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通过d带中心调控实现Ni-Co双位点将稀释的CO高效光还原为可调合成气

Efficient Photoreduction of Diluted CO to Tunable Syngas by Ni-Co Dual Sites through d-band Center Manipulation.

作者信息

Qian Gan, Lyu Wenyuan, Zhao Xin, Zhou Jingyi, Fang Ruiqi, Wang Fengliang, Li Yingwei

机构信息

School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China.

State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, 510640, China.

出版信息

Angew Chem Int Ed Engl. 2022 Oct 17;61(42):e202210576. doi: 10.1002/anie.202210576. Epub 2022 Sep 12.

Abstract

Photocatalytic conversion of CO into syngas is a promising way to address the energy and environmental challenges. Here we report the integration of Ni-Co dual sites on Ni doped Co O ultrathin nanosheets assembled double-hollow nanotube (Ni-Co O NSDHN) for efficient photoreduction of low-concentration CO . Quasi in situ spectra and density functional theory calculations demonstrate that the declining of d-band center of Ni-Co dual sites enables the electrons accumulation in the d /d -2π* and d -5σ orbitals. As a result, the binding strength of *CO is weakened and the *H adsorption site is modulated from metal sites to an oxygen site. Remarkably, Ni-Co O NSDHN exhibits superior diluted CO photoconversion activity and controllable selectivity under the irradiation of visible light or even natural sunlight. A syngas evolution rate of 170.0 mmol g  h with an apparent quantum yield of 3.7 % and continuously adjustable CO/H ratios from 1 : 10 to 10 : 1 are achieved.

摘要

将CO光催化转化为合成气是应对能源和环境挑战的一种很有前景的方法。在此,我们报道了在镍掺杂的氧化钴超薄纳米片组装的双空心纳米管(Ni-Co O NSDHN)上集成镍-钴双位点,用于高效光还原低浓度CO。准原位光谱和密度泛函理论计算表明,镍-钴双位点的d带中心下降使得电子在d /d -2π*和d -5σ轨道中积累。结果,*CO的结合强度减弱,*H吸附位点从金属位点调制到氧位点。值得注意的是,Ni-Co O NSDHN在可见光甚至自然阳光照射下表现出优异的稀释CO光转化活性和可控选择性。实现了170.0 mmol g  h的合成气析出速率,表观量子产率为3.7 %,CO/H比可在1 : 10至10 : 1之间连续调节。

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