Vibrational Stark shift spectroscopy of catalysts under the influence of electric fields at electrode-solution interfaces.
Dhritiman Bhattacharyya, Pablo E Videla, Mauricio Cattaneo, Victor S Batista, Tianquan Lian, Clifford P Kubiak
Author Information
Dhritiman Bhattacharyya: Department of Chemistry, Emory University 1515 Dickey Drive Northeast Atlanta Georgia 30322 USA tlian@emory.edu. ORCID
Pablo E Videla: Department of Chemistry and Energy Sciences Institute, Yale University 225 Prospect Street New Haven Connecticut 06520 USA victor.batista@yale.edu.
Mauricio Cattaneo: INQUINOA-UNT-CONICET, Facultad de Bioquímica, Química y Farmacia, Instituto de Química Física, Universidad Nacional de Tucumán Ayacucho 471 (4000) San Miguel de Tucumán Argentina.
Victor S Batista: Department of Chemistry and Energy Sciences Institute, Yale University 225 Prospect Street New Haven Connecticut 06520 USA victor.batista@yale.edu.
Tianquan Lian: Department of Chemistry, Emory University 1515 Dickey Drive Northeast Atlanta Georgia 30322 USA tlian@emory.edu. ORCID
Clifford P Kubiak: Department of Chemistry and Biochemistry, University of California, San Diego 9500 Gilman Drive, MC 0358 La Jolla California 92093 USA ckubiak@ucsd.edu. ORCID
External control of chemical processes is a subject of widespread interest in chemical research, including control of electrocatalytic processes with significant promise in energy research. The electrochemical double-layer is the nanoscale region next to the electrode/electrolyte interface where chemical reactions typically occur. Understanding the effects of electric fields within the electrochemical double layer requires a combination of synthesis, electrochemistry, spectroscopy, and theory. In particular, vibrational sum frequency generation (VSFG) spectroscopy is a powerful technique to probe the response of molecular catalysts at the electrode interface under bias. Fundamental understanding can be obtained synthetic tuning of the adsorbed molecular catalysts on the electrode surface and by combining experimental VSFG data with theoretical modelling of the Stark shift response. The resulting insights at the molecular level are particularly valuable for the development of new methodologies to control and characterize catalysts confined to electrode surfaces. This Perspective article is focused on how systematic modifications of molecules anchored to surfaces report information concerning the geometric, energetic, and electronic parameters of catalysts under bias attached to electrode surfaces.
References
Acc Chem Res. 2019 May 21;52(5):1289-1300
[PMID: 31056907]
