Elucidating the bimodal acid-base behavior of the water-silica interface from first principles

Journal of the American Chemical Society
Kevin LeungLouise J Criscenti

Abstract

Understanding the acid-base behavior of silica surfaces is critical for many nanoscience and bionano interface applications. Silanol groups (SiOH) on silica surfaces exhibit two acidity constants-one as acidic as vinegar-but their structural basis remains controversial. The atomic details of the more acidic silanol site govern not just the overall surface charge density at near neutral solution pH but also how ions and biomolecules interact with and bind to silica immersed in water. Using ab initio molecular dynamics simulations and multiple representative crystalline silica surfaces, we determine the deprotonation free energies of silanol groups with different structural motifs. We show that previously proposed motifs related to chemical connectivity or intersilanol hydrogen bonds do not yield high acidity. Instead, a plausible candiate for pK(a) = 4.5 silanol groups may be found in locally strained or defected regions with sparse silanol coverage. In the process, irreversible ring-opening reactions of strained silica trimer rings in contact with liquid water are observed.

References

Oct 15, 1996·Physical Review. B, Condensed Matter·G Kresse, J Furthmüller
Nov 25, 1985·Physical Review Letters·R Car, M Parrinello
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Mar 17, 2001·Science·P L GeisslerM Parrinello
Sep 25, 2002·Proceedings of the National Academy of Sciences of the United States of America·Alessandro Laio, Michele Parrinello
Jul 15, 2003·Physical Review Letters·Marcella IannuzziMichele Parrinello
Jan 31, 2004·Science·I-Feng W Kuo, Christopher J Mundy
Apr 20, 2004·Physical Review Letters·Jianjun YangE G Wang
Aug 25, 2004·Physical Review Letters·Derek SteinCees Dekker
Oct 21, 2004·Journal of the American Chemical Society·Yi FuDaniel A Higgins
Nov 17, 2004·Langmuir : the ACS Journal of Surfaces and Colloids·Irene LiMary Jane Shultz
Feb 11, 2005·Journal of the American Chemical Society·Josephine P O'ReillyAndrew M Shaw
Mar 24, 2005·Physical Review Letters·Victor OstroverkhovY R Shen
Aug 24, 2005·Langmuir : the ACS Journal of Surfaces and Colloids·Xuejun WangPaul W Bohn
Feb 14, 2006·The Journal of Physical Chemistry. B·Pedro E M LopesAlexander D Mackerell
Mar 24, 2006·The Journal of Physical Chemistry. B·Ivaylo IvanovMichael L Klein
Apr 12, 2006·Physical Review Letters·Kevin LeungChristian D Lorenz
Apr 13, 2006·Chemical Reviews·Kenneth B Eisenthal
Jul 21, 2006·The Journal of Physical Chemistry. B·Jeffrey P FittsKenneth B Eisenthal
Jul 21, 2006·The Journal of Physical Chemistry. B·Shuichi TakaharaMarie-Claire Bellissent-Funel
Jul 21, 2006·The Journal of Physical Chemistry. B·Jonathan D FiskAndrew M Shaw
Aug 31, 2006·Journal of the American Chemical Society·Jung Mee ParkMichele Parrinello
Oct 27, 2006·The Journal of Physical Chemistry. B·Eduardo R Cruz-ChuKlaus Schulten
Sep 7, 2007·The Journal of Physical Chemistry. B·Ali A Hassanali, Sherwin J Singer
Jan 24, 2008·Journal of the American Chemical Society·Giancarlo CiceroGiulia Galli
Feb 26, 2008·Nature Materials·Rong FanPeidong Yang
Mar 4, 2008·Journal of the American Chemical Society·Konstantin N Kudin, Roberto Car
May 22, 2008·Journal of the American Chemical Society·Luning ZhangY Ron Shen
Oct 4, 2008·Journal of the American Chemical Society·Nisanth N NairDominik Marx
Nov 14, 2008·Journal of the American Chemical Society·Julianne M Gibbs-DavisFranz M Geiger
Mar 12, 2009·Langmuir : the ACS Journal of Surfaces and Colloids·Shuangyan XuStephen H Garofalini
Jun 25, 2009·The Journal of Chemical Physics·Li-Min LiuAngelos Michaelides
Jul 9, 2009·Journal of the American Chemical Society·Shikha Nangia, Barbara J Garrison
Feb 4, 2010·The Journal of Physical Chemistry. C, Nanomaterials and Interfaces·Eduardo R Cruz-ChuKlaus Schulten
Mar 12, 2010·Journal of Computational and Theoretical Nanoscience·Kevin Leung, Susan B Rempe

❮ Previous
Next ❯

Citations

Sep 10, 2013·Journal of Colloid and Interface Science·Philippe LeroyMohamed Bizi
Sep 9, 2011·Journal of the American Chemical Society·Nicolas FollietThierry Azaïs
Jun 15, 2011·Journal of the American Chemical Society·Damien BoudinetAntonio Facchetti
Jun 5, 2010·Journal of the American Chemical Society·Federico ZipoliAnnabella Selloni
Jun 9, 2011·Langmuir : the ACS Journal of Surfaces and Colloids·A A SkeltonP T Cummings
Jul 19, 2012·Physical Chemistry Chemical Physics : PCCP·Jun Cheng, Michiel Sprik
Jun 22, 2012·Journal of Environmental Monitoring : JEM·Christoffer J Goffinet, Sara E Mason
Feb 12, 2014·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Ali A HassanaliMichele Parrinello
Sep 22, 2015·Langmuir : the ACS Journal of Surfaces and Colloids·Xiaolin WangThibaud Coradin
May 28, 2016·Chemical Reviews·Olle BjörneholmHendrik Bluhm
Jun 11, 2016·Langmuir : the ACS Journal of Surfaces and Colloids·Nalvi DuroSameer Varma
Aug 24, 2016·Journal of Colloid and Interface Science·Jihoon SeoUngyu Paik
Apr 11, 2017·Analytical Sciences : the International Journal of the Japan Society for Analytical Chemistry·Shinya TaguchiNaoki Matsuda
Oct 13, 2015·Physical Chemistry Chemical Physics : PCCP·Filomena SanninoSerena Esposito
Jun 22, 2017·Langmuir : the ACS Journal of Surfaces and Colloids·Sabrina ValettiMartin Trulsson
Sep 12, 2018·Chemical Society Reviews·Lukáš GrajciarPetr Nachtigall
Mar 8, 2012·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Kevin Leung, Louise J Criscenti
May 28, 2014·Journal of Physics. Condensed Matter : an Institute of Physics Journal·J Cheng, M Sprik
Nov 8, 2014·Physical Chemistry Chemical Physics : PCCP·Xiandong LiuRucheng Wang
Sep 8, 2019·The Journal of Chemical Physics·Toshinori Suzuki
Mar 8, 2012·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Marie-Pierre GaigeotMarialore Sulpizi
Jul 8, 2017·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Kevin Leung, Louise J Criscenti
May 28, 2014·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Md Shafiul AzamJulianne M Gibbs-Davis
Oct 28, 2016·Physical Chemistry Chemical Physics : PCCP·B M LoweN G Green
Jul 22, 2017·Science·Carlos Macias-RomeroSylvie Roke
May 24, 2019·The Journal of Chemical Physics·Grace E Purnell, Robert A Walker
Dec 7, 2014·Journal of Materials Chemistry. B, Materials for Biology and Medicine·Sanghoon KimAndreea Pasc
Jun 9, 2016·Nanotechnology·Jean-Pierre CloarecAbdelkader Souifi
Mar 3, 2019·The Journal of Chemical Physics·Dolores MelgarNiall J English
Jan 24, 2020·The Journal of Chemical Physics·Dilini Singappuli-Arachchige, Igor I Slowing
May 28, 2014·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Álvaro CimasDominique Costa
Oct 25, 2020·Proceedings of the National Academy of Sciences of the United States of America·Cristina PavanBice Fubini

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Related Papers

Journal of Physics. Condensed Matter : an Institute of Physics Journal
Kevin Leung, Louise J Criscenti
Advances in Colloid and Interface Science
Sudam K ParidaB K Mishra
The Journal of Physical Chemistry. a
Masoud AryanpourJames D Kubicki
Proceedings of the National Academy of Sciences of the United States of America
James R Rustad, Piotr Zarzycki
© 2022 Meta ULC. All rights reserved