Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces

doi:10.1021/acs.jpcc.7b01272

Title: Inferring Protonation States of Hydroxamate Adsorbates on TiO ₂ Surfaces

Full Record
Other Related Research

Abstract

We explore the protonation states of benzohydroxamic acid adsorbates bound to the {101} facet of TiO ₂ anatase by using a combination of density functional theory, simulations of UV–vis spectra based on a tight-binding Hamiltonian, and direct comparisons to experimental measurements. We find that the characteristic red-shifted spectrum of nonmethylated, relative to the methylated, hydroxamic acids can only be explained by proposing a monodeprotonated monodentate mode as the main adsorption mode. The reported analysis suggests a simple, yet general, spectroscopic method based on UV–vis absorption measurements and tight-binding calculations for inferring changes of pK _a of molecular adsorbates interacting with semiconductor electrode surfaces.

Authors:

^[1]; Negre, Christian F. A. ^[2]; Oliboni, Robson S. ^[3]; Monti, Adriano ^[1]; Chen, Jeffrey ^[1];

^[1]; Rego, Luis G. C. ^[3];

^[1]

Yale Univ., New Haven, CT (United States). Dept. of Chemistry and Energy Sciences Inst.
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Federal Univ. of Santa Catarina, Florianopolis, Santa Catarina (Brazil). Dept. of Physics

Publication Date:: 2017-05-24

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1480466

Grant/Contract Number:: SC0001059

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 121; Journal Issue: 22; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Citation Formats


                    Rudshteyn, Benjamin, Negre, Christian F.  A., Oliboni, Robson S., Monti, Adriano, Chen, Jeffrey, Crabtree, Robert H., Rego, Luis G.  C., and Batista, Victor S. Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces.  United States: N. p., 2017. 
        Web.  doi:10.1021/acs.jpcc.7b01272.

Copy to clipboard


                    Rudshteyn, Benjamin, Negre, Christian F.  A., Oliboni, Robson S., Monti, Adriano, Chen, Jeffrey, Crabtree, Robert H., Rego, Luis G.  C., & Batista, Victor S. Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces.  United States.  doi:10.1021/acs.jpcc.7b01272.

Copy to clipboard


                    Rudshteyn, Benjamin, Negre, Christian F.  A., Oliboni, Robson S., Monti, Adriano, Chen, Jeffrey, Crabtree, Robert H., Rego, Luis G.  C., and Batista, Victor S. Wed .  
        "Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces".  United States.  doi:10.1021/acs.jpcc.7b01272.  https://www.osti.gov/servlets/purl/1480466.

Copy to clipboard


                    
@article{osti_1480466,

  title        = {Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces},

  author       = {Rudshteyn, Benjamin and Negre, Christian F.  A. and Oliboni, Robson S. and Monti, Adriano and Chen, Jeffrey and Crabtree, Robert H. and Rego, Luis G.  C. and Batista, Victor S.},

  abstractNote = {We explore the protonation states of benzohydroxamic acid adsorbates bound to the {101} facet of TiO2 anatase by using a combination of density functional theory, simulations of UV–vis spectra based on a tight-binding Hamiltonian, and direct comparisons to experimental measurements. We find that the characteristic red-shifted spectrum of nonmethylated, relative to the methylated, hydroxamic acids can only be explained by proposing a monodeprotonated monodentate mode as the main adsorption mode. The reported analysis suggests a simple, yet general, spectroscopic method based on UV–vis absorption measurements and tight-binding calculations for inferring changes of pKa of molecular adsorbates interacting with semiconductor electrode surfaces.},

  doi          = {10.1021/acs.jpcc.7b01272},

  journal      = {Journal of Physical Chemistry. C},

  number       = 22,

  volume       = 121,

  place        = {United States},

  year         = {2017},

  month        = {5}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1021/acs.jpcc.7b01272

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Adsorption mechanism of alkyl hydroxamic acid onto bastnäsite: Fundamental steps toward rational collector design for rare earth elements

Journal Article Wanhala, Anna Kristiina ; Doughty, Benjamin L. ; Bryantsev, Vyacheslav ; ... - Journal of Colloid and Interface Science

Rare earth element (REE) production is limited in part by inefficient strategies for beneficiation. Hydroxamic acid ligands are promising reagents for the selective flotation of bastnäsite [(Ce,La)FCO ₃], a major REE ore mineral, but the mechanism and energetics of adsorption are not understood, interfering with the design of new, more efficient reagents. In this work, the adsorption of octyl hydroxamic acid onto bastnäsite was calculated using a combination of experimental and computational methods. In-situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy revealed changes in the hydroxamate functional group vibrational frequencies, corresponding to chelation with cerium cations at the bastnäsitemore »« less
DOI: 10.1016/j.jcis.2019.06.025
The adsorption of α-cyanoacrylic acid on anatase TiO{sub 2} (101) and (001) surfaces: A density functional theory study

Journal Article Ma, Jin-Gang ; Gong, Ji-Jun ; Zhang, Hai-Min ; ... - Journal of Chemical Physics

The adsorption of α-cyanoacrylic acid (CAA) on anatase TiO{sub 2} (101) and (001) surfaces, including adsorption energies, structures, and electronic properties, have been studied by means of density functional theory calculations in connection with ultrasoft pseudopotential and generalized gradient approximation based upon slab models. The most stable structure of CAA on anatase TiO{sub 2} (101) surface is the dissociated bidentate configuration where the cyano N and carbonyl O bond with two adjacent surface Ti atoms along [010] direction and the dissociated H binds to the surface bridging O which connects the surface Ti bonded with carbonyl O. While for themore »« less
DOI: 10.1063/1.4903790
Kinetics and Mechanism of Methanol Conversion over Anatase Titania Nanoshapes

Journal Article Foo, Guo Shiou ; Hu, Guoxiang ; Hood, Zachary D. ; ... - ACS Catalysis

The kinetics and mechanism of methanol dehydration, redox, and oxidative coupling were explored at 300 °C under dilute oxygen concentration over anatase TiO ₂ nanoplates and truncated-bipyramidal nanocrystals in order to understand the surface structure effect of TiO ₂. The two TiO ₂ nanoshapes displayed both (001) and (101) facets, with a higher fraction of the (001) facet exposed on the nanoplates, while truncated-bipyramidal nanocrystals were dominated by the (101) facet. A kinetic study using in situ titration with ammonia reflects that the active sites for methanol dehydration are acidic and nonequivalent in comparison to redox and oxidative coupling. Inmore »« less
Cited by 4
DOI: 10.1021/acscatal.7b01456

Full Text Available
Comparing Quasiparticle H ₂O Level Alignment on Anatase and Rutile TiO ₂

Journal Article Sun, Huijuan ; Mowbray, Duncan J. ; Migani, Annapaola ; ... - ACS Catalysis, 5(7):4242–4254

Knowledge of the alignment of molecular frontier levels in the ground state can be used to predict the photocatalytic activity of an interface. The position of the adsorbate’s highest occupied molecular orbital (HOMO) levels relative to the substrate’s valence band maximum (VBM) in the interface describes the favorability of photogenerated hole transfer from the VBM to the adsorbed molecule. This is a key quantity for assessing and comparing H ₂O photooxidation activities on two prototypical photocatalytic TiO ₂ surfaces: anatase (A)-TiO ₂(101) and rutile (R)-TiO ₂(110). Using the projected density of states (DOS) from state-of-the-art quasiparticle (QP) G ₀W ₀more »« less
DOI: 10.1021/acscatal.5b00529
Interfacial electron transfer dynamics of ru(II)-polypy6ridine sensitized TiO2

Journal Article Jakubikova, Elena ; Martin, Richard L ; Batista, Enrique R ; ... - Journal of Physical Chemistry A

Quantum dynamics simulations combined with density functional theory calculations are applied to study interfacial electron transfer (IET) from pyridine-4-phosphonic acid, [Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 2+} and [Ru(tpy)(bpy)(H{sub 2}O)-Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 4+} into the (101) surface of anatase TiO{sub 2}. IET rate from pyridine-4-phosphonic acid attached to the nanoparticle in bidentate mode ({tau} {approx} 100 fs) is an order of magnitude faster than the IET rate of the adsorbate attached in the monodentate mode ({tau} {approx} 1 ps). Upon excitation with visible light, [Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 2+} attached to TiO{sub 2} in bidentate binding mode will undergo IET with the rate ofmore »« less
DOI: 10.1021/jp903966n

Full Text Available

Similar Records

Title: Inferring Protonation States of Hydroxamate Adsorbates on TiO 2 Surfaces

Abstract

Citation Formats

Title: Inferring Protonation States of Hydroxamate Adsorbates on TiO ₂ Surfaces