Atomic-Scale Understanding of Catalyst Activation: Carboxylic Acid Solutions, but Not the Acid Itself, Increase the Reactivity of Anatase (001) Faceted Nanocatalysts

DeBenedetti, William J.  I.; Skibinski, Erik S.; Jing, Dapeng; Song, Anqi; Hines, Melissa A.

doi:10.1021/acs.jpcc.7b11054

Title: Atomic-Scale Understanding of Catalyst Activation: Carboxylic Acid Solutions, but Not the Acid Itself, Increase the Reactivity of Anatase (001) Faceted Nanocatalysts

Abstract

Our ability to predict nanocatalyst reactivity has been hindered by our lack of atomic-scale understanding of nanocatalyst surface structure. Do nanocatalyst surfaces adopt a bulk-terminated structure or do they reconstruct to minimize their free energy, thereby lowering their reactivity as often observed in vacuum? Similarly, do nanocatalysts processed at high temperatures maintain their low reactivity, reconstructed surfaces when used at low temperatures? Using a new technique for the preparation of anatase nanocatalysts suitable for atomic-scale imaging and surface spectroscopy, we show that solution-prepared anatase is terminated by a monolayer of fluorine, which acts as an atomic-scale oleophobic coating, preventing the accumulation of adventitious carbon. We further show that the most common TiO₂ functionalization chemistry, a carboxylic acid solution, causes the spontaneous reorganization of a reconstructed anatase nanocatalyst, leading to a five-fold increase in reactive sites. This reorganization is not observed when carboxylic acids are deposited from the gas phase, suggesting that model experiments in vacuum environments can lead to a nonequilibrium, kinetically trapped state that may not be catalytically relevant. Aqueous carboxylic acid solutions produce densely packed carboxylate monolayers with richer adsorption geometries than previously predicted. Ab initio simulations show that although the carboxylate termination is somewhat less effective atmore »« less

Authors:

DeBenedetti, William J. I. ^[1]; Skibinski, Erik S. ^[1];

^[1]; Song, Anqi ^[1];

^[1]

Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology

Publication Date:: 2018-02-08

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); National Science Foundation (NSF)

OSTI Identifier:: 1483673

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 8; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    DeBenedetti, William J.  I., Skibinski, Erik S., Jing, Dapeng, Song, Anqi, and Hines, Melissa A. Atomic-Scale Understanding of Catalyst Activation: Carboxylic Acid Solutions, but Not the Acid Itself, Increase the Reactivity of Anatase (001) Faceted Nanocatalysts.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcc.7b11054.

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                    DeBenedetti, William J.  I., Skibinski, Erik S., Jing, Dapeng, Song, Anqi, & Hines, Melissa A. Atomic-Scale Understanding of Catalyst Activation: Carboxylic Acid Solutions, but Not the Acid Itself, Increase the Reactivity of Anatase (001) Faceted Nanocatalysts.  United States.  https://doi.org/10.1021/acs.jpcc.7b11054

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                    DeBenedetti, William J.  I., Skibinski, Erik S., Jing, Dapeng, Song, Anqi, and Hines, Melissa A. Thu .  
"Atomic-Scale Understanding of Catalyst Activation: Carboxylic Acid Solutions, but Not the Acid Itself, Increase the Reactivity of Anatase (001) Faceted Nanocatalysts".  United States.  https://doi.org/10.1021/acs.jpcc.7b11054.  https://www.osti.gov/servlets/purl/1483673.

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@article{osti_1483673,

  title        = {Atomic-Scale Understanding of Catalyst Activation: Carboxylic Acid Solutions, but Not the Acid Itself, Increase the Reactivity of Anatase (001) Faceted Nanocatalysts},

  author       = {DeBenedetti, William J.  I. and Skibinski, Erik S. and Jing, Dapeng and Song, Anqi and Hines, Melissa A.},

  abstractNote = {Our ability to predict nanocatalyst reactivity has been hindered by our lack of atomic-scale understanding of nanocatalyst surface structure. Do nanocatalyst surfaces adopt a bulk-terminated structure or do they reconstruct to minimize their free energy, thereby lowering their reactivity as often observed in vacuum? Similarly, do nanocatalysts processed at high temperatures maintain their low reactivity, reconstructed surfaces when used at low temperatures? Using a new technique for the preparation of anatase nanocatalysts suitable for atomic-scale imaging and surface spectroscopy, we show that solution-prepared anatase is terminated by a monolayer of fluorine, which acts as an atomic-scale oleophobic coating, preventing the accumulation of adventitious carbon. We further show that the most common TiO2 functionalization chemistry, a carboxylic acid solution, causes the spontaneous reorganization of a reconstructed anatase nanocatalyst, leading to a five-fold increase in reactive sites. This reorganization is not observed when carboxylic acids are deposited from the gas phase, suggesting that model experiments in vacuum environments can lead to a nonequilibrium, kinetically trapped state that may not be catalytically relevant. Aqueous carboxylic acid solutions produce densely packed carboxylate monolayers with richer adsorption geometries than previously predicted. Ab initio simulations show that although the carboxylate termination is somewhat less effective at removing surface stress than the reconstruction, it is more effective in lowering the surface energy. This observation suggests that bulk-terminated metal-oxide nanocrystals may be common in reactive environments, even if high temperatures are used to process the nanocatalyst or if the reactant is later rinsed off. As such, the assumption of a bulk-terminated surface may be a reasonable starting point for “materials-by-design” approaches to computationally engineered nanocatalysts.},

  doi          = {10.1021/acs.jpcc.7b11054},

  journal      = {Journal of Physical Chemistry. C},

  number       = 8,

  volume       = 122,

  place        = {United States},

  year         = {2018},

  month        = {2}

}

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https://doi.org/10.1021/acs.jpcc.7b11054

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Figure 1: (a) Side and (b) top views of bulk-terminated anatase (001) . The Ti and O atoms are blue and red. (c) Side view of (1 × 4) reconstructed anatase with red arrows indicating stress relaxation. The numbers in (a, c) indicate Ti–O–Ti bond angles. The Ti–O–Ti bond anglemore »

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