SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2020, Vol. 28 ›› Issue (3): 889-895.DOI: 10.1016/j.cjche.2019.10.003

• Materials and Product Engineering • Previous Articles     Next Articles

Interfacial potassium induced enhanced Raman spectroscopy for single-crystal TiO2 nanowhisker

Fan Pan1, Guobing Zhou2, Liangliang Huang2, Wei Li3, Mingshen Lin4, Chang Liu1   

  1. 1 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
    2 School of Chemical, Biological & Materials Engineering, University of Oklahoma, Norman, 73019, United States;
    3 European Bioenergy Research Institute and Aston Institute of Materials Research, Aston University, Birmingham B4 7ET, United Kingdom;
    4 TA Instruments-Waters LLC, Shanghai 200233, China
  • Received:2019-07-14 Revised:2019-09-10 Online:2020-06-11 Published:2020-03-28
  • Contact: Chang Liu
  • Supported by:
    This work was supported by National Natural Science Foundation of China (21878143, 21476106, and 21838004), Joint Research Fund for Overseas Chinese Scholars and Scholars in Hong Kong and Macao Young Scholars (21729601), the fund of State Key Laboratory of MaterialsOriented Chemical Engineering (ZK201702, KL16-01), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD). Zhou and Huang acknowledge the U.S. National Science Foundation (NSF) for support through Grant No. CHE-1710102. We are grateful to the High-Performance Computing Center of Nanjing Tech University for supporting the computational resources.

Interfacial potassium induced enhanced Raman spectroscopy for single-crystal TiO2 nanowhisker

Fan Pan1, Guobing Zhou2, Liangliang Huang2, Wei Li3, Mingshen Lin4, Chang Liu1   

  1. 1 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
    2 School of Chemical, Biological & Materials Engineering, University of Oklahoma, Norman, 73019, United States;
    3 European Bioenergy Research Institute and Aston Institute of Materials Research, Aston University, Birmingham B4 7ET, United Kingdom;
    4 TA Instruments-Waters LLC, Shanghai 200233, China
  • 通讯作者: Chang Liu
  • 基金资助:
    This work was supported by National Natural Science Foundation of China (21878143, 21476106, and 21838004), Joint Research Fund for Overseas Chinese Scholars and Scholars in Hong Kong and Macao Young Scholars (21729601), the fund of State Key Laboratory of MaterialsOriented Chemical Engineering (ZK201702, KL16-01), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD). Zhou and Huang acknowledge the U.S. National Science Foundation (NSF) for support through Grant No. CHE-1710102. We are grateful to the High-Performance Computing Center of Nanjing Tech University for supporting the computational resources.

Abstract: Structural control and element doping are two popular strategies to produce semiconductors with surface enhanced Raman spectroscopy (SERS) properties. For TiO2 based SERS substrates, maintaining a good crystallinity is critical to achieve excellent Raman scattering. At elevated temperatures (>600 ℃), the phase transition from anatase to rutile TiO2 could result in a poor SERS performance. In this work, we report the successful synthesis of TiO2 nanowhiskers with excellent SERS properties. The enhancement factor, an index of SERS performance, is 4.96×106 for methylene blue molecule detecting, with a detection sensitivity around 10-7 mol·L-1. Characterizations, such as XRD, Raman, TEM, UV-vis and Zeta potential measurement, have been performed to decrypt structural and chemical characteristics of the newly synthesized TiO2 nanowhiskers. The photo absorption onset of MB adsorbed TiO2 nanowhiskers was similar to that of bare TiO2 nanowhiskers. In addition, no new band was observed from the UV-vis of MB modified TiO2 nanowhiskers. Both results suggest that the high enhancement factor cannot be explained by the charge-transfer mechanism. With the support of ab initio density functional theory calculations, we reveal that interfacial potassium is critical to maintain thermal stability of the anatase phase up to 900 ℃. In addition, the deposition of potassium results in a negatively charged TiO2 nanowhisker surface, which favors specific adsorption of methylene blue molecules and significantly improves SERS performance via the electrostatic adsorption effect.

Key words: TiO2 nanowhisker, SERS, potassium induced

摘要: Structural control and element doping are two popular strategies to produce semiconductors with surface enhanced Raman spectroscopy (SERS) properties. For TiO2 based SERS substrates, maintaining a good crystallinity is critical to achieve excellent Raman scattering. At elevated temperatures (>600 ℃), the phase transition from anatase to rutile TiO2 could result in a poor SERS performance. In this work, we report the successful synthesis of TiO2 nanowhiskers with excellent SERS properties. The enhancement factor, an index of SERS performance, is 4.96×106 for methylene blue molecule detecting, with a detection sensitivity around 10-7 mol·L-1. Characterizations, such as XRD, Raman, TEM, UV-vis and Zeta potential measurement, have been performed to decrypt structural and chemical characteristics of the newly synthesized TiO2 nanowhiskers. The photo absorption onset of MB adsorbed TiO2 nanowhiskers was similar to that of bare TiO2 nanowhiskers. In addition, no new band was observed from the UV-vis of MB modified TiO2 nanowhiskers. Both results suggest that the high enhancement factor cannot be explained by the charge-transfer mechanism. With the support of ab initio density functional theory calculations, we reveal that interfacial potassium is critical to maintain thermal stability of the anatase phase up to 900 ℃. In addition, the deposition of potassium results in a negatively charged TiO2 nanowhisker surface, which favors specific adsorption of methylene blue molecules and significantly improves SERS performance via the electrostatic adsorption effect.

关键词: TiO2 nanowhisker, SERS, potassium induced