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Atmospheric CO2 capture and photofixation to near-unity CO by Ti3+-Vo-Ti3+ sites confined in TiO2 ultrathin layers

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Abstract

To realize efficient atmospheric CO2 chemisorption and activation, abundant Ti3+ sites and oxygen vacancies in TiO2 ultrathin layers were designed. Positron annihilation lifetime spectroscopy and theoretical calculations first unveil each oxygen vacancy is associated with the formation of two Ti3+ sites, giving a Ti3+-Vo-Ti3+ configuration. The Ti3+-Vo-Ti3+ sites could bond with CO2 molecules to form a stable configuration, which converted the endoergic chemisorption step to an exoergic process, verified by in-situ Fourier-transform infrared spectra and theoretical calculations. Also, the adjacent Ti3+ sites not only favor CO2 activation into COOH* via forming a stable Ti3+-C-O-Ti3+ configuration, but also facilitate the rate-limiting COOH* scission to CO* by reducing the energy barrier from 0.75 to 0.45 eV. Thus, the Ti3+-Vo-TiO2 ultrathinlayers could directly capture and photofix atmospheric CO2 into near-unity CO, with the corresponding CO2-to-CO conversion ratio of ca. 20.2%.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2019YFA0210004, 2017YFA0207301, 2017YFA0303500), the National Natural Science Foundation of China (21975242, U2032212, 21890754, 21805267, 21703222, 11975225), the 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), The University Synergy Innovation Program of Anhui Province (GXXT-2020-001), and the Fok Ying-Tong Education Foundation (161012). Supercomputing USTC and National Supercomputing Center in Shenzhen are acknowledged for computational support.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Hefei National Laboratory for Physical Science at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230026, China

    Liang Liang, Peiquan Ling, Yuhuan Li, Li Li, Jiandang Liu, Hongjun Zhang, Qian Xu, Yang Pan, Junfa Zhu, Bangjiao Ye & Yongfu Sun

  2. Institute of Physical Science and Information Technology, Anhui University, Anhui, 230601, China

    Qiquan Luo

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  1. Liang Liang
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  4. Li Li
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Correspondence to Qiquan Luo, Hongjun Zhang or Yongfu Sun.

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Liang, L., Ling, P., Li, Y. et al. Atmospheric CO2 capture and photofixation to near-unity CO by Ti3+-Vo-Ti3+ sites confined in TiO2 ultrathin layers. Sci. China Chem. 64, 953–958 (2021). https://doi.org/10.1007/s11426-021-9967-9

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