skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Surface structure and stability of partially hydroxylated silica surfaces

Abstract

Surface energies of silicates influence crack propagation during brittle fracture and decrease with surface relaxation caused by annealing and hydroxylation. Molecular-level simulations are particularly suited for the investigation of surface processes. In this work, classical MD simulations of silica surfaces are performed with two force fields (ClayFF and ReaxFF) to investigate the effect of force field reactivity on surface structure and energy as a function of surface hydroxylation. An unhydroxylated fracture surface energy of 5.1 J/m 2 is calculated with the ClayFF force field, and 2.0 J/m 2 is calculated for the ReaxFF force field. The ClayFF surface energies are consistent with the experimental results from double cantilever beam fracture tests (4.5 J/m 2), whereas ReaxFF underestimated these surface energies. Surface relaxation via annealing and hydroxylation was performed by creating a low-energy equilibrium surface. Annealing condensed neighboring siloxane bonds increased the surface connectivity, and decreased the surface energies by 0.2 J/m 2 for ClayFF and 0.8 J/m 2 for ReaxFF. Posthydroxylation surface energies decreased further to 4.6 J/m 2 with the ClayFF force field and to 0.2 J/m 2 with the ReaxFF force field. Experimental equilibrium surface energies are ~0.35 J/m 2, consistent with the ReaxFF force field. Although neithermore » force field was capable of replicating both the fracture and equilibrium surface energies reported from experiment, each was consistent with one of these conditions. Furthermore, future computational investigations that rely on accurate surface energy values should consider the surface state of the system and select the appropriate force field.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Sandia National Laboratories, Livermore, CA
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1356827
Report Number(s):
SAND2017-2690J
Journal ID: ISSN 0743-7463; 651669
Grant/Contract Number:
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 33; Journal Issue: 15; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Rimsza, J. M., Jones, R. E., and Criscenti, L. J. Surface structure and stability of partially hydroxylated silica surfaces. United States: N. p., 2017. Web. doi:10.1021/acs.langmuir.7b00041.
Rimsza, J. M., Jones, R. E., & Criscenti, L. J. Surface structure and stability of partially hydroxylated silica surfaces. United States. doi:10.1021/acs.langmuir.7b00041.
Rimsza, J. M., Jones, R. E., and Criscenti, L. J. Tue . "Surface structure and stability of partially hydroxylated silica surfaces". United States. doi:10.1021/acs.langmuir.7b00041. https://www.osti.gov/servlets/purl/1356827.
@article{osti_1356827,
title = {Surface structure and stability of partially hydroxylated silica surfaces},
author = {Rimsza, J. M. and Jones, R. E. and Criscenti, L. J.},
abstractNote = {Surface energies of silicates influence crack propagation during brittle fracture and decrease with surface relaxation caused by annealing and hydroxylation. Molecular-level simulations are particularly suited for the investigation of surface processes. In this work, classical MD simulations of silica surfaces are performed with two force fields (ClayFF and ReaxFF) to investigate the effect of force field reactivity on surface structure and energy as a function of surface hydroxylation. An unhydroxylated fracture surface energy of 5.1 J/m2 is calculated with the ClayFF force field, and 2.0 J/m2 is calculated for the ReaxFF force field. The ClayFF surface energies are consistent with the experimental results from double cantilever beam fracture tests (4.5 J/m2), whereas ReaxFF underestimated these surface energies. Surface relaxation via annealing and hydroxylation was performed by creating a low-energy equilibrium surface. Annealing condensed neighboring siloxane bonds increased the surface connectivity, and decreased the surface energies by 0.2 J/m2 for ClayFF and 0.8 J/m2 for ReaxFF. Posthydroxylation surface energies decreased further to 4.6 J/m2 with the ClayFF force field and to 0.2 J/m2 with the ReaxFF force field. Experimental equilibrium surface energies are ~0.35 J/m2, consistent with the ReaxFF force field. Although neither force field was capable of replicating both the fracture and equilibrium surface energies reported from experiment, each was consistent with one of these conditions. Furthermore, future computational investigations that rely on accurate surface energy values should consider the surface state of the system and select the appropriate force field.},
doi = {10.1021/acs.langmuir.7b00041},
journal = {Langmuir},
number = 15,
volume = 33,
place = {United States},
year = {Tue Apr 04 00:00:00 EDT 2017},
month = {Tue Apr 04 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

Save / Share:
  • The reactions of molecular oxygen with bridging hydroxyl groups, OHb, formed by H2O dissociation on bridging oxygen vacancies of TiO2 (110) are studied at low and high OHb coverages as a function of the O2 exposure, using scanning tunneling microscopy (STM), temperature programmed desorption (TPD), and electron simulated desorption (ESD) techniques. On partially hydroxylated surfaces, the sudden simultaneous disappearance of oxygen vacancies and oxygen adatoms formed by O2 dissociation is observed at high O2 exposures. On fully hydroxylated TiO2 surfaces, which enable us to compare results of STM, TPD and ESD studies, most of OHb’s are removed via reacting withmore » O2. Hence, fully hydroxylated TiO2 surfaces can be converted to nearly stoichiometric surfaces, albeit with some amount of adsorbed molecular water. Formation of mobile H2O molecules and water-assisted diffusion of the reactants plays an important role in the kinetics of the processes on both partially and fully hydroxylated surfaces.« less
  • The adsorption of Mo(CO){sub 6} on partially dehydroxylated alumina (PDA) and hydroxylated alumina (HA) has been studied using IR and UV-vis spectroscopy. The results from these experiments suggest that the initially physisorbed Mo(CO){sub 6} coordinates to two distinct Lewis acid sites on the surface of PDA, one much more abundant than the other, with an apparent single rate constant 2.3 x 10{sup {minus}3} s{sup {minus}1} at 298 K. The Mo(CO){sub 6}(ads) in turn loses CO reversibly, with an apparent single rate constant 1.8 x 10{sup {minus}4} s{sup {minus}1} at 298 K to form Mo(CO){sub 5}(ads). Upon removal of gas phasemore » CO released in the first step, Mo(CO){sub 5}(ads) loses two additional COs to form Mo(CO){sub 3}(ads). Alternatively, on HA physisorbed Mo(CO){sub 6} undergoes nucleophilic attack by hydroxyl groups, which results in cis-labilization of a carbonyl group, leading in turn to the formation of Mo(CO){sub 5}(L), where L is a surface hydroxyl. The Mo(CO){sub 5}(L) so formed loses additional carbonyls to form a lower subcarbonyl. The decarbonylation process appears to be faster than on PDA. The experimental data indicate that there are no Al{sup 31} exposed on HA. All the observed decarbonylation processes are reversible under CO at room temperature on both HA and PDA. The addition of CO{sub 2} to the subcarbonyl on HA results in the formation of a bicarbonate, with displacement of the subcarbonyls. 24 refs., 11 figs., 1 tab.« less
  • The structure of hydroxylated oxide films (passive films) formed on Cr(110) in 0.5 M H{sub 2}SO{sub 4} at +0.35, +0.55, and +0.75 V/SHE has been investigated by in situ scanning tunneling microscopy (STM). Cathodic reduction pretreatments at {minus}0.54, {minus}0.64, and {minus}0.74 V/SHE destroy the well-defined topography of the single-crystal electrode and they have been excluded from the passivation procedure. Two different passive film structures have been observed, depending on the potential and time of passivation. At low potential (+0.35 V/SHE), the passive film, consisting mostly of chromium hydroxide, has a noncrystalline and granular structure whose roughness suggests local variations ofmore » thickness of ca. {+-} 0.5 nm. A similar structure is observed at higher potential (+0.55 V/SHE), but only for a short polarization time. For longer polarization at 0.55 V/SHE, and at higher potentials (+0.75 V/SHE), a crystalline structure is formed; the higher the potential, the faster the crystallization. It corresponds to the growth of a chromium oxide layer in the passive film. This chromium oxide layer is (0001) oriented. A structural model of the passive film is proposed, with termination of this oxide layer by a monolayer of hydroxyl groups or of chromium hydroxide in (1 {times} 1) epitaxy with the underlying oxide, and with surface steps resulting from the emergence of stacking faults of the Cr{sup 3+} planes in the oxide layer. Energy band models of the electronic structure of the semiconductive passive films show that the tunneling mechanism of the STM imaging involves empty electronic states located in the band gap of the passive film. The growth of the oxide layer in the passive film is governed by a combined reaction of dehydration of chromium hydroxide and oxidation of chromium: Cr(OH){sub 3} (film) + Cr (metal) {yields} Cr{sub 2}O{sub 3} (film) + 3 H{sup +} + 3 e{sup {minus}}.« less
  • The effect of hydroxylation on the surface structure of amorphous alumina is investigated using classical molecular dynamics simulations. It is found that the hydroxylated amorphous alumina surface is terminated by hydroxyl groups singly and doubly coordinated to aluminum. Root-mean-square roughness calculations and density profiles across the film indicate that hydroxylated surfaces are rougher than non-hydroxylated surfaces. The power spectrum identifies different vibrational stretching frequencies for the singly and doubly coordinated surface OH groups. The role of the surface OH groups in surface reactivity is discussed.
  • Silica gel is one of the most widely used components of catalytic systems. This paper simulates the bulk of the SiO/sub 2/ structure, as well as certain sites formed on the SiO/sub 2/ surface. They were simulated with an approach based on a model of a cyclic cluster which is essentially a unit cell with cyclic boundary conditions imposed on its molecular orbitals. This paper also examines the defects on an SiO/sub 2/ surface. The calculated charges on atoms and the energy parameters of cyclic clusters are presented.