Wide-range tuning of the titanium dioxide flat-band potential by adsorption of fluoride and hydrofluoric acid

Chong Mou Wang; Thomas E. Mallouk

doi:10.1021/j100373a072

Wide-range tuning of the titanium dioxide flat-band potential by adsorption of fluoride and hydrofluoric acid

Chong Mou Wang, Thomas E. Mallouk

Department of Chemistry

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57 Citations (Scopus)

Abstract

The adsorption of fluoride, (HF)_nF_- ions, and hydrofluoric acid at the surface of n-type TiO_2-xF_x (x ≈ 0.001) electrodes was studied by electrochemical methods. Adsorption of F_- from acetonitrile/tetraethylammonium fluoride (TEAF) solution follows a Langmuir isotherm above a fractional coverage of about 0.5, and the equilibrium constant for adsorption is 8300 M_-1. Specific adsorption of fluoride ions, at millimolar concentration in acetonitrile, results in a large negative shift in the flat-band potential, as manifested by capacitance measurements and cyclic voltammetry of Ru(bpy)³²⁺. Fluoride ions are strongly complexed by HF in acetonitrile to form (HF)_nF_- ions (n = 1, 2), which are also specifically adsorbed at the TiO_2-xF_x(001 ) surface. The flat-band potential can be shifted by ca. 2 V, from -1.8 V vs Cu/CuF₂ in pure acetonitrile/0.5 M TEAF to +0.2 V in acetonitrile/0.9 M TEAF/36 M HF. Addition of relatively small amounts (ca. 2 M) HF to acetonitrile/0.5 M TEAF causes the valence band edge to shift to a sufficiently positive potential that elemental fluorine can be evolved photoelectrochemically.

Original language	English
Pages (from-to)	4276-4280
Number of pages	5
Journal	Journal of Physical Chemistry®
Volume	94
Issue number	10
DOIs	https://doi.org/10.1021/j100373a072
Publication status	Published - 1990 Jan 1

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Engineering(all)
Physical and Theoretical Chemistry

Cite this

Wang, C. M., & Mallouk, T. E. (1990). Wide-range tuning of the titanium dioxide flat-band potential by adsorption of fluoride and hydrofluoric acid. Journal of Physical Chemistry®, 94(10), 4276-4280. https://doi.org/10.1021/j100373a072

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abstract = "The adsorption of fluoride, (HF)nF- ions, and hydrofluoric acid at the surface of n-type TiO2-xFx (x ≈ 0.001) electrodes was studied by electrochemical methods. Adsorption of F- from acetonitrile/tetraethylammonium fluoride (TEAF) solution follows a Langmuir isotherm above a fractional coverage of about 0.5, and the equilibrium constant for adsorption is 8300 M-1. Specific adsorption of fluoride ions, at millimolar concentration in acetonitrile, results in a large negative shift in the flat-band potential, as manifested by capacitance measurements and cyclic voltammetry of Ru(bpy)32+. Fluoride ions are strongly complexed by HF in acetonitrile to form (HF)nF- ions (n = 1, 2), which are also specifically adsorbed at the TiO2-xFx(001 ) surface. The flat-band potential can be shifted by ca. 2 V, from -1.8 V vs Cu/CuF2 in pure acetonitrile/0.5 M TEAF to +0.2 V in acetonitrile/0.9 M TEAF/36 M HF. Addition of relatively small amounts (ca. 2 M) HF to acetonitrile/0.5 M TEAF causes the valence band edge to shift to a sufficiently positive potential that elemental fluorine can be evolved photoelectrochemically.",

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N2 - The adsorption of fluoride, (HF)nF- ions, and hydrofluoric acid at the surface of n-type TiO2-xFx (x ≈ 0.001) electrodes was studied by electrochemical methods. Adsorption of F- from acetonitrile/tetraethylammonium fluoride (TEAF) solution follows a Langmuir isotherm above a fractional coverage of about 0.5, and the equilibrium constant for adsorption is 8300 M-1. Specific adsorption of fluoride ions, at millimolar concentration in acetonitrile, results in a large negative shift in the flat-band potential, as manifested by capacitance measurements and cyclic voltammetry of Ru(bpy)32+. Fluoride ions are strongly complexed by HF in acetonitrile to form (HF)nF- ions (n = 1, 2), which are also specifically adsorbed at the TiO2-xFx(001 ) surface. The flat-band potential can be shifted by ca. 2 V, from -1.8 V vs Cu/CuF2 in pure acetonitrile/0.5 M TEAF to +0.2 V in acetonitrile/0.9 M TEAF/36 M HF. Addition of relatively small amounts (ca. 2 M) HF to acetonitrile/0.5 M TEAF causes the valence band edge to shift to a sufficiently positive potential that elemental fluorine can be evolved photoelectrochemically.

AB - The adsorption of fluoride, (HF)nF- ions, and hydrofluoric acid at the surface of n-type TiO2-xFx (x ≈ 0.001) electrodes was studied by electrochemical methods. Adsorption of F- from acetonitrile/tetraethylammonium fluoride (TEAF) solution follows a Langmuir isotherm above a fractional coverage of about 0.5, and the equilibrium constant for adsorption is 8300 M-1. Specific adsorption of fluoride ions, at millimolar concentration in acetonitrile, results in a large negative shift in the flat-band potential, as manifested by capacitance measurements and cyclic voltammetry of Ru(bpy)32+. Fluoride ions are strongly complexed by HF in acetonitrile to form (HF)nF- ions (n = 1, 2), which are also specifically adsorbed at the TiO2-xFx(001 ) surface. The flat-band potential can be shifted by ca. 2 V, from -1.8 V vs Cu/CuF2 in pure acetonitrile/0.5 M TEAF to +0.2 V in acetonitrile/0.9 M TEAF/36 M HF. Addition of relatively small amounts (ca. 2 M) HF to acetonitrile/0.5 M TEAF causes the valence band edge to shift to a sufficiently positive potential that elemental fluorine can be evolved photoelectrochemically.

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10.1021/j100373a072