Effect of nanoconfinement and pore geometry on point of zero charge in synthesized mesoporous siliceous materials

Andrew T. Jacobson; Chen Chen; Janet C. Dewey; Grant C. Copeland; Wayne T. Allen; Bryony Richards; John P. Kaszuba; Adri C.T. van Duin; Hyeyoung Cho; Milind Deo; Yuqi She; Thomas P. Martin

doi:10.1016/j.jciso.2022.100069

Effect of nanoconfinement and pore geometry on point of zero charge in synthesized mesoporous siliceous materials

Andrew T. Jacobson, Chen Chen, Janet C. Dewey, Grant C. Copeland, Wayne T. Allen, Bryony Richards, John P. Kaszuba, Adri C.T. van Duin, Hyeyoung Cho, Milind Deo, Yuqi She, Thomas P. Martin

Research output: Contribution to journal › Article › peer-review

Abstract

Fluid-rock interactions may differ in mesopores (2–50 nm diameter) compared to macropores (>50 nm diameter). This study evaluates the influence of nano-confinement and pore geometry on point of zero charge (PZC) and hence surface charge and adsorption. PZC was determined for a suite of synthetic mesoporous amorphous silica materials and compared to the PZC of macroporous and non-porous amorphous silica. Reactive molecular dynamics simulations using ReaxFF determined surface equilibrium constants (pK) and clarified the large range of PZC values reported for macroporous and non-porous amorphous silica. Potentiometric titrations measured PZC and pK values of three mesoporous amorphous silica materials (SBA-15, SBA-16, and MCM-41) possessing a range of pore diameters (∼4–13 nm) and distinct pore geometries (cylindrical pores in a hexagonal lattice, spherical pores in a body-centered-cubic lattice, and hexagonal pores arranged in a hexagonal lattice); fluids were pre-saturated with silica to inhibit reaction with pore walls. Results are integrated with data from more than 150 published experimental studies. Neither nano-confinement nor pore geometry affects the PZC of the mesoporous amorphous silica materials. These results have implications for adsorption chemistry under confinement in mesoporous siliceous natural systems such as shales.

Original language	English (US)
Article number	100069
Journal	JCIS Open
Volume	8
DOIs	https://doi.org/10.1016/j.jciso.2022.100069
State	Published - Dec 2022

All Science Journal Classification (ASJC) codes

Materials Chemistry
Surfaces, Coatings and Films
Physical and Theoretical Chemistry
Colloid and Surface Chemistry

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10.1016/j.jciso.2022.100069

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@article{2333a40b0bbf43a9ab14bf8c7c49f752,

title = "Effect of nanoconfinement and pore geometry on point of zero charge in synthesized mesoporous siliceous materials",

abstract = "Fluid-rock interactions may differ in mesopores (2–50 nm diameter) compared to macropores (>50 nm diameter). This study evaluates the influence of nano-confinement and pore geometry on point of zero charge (PZC) and hence surface charge and adsorption. PZC was determined for a suite of synthetic mesoporous amorphous silica materials and compared to the PZC of macroporous and non-porous amorphous silica. Reactive molecular dynamics simulations using ReaxFF determined surface equilibrium constants (pK) and clarified the large range of PZC values reported for macroporous and non-porous amorphous silica. Potentiometric titrations measured PZC and pK values of three mesoporous amorphous silica materials (SBA-15, SBA-16, and MCM-41) possessing a range of pore diameters (∼4–13 nm) and distinct pore geometries (cylindrical pores in a hexagonal lattice, spherical pores in a body-centered-cubic lattice, and hexagonal pores arranged in a hexagonal lattice); fluids were pre-saturated with silica to inhibit reaction with pore walls. Results are integrated with data from more than 150 published experimental studies. Neither nano-confinement nor pore geometry affects the PZC of the mesoporous amorphous silica materials. These results have implications for adsorption chemistry under confinement in mesoporous siliceous natural systems such as shales.",

author = "Jacobson, {Andrew T.} and Chen Chen and Dewey, {Janet C.} and Copeland, {Grant C.} and Allen, {Wayne T.} and Bryony Richards and Kaszuba, {John P.} and {van Duin}, {Adri C.T.} and Hyeyoung Cho and Milind Deo and Yuqi She and Martin, {Thomas P.}",

note = "Funding Information: This work was supported as part of the EFRC-MUSE, an Energy Frontier Research Center funded by the U.S. Department of Energy , Office of Science , Basic Energy Sciences under Award # DE-SC0019285 . We would like to thank a critical review during the revision process for the addition of significant contributions to the manuscript. Publisher Copyright: {\textcopyright} 2022 The Authors",

year = "2022",

month = dec,

doi = "10.1016/j.jciso.2022.100069",

language = "English (US)",

volume = "8",

journal = "JCIS Open",

issn = "2666-934X",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - Effect of nanoconfinement and pore geometry on point of zero charge in synthesized mesoporous siliceous materials

AU - Jacobson, Andrew T.

AU - Chen, Chen

AU - Dewey, Janet C.

AU - Copeland, Grant C.

AU - Allen, Wayne T.

AU - Richards, Bryony

AU - Kaszuba, John P.

AU - van Duin, Adri C.T.

AU - Cho, Hyeyoung

AU - Deo, Milind

AU - She, Yuqi

AU - Martin, Thomas P.

N1 - Funding Information: This work was supported as part of the EFRC-MUSE, an Energy Frontier Research Center funded by the U.S. Department of Energy , Office of Science , Basic Energy Sciences under Award # DE-SC0019285 . We would like to thank a critical review during the revision process for the addition of significant contributions to the manuscript. Publisher Copyright: © 2022 The Authors

PY - 2022/12

Y1 - 2022/12

N2 - Fluid-rock interactions may differ in mesopores (2–50 nm diameter) compared to macropores (>50 nm diameter). This study evaluates the influence of nano-confinement and pore geometry on point of zero charge (PZC) and hence surface charge and adsorption. PZC was determined for a suite of synthetic mesoporous amorphous silica materials and compared to the PZC of macroporous and non-porous amorphous silica. Reactive molecular dynamics simulations using ReaxFF determined surface equilibrium constants (pK) and clarified the large range of PZC values reported for macroporous and non-porous amorphous silica. Potentiometric titrations measured PZC and pK values of three mesoporous amorphous silica materials (SBA-15, SBA-16, and MCM-41) possessing a range of pore diameters (∼4–13 nm) and distinct pore geometries (cylindrical pores in a hexagonal lattice, spherical pores in a body-centered-cubic lattice, and hexagonal pores arranged in a hexagonal lattice); fluids were pre-saturated with silica to inhibit reaction with pore walls. Results are integrated with data from more than 150 published experimental studies. Neither nano-confinement nor pore geometry affects the PZC of the mesoporous amorphous silica materials. These results have implications for adsorption chemistry under confinement in mesoporous siliceous natural systems such as shales.

AB - Fluid-rock interactions may differ in mesopores (2–50 nm diameter) compared to macropores (>50 nm diameter). This study evaluates the influence of nano-confinement and pore geometry on point of zero charge (PZC) and hence surface charge and adsorption. PZC was determined for a suite of synthetic mesoporous amorphous silica materials and compared to the PZC of macroporous and non-porous amorphous silica. Reactive molecular dynamics simulations using ReaxFF determined surface equilibrium constants (pK) and clarified the large range of PZC values reported for macroporous and non-porous amorphous silica. Potentiometric titrations measured PZC and pK values of three mesoporous amorphous silica materials (SBA-15, SBA-16, and MCM-41) possessing a range of pore diameters (∼4–13 nm) and distinct pore geometries (cylindrical pores in a hexagonal lattice, spherical pores in a body-centered-cubic lattice, and hexagonal pores arranged in a hexagonal lattice); fluids were pre-saturated with silica to inhibit reaction with pore walls. Results are integrated with data from more than 150 published experimental studies. Neither nano-confinement nor pore geometry affects the PZC of the mesoporous amorphous silica materials. These results have implications for adsorption chemistry under confinement in mesoporous siliceous natural systems such as shales.

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UR - http://www.scopus.com/inward/citedby.url?scp=85143523958&partnerID=8YFLogxK

U2 - 10.1016/j.jciso.2022.100069

DO - 10.1016/j.jciso.2022.100069

M3 - Article

AN - SCOPUS:85143523958

SN - 2666-934X

VL - 8

JO - JCIS Open

JF - JCIS Open

M1 - 100069

ER -

Effect of nanoconfinement and pore geometry on point of zero charge in synthesized mesoporous siliceous materials

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