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

doi:10.1016/j.cjche.2019.10.003

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 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 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

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

Fan Pan, Guobing Zhou, Liangliang Huang, Wei Li, Mingshen Lin, Chang Liu. Interfacial potassium induced enhanced Raman spectroscopy for single-crystal TiO₂ nanowhisker[J]. Chinese Journal of Chemical Engineering, 2020, 28(3): 889-895.

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

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

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