Monitoring Local Electric Fields using Stark Shifts on Napthyl Nitrile-Functionalized Silicon Photoelectrodes

Shi, Haotian; Pekarek, Ryan T.; Chen, Ran; Zhang, Boxin; Wang, Yu; Aravind, Indu; Cai, Zhi; Jensen, Lasse; Neale, Nathan R.; Cronin, Stephen B.

doi:10.1021/acs.jpcc.0c03966

Monitoring Local Electric Fields using Stark Shifts on Napthyl Nitrile-Functionalized Silicon Photoelectrodes

Journal Article · Fri Jul 10 00:00:00 EDT 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c03966· OSTI ID:1677449

Shi, Haotian ^[1]; Pekarek, Ryan T. ^[2]; Chen, Ran ^[3]; Zhang, Boxin ^[1]; ^[1]; Aravind, Indu ^[1]; Cai, Zhi ^[1]; ^[3]; ^[2]; ^[1]

Univ. of Southern California, Los Angeles, CA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Pennsylvania State Univ., University Park, PA (United States)

in this paper, we report spectroscopic measurements of the local electric field using vibrational Stark shifts of napthyl nitrile-functionalized silicon under electrochemical working conditions. The C$$\equiv$$N bond is particularly sensitive to applied electric fields and serves as a good probe for the local electric fields at the silicon–aqueous interface. Here, surface-enhanced Raman spectra (SERS) are collected at a silicon surface using a water immersion lens as a function of the reference potential in a three-terminal potentiostat. In deionized (DI) water and KCl solutions, the nitrile (i.e., C$$\equiv$$N) stretch downshifts by 4.7 and 8.6 cm^–1, respectively, under an applied potential of –1 V vs Ag/AgCl. Density functional theory (DFT) calculations of the napthyl nitrile complex carried out under various electric fields establish the Stark tuning rate to be 0.5622 cm–1/(MV cm^–1). Based on this relation, electric fields of –8.4 and –15.2 MV/cm were obtained under negative applied potentials. These measurements report the electric field strength within the double (i.e., Helmholtz) layer, which is responsible for pulling positively charged ions (e.g., H⁺) toward the surface in reduction reaction processes.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); US Army Research Office (ARO); US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC36-08GO28308; SC0019322

OSTI ID:: 1677449

Report Number(s):: NREL/JA--5900-76691; MainId:9352; UUID:9004cbc7-766e-4773-943b-ce372da86f51; MainAdminID:18638

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 31 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Monitoring Local Electric Fields using Stark Shifts on Napthyl Nitrile-Functionalized Silicon Photoelectrodes

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