Vibrational relaxation dynamics of catalysts on TiO₂ Rutile (1 1 0) single crystal surfaces and anatase nanoporous thin films

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• 作者：Allen M. Ricks ; Chantelle L. Anfuso ; William Rodr¨ªguez-C¨®rdoba ; Tianquan Lian
• 关键词：Vibrational relaxation ; Interfacial dynamics ; Time-resolved sum-frequency generation spectroscopy ; CO2 reduction catalyst
• 刊名：Chemical Physics
• 出版年：2013
• 出版时间：30 August, 2013
• 年：2013
• 卷：422
• 期：Complete
• 页码：264-271
• 全文大小：960 K

文摘

Time-resolved vibrational sum frequency generation (VSFG) spectroscopy has been used to investigate the vibrational relaxation dynamics of the rhenium bipyridyl CO₂-reduction catalyst Re(CO)₃Cl(dcbpy) [dcbpy = 4,4¡ä-dicarboxy-2,2¡ä-bipyridine] adsorbed onto the (1 1 0) surface of a Rutile TiO₂ single crystal. IR pump-VSFG probe spectra of the a¡ä(1) CO stretching mode indicate a ultrafast population equilibration between three CO stretching modes followed by their population relaxation via intramolecular vibrational energy transfer. Similar vibational relaxation dynamics was also observed for the same complex on anatase TiO₂ nanocrystalline thin films measured by IR pump-IR probe transient absorption spectroscopy. The relaxation dynamics of ReCOA on TiO₂, in DMF solution, and immobilized on Au through alkane thiol linkers were compared to examine possible effects of adsorbate-TiO₂ interaction.