Voltammetric Measurement of Rates and Energetics for Surface Methoxylation of Si(100) in Methanol with Dissolved Electron Acceptors Using Si Ultramicroelectrodes

Liu, Zhihui; Pishgar, Sahar; Lancaster, Mitchell; Maldonado, Stephen

doi:10.1021/acs.analchem.2c05276

Voltammetric Measurement of Rates and Energetics for Surface Methoxylation of Si(100) in Methanol with Dissolved Electron Acceptors Using Si Ultramicroelectrodes

Journal Article · Wed Apr 19 00:00:00 EDT 2023 · Analytical Chemistry

DOI:https://doi.org/10.1021/acs.analchem.2c05276· OSTI ID:1991313

Liu, Zhihui ^[1]; Pishgar, Sahar ^[2]; Lancaster, Mitchell ^[2]; ^[2]

University of Michigan, Ann Arbor, MI (United States); University of Michigan
University of Michigan, Ann Arbor, MI (United States)

The steady-state voltammetric responses of n-type Si(100) semiconductor ultramicroelectrodes (SUMEs) immersed in air- and water-free methanolic electrolytes have been measured. The response characteristics of these SUMEs in the absence of illumination were modeled and understood through a framework that describes the distribution of the applied potential across the semiconductor/electrolyte contact using four discrete regions: the semiconductor space charge, surface, Helmholtz, and diffuse layers. The latter region was described by the full Gouy–Chapman model. This framework afforded insight on how relevant parameters such as the semiconductor band edge potentials, the reorganization energies for charge transfer, the standard potential of redox species in solution, the density and energy of surface state populations, and the presence of an insulating (tunneling) layer individually and collectively dictate the observable current–potential responses. With this information, the methoxylation of Si surfaces was evaluated by analysis of the change in voltammetric responses during the course of prolonged immersion in methanol. Here, the electrochemical data were consistent with a surface methoxylation mechanism that depended on the standard potential of redox species dissolved in solution. Estimates of the enthalpies of adsorption as well as the potential-dependent rate constant for surface methoxylation were obtained. Collectively, these measurements supported the contention that the rates of Si surface reactions can be systematically tuned by exposure to dissolved outer-sphere electron acceptors. Moreover, the data represent the quantitative utility of voltammetry with SUMEs for the measurement of semiconductor/liquid contacts.

View Accepted Manuscript (DOE)

Research Organization:: University of Michigan, Ann Arbor, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0006628

OSTI ID:: 1991313

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 17 Vol. 95; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Voltammetric Measurement of Rates and Energetics for Surface Methoxylation of Si(100) in Methanol with Dissolved Electron Acceptors Using Si Ultramicroelectrodes

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