Spontaneous liquid water dissociation on hybridised boron nitride and graphene atomic layers from <i>ab initio</i> molecular dynamics simulations

Grosjean, Benoît; Robert, Anton; Vuilleumier, Rodolphe; Bocquet, Marie‐Laure

doi:10.1039/c9cp06765e

Cited by 8 publications

(6 citation statements)

References 55 publications

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“…Apart from such genuine chemical wall effects on confined aqueous solutions, it remains to be investigated in future work whether this enhancement of water self-dissociation in extreme planar confinement versus bulk exists not only at high temperatures and pressures but over a wider range of thermodynamic conditions, in particular taking into account the previous findings regarding the temperature dependence of the dielectric tensor components in CNTs …”

Section: Confinement-controlled Self-dissociation Of Watermentioning

confidence: 96%

“…Moreover, the decrease of the autodissociation free energy barrier Δ F ⧧ due to nanoconfinement of water at 500 K (and 20 MPa), being almost equal to that found when reducing the temperature from 500 to 350 K in isotropic bulk water (at 20 MPa), implies an even greater reduction of the p K w value because of the higher thermal energy k B T at 500 K than at 350 K, recalling that p K w ≈ – 2.303Δ F ⧧ / k B T . In contrast to such chemically inert slit pores, water self-dissociation could be furthermore affected by the presence of defects, substitutions, or 2D heterostructures, e.g., in the realm of graphene or hBN nanostructures, which in conjunction with the effects of nanoconfinement on autoprotolysis just exposed opens up an exciting additional dimension for modulating the pH of nanoconfined aqueous solutions.…”

Section: Confinement-controlled Self-dissociation Of Watermentioning

confidence: 99%

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Confinement-Controlled Aqueous Chemistry within Nanometric Slit Pores

Muñoz‐Santiburcio

Marx

2021

Chem. Rev.

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In this Focus Review, we put the spotlight on very recent insights into the fascinating world of wet chemistry in the realm offered by nanoconfinement of water in mechanically rather rigid and chemically inert planar slit pores wherein only monolayer and bilayer water lamellae can be hosted. We review the effect of confinement on different aspects such as hydrogen bonding, ion diffusion, and charge defect migration of H + (aq) and OH − (aq) in nanoconfined water depending on slit pore width. A particular focus is put on the strongly modulated local dielectric properties as quantified in terms of anisotropic polarization fluctuations across such extremely confined water films and their putative effects on chemical reactions therein. The stunning findings disclosed only recently extend wet chemistry in particular and solvation science in general toward extreme molecular confinement conditions.

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Section: Confinement-controlled Self-dissociation Of Watermentioning

confidence: 96%

Section: Confinement-controlled Self-dissociation Of Watermentioning

confidence: 99%

Confinement-Controlled Aqueous Chemistry within Nanometric Slit Pores

Muñoz‐Santiburcio

Marx

2021

Chem. Rev.

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“…Grosjean performed ab initio MD on the aqueous reactivity of hybridized monolayers formed by joining BN and GR sheets. They observed the spontaneous chemisorption and dissociation of interfacial water molecules into its self-ions, and therefore they predict that this type of heterostructure is prone to ionize liquid water already in the absence of any electrical gating . Furthermore, Marx et al have performed extensive ab initio simulations on the chemistry and dynamics of nanoconfined water including hydrogen bonds, dissociation, proton transfer, etc. , However, an extension of direct first-principles simulations to long time and length scales has remained a formidable challenge.…”

mentioning

confidence: 99%

Insights into Water Permeation through hBN Nanocapillaries by Ab Initio Machine Learning Molecular Dynamics Simulations

Ghorbanfekr-Kalashami

Behler

Peeters

2020

J. Phys. Chem. Lett.

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Water permeation between stacked layers of hBN sheets forming 2D nanochannels is investigated using large-scale ab initio-quality molecular dynamics simulations. A high-dimensional neural network potential trained on densityfunctional theory calculations is employed. We simulate water in van der Waals nanocapillaries and study the impact of nanometric confinement on the structure and dynamics of water using both equilibrium and nonequilibrium methods. At an interlayer distance of 10.2 Å confinement induces a first-order phase transition resulting in a well-defined AA-stacked bilayer of hexagonal ice. In contrast, for h < 9 Å, the 2D water monolayer consists of a mixture of different locally ordered patterns of squares, pentagons, and hexagons. We found a significant change in the transport properties of confined water, particularly for monolayer water where the water−solid friction coefficient decreases to half and the diffusion coefficient increases by a factor of 4 as compared to bulk water. Accordingly, the slip-velocity is found to increase under confinement and we found that the overall permeation is dominated by monolayer water adjacent to the hBN membranes at extreme confinements. We conclude that monolayer water in addition to bilayer ice has a major contribution to water transport through 2D nanochannels.

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“…Similarly, water self-dissociation is greatly enhanced under confinements due to increase in parallel component of the dielectric tensor, stabilizing H + and OH – ions . Water self-dissociation could be furthermore altered by the surface defects, heterogeneities, or thermodynamic conditions . However, extreme nanoconfinements (e.g., pore size <1 nm), could destabilize the formation of proton and hydroxide ions from water due to severe restriction on H-bond topology .…”

Section: Resultsmentioning

confidence: 99%

Effects of Surface Hydrophilicity and Heterogeneity on CO₂ Conversion to H₂CO₃ in the Nanopores of Layered Materials

Dasgupta,

Ho,

Rempe

et al. 2024

J. Phys. Chem. C

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CO 2 conversion to H 2 CO 3 in water is an important reaction in many environmental and industrial processes, including CO 2 capture and storage. While this conversion reaction is wellstudied in bulk water, it has been poorly investigated in confined water. Here we study the conversion reaction of CO 2 to H 2 CO 3 in hydrophilic gibbsite and heterogeneous (hydrophilic/hydrophobic) Na-beidellite nanopores. We calculate the free energy of the reaction in the nanopores formed from these materials using ReaxFF metadynamics molecular simulations. We find that, regardless of the nature of the surfaces in these geological nanopores, both the activation free energy barrier and free energy of the reaction decrease compared to the reaction in the bulk environment. The activation free energy barrier is found to be higher in hydrophilic gibbsite and heterogeneous beidellite nanopores compared to the hydrophobic pyrophyllite nanopore. We observe the free energy of activation and reaction decrease with decreased pore size and surface hydrophobicity, favoring the formation of H 2 CO 3 . The water coordination structures obtained at reactant, product, and transition state basins support our free energy interpretations. The impeding factors in heterogeneous nanoconfinement for the formation of carbonic acid from carbon dioxide are interlayer cations and surface charge, whereas it is the surface hydroxyls for hydrophilic nanoconfinement.

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Spontaneous liquid water dissociation on hybridised boron nitride and graphene atomic layers from ab initio molecular dynamics simulations

Abstract: By means of ab initio simulations we unveil the high reactivity of boron nitride–graphene planar heterostructure immersed in liquid water: an interfacial water molecule is found to spontaneously chemisorb and deprotonate at one composite border.

Cited by 8 publications

References 55 publications

Confinement-Controlled Aqueous Chemistry within Nanometric Slit Pores

Confinement-Controlled Aqueous Chemistry within Nanometric Slit Pores

Insights into Water Permeation through hBN Nanocapillaries by Ab Initio Machine Learning Molecular Dynamics Simulations

Effects of Surface Hydrophilicity and Heterogeneity on CO₂ Conversion to H₂CO₃ in the Nanopores of Layered Materials

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Spontaneous liquid water dissociation on hybridised boron nitride and graphene atomic layers from ab initio molecular dynamics simulations

Abstract: By means of ab initio simulations we unveil the high reactivity of boron nitride–graphene planar heterostructure immersed in liquid water: an interfacial water molecule is found to spontaneously chemisorb and deprotonate at one composite border.

Cited by 8 publications

References 55 publications

Confinement-Controlled Aqueous Chemistry within Nanometric Slit Pores

Confinement-Controlled Aqueous Chemistry within Nanometric Slit Pores

Insights into Water Permeation through hBN Nanocapillaries by Ab Initio Machine Learning Molecular Dynamics Simulations

Effects of Surface Hydrophilicity and Heterogeneity on CO2 Conversion to H2CO3 in the Nanopores of Layered Materials

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Product

Resources

About

Effects of Surface Hydrophilicity and Heterogeneity on CO₂ Conversion to H₂CO₃ in the Nanopores of Layered Materials