HCOOH was easier than the endoergic overoxidation to CO, accounting for the selective production of liquid oxygenates. As a result, the formation rate of liquid oxygenates over ZnO nanosheets reached 2.21 mmol g(-1) h(-1) with a selectivity of 90.7% at atmospheric pressure and approximately 50 degrees C, outperforming previously reported photocatalysts under similar conditions.
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