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Probing the Catalytic Center of TiO2/SO4 2− Solid Superacid Catalyst by X-Band In Situ High-Temperature EPR Spectroscopy

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Abstract

Paramagnetic centers of the solid superacid catalyst in the sulfated TiO2 are prone to the electron paramagnetic resonance (EPR) spectroscopy. The induction of the catalytic-active sites in TiO2 powder presubmerged in H2SO4 solution as a function of the calcinated temperature of 293–873 K is investigated by X-band in situ continuous-wave EPR measurements. Sulfated-acid sites composed of the Ti3+ ion are formed upon calcination. The overall experimental results show that the population of these sites goes uphill with the elevating temperature, reaches a maximum at ~623 K and decreases afterward to close zero. During the process, the decomposition of the TiO2/SO4 2− leads to the formation of Ti3+ species and then to the increasing EPR signal amplitude, and the consecutive decomposition of the sulfur at higher temperature (>650 K) to the diminishing signal. The X-ray diffraction indicates that the introduction of SO4 2− stabilizes the geometric structure in the anatase phase.

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Acknowledgments

This work was financially supported by grants of the National Natural Science Foundation of China (No. 20771097, 31070211), Initial Funding of University of Science and Technology of China (ZC9850290071), and Open Fund (CL201001) Institute of Physical Chemistry, Zhejiang Normal University, the Anhui Provincial Natural Science Foundation (11040606M53).

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Authors and Affiliations

  1. Hefei National Laboratory for Physical Sciences at Microscale, Department of Morden Physics, University of Science and Technology of China (USTC), Hefei, 230026, Anhui, People’s Republic of China

    Chunhua Zhu, Jiafu Chen & Ji-Hu Su

  2. Department of Chemical Engineering, Nanjing Forestry University, Nanjing, 210037, Jiangsu, People’s Republic of China

    Mingcui Guo & Xinbao Zhu

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  1. Chunhua Zhu
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  2. Mingcui Guo
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  3. Xinbao Zhu
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  4. Jiafu Chen
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  5. Ji-Hu Su
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Correspondence to Ji-Hu Su.

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Zhu, C., Guo, M., Zhu, X. et al. Probing the Catalytic Center of TiO2/SO4 2− Solid Superacid Catalyst by X-Band In Situ High-Temperature EPR Spectroscopy. Appl Magn Reson 42, 313–320 (2012). https://doi.org/10.1007/s00723-011-0277-6

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  • DOI: https://doi.org/10.1007/s00723-011-0277-6

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