Membrane Charge Effects on Solute Transport in Nanofiltration: Experiments and Molecular Dynamics Simulations
Polyamide membranes, such as nanofiltration (NF) membranes, are widely used for water purification. However, the mechanisms of solute transport and solute rejection due to solute charge interactions with the membrane remain unclear at the molecular level. Here, we use molecular dynamics simulations...
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2025-06-01
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| author | Suwei Liu Zihao Foo John H. Lienhard Sinan Keten Richard M. Lueptow |
| author_facet | Suwei Liu Zihao Foo John H. Lienhard Sinan Keten Richard M. Lueptow |
| author_sort | Suwei Liu |
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| description | Polyamide membranes, such as nanofiltration (NF) membranes, are widely used for water purification. However, the mechanisms of solute transport and solute rejection due to solute charge interactions with the membrane remain unclear at the molecular level. Here, we use molecular dynamics simulations to examine the transport of single-solute feeds through charged nanofiltration membranes with different membrane charge concentrations of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mi>COO</mi><mo>−</mo></msup></mrow></semantics></math></inline-formula> and NH<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mmultiscripts><mspace width="-0.166667em"></mspace><none></none><mo>+</mo><mprescripts></mprescripts><mn>2</mn><none></none></mmultiscripts></mrow></semantics></math></inline-formula> resulting from the deprotonation or protonation of polymeric end groups according to the pH level that the membrane experiences. The results show that <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mi>Na</mi><mo>+</mo></msup></mrow></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mi>Cl</mi><mo>−</mo></msup></mrow></semantics></math></inline-formula> solute ions are better rejected when the membrane has a higher concentration of negatively charged groups, corresponding to a higher pH, whereas <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mi>CaCl</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> is well rejected at all pH levels studied. These results are consistent with those of experiments performed at the same pH conditions as the simulation setup. Moreover, solute transport behavior depends on the membrane functional group distribution. When <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mi>COO</mi><mo>−</mo></msup></mrow></semantics></math></inline-formula> functional groups are concentrated at membrane feed surface, ion permeation into the membrane is reduced. Counter-ions tend to associate with charged functional groups while co-ions seem to pass by the charged groups more easily. In addition, steric effects play a role when ions of opposite charge cluster in pores of the membrane. This study reveals solute transport and rejection mechanisms related to membrane charge and provides insights into how membranes might be designed to achieve specific desired solute rejection. |
| format | Article |
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| institution | DOAJ |
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| publishDate | 2025-06-01 |
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| spelling | doaj-art-b515700a133146269ccb4ff3deefa6a12025-08-20T03:16:34ZengMDPI AGMembranes2077-03752025-06-0115618410.3390/membranes15060184Membrane Charge Effects on Solute Transport in Nanofiltration: Experiments and Molecular Dynamics SimulationsSuwei Liu0Zihao Foo1John H. Lienhard2Sinan Keten3Richard M. Lueptow4Department of Mechanical Engineering, Northwestern University, Evanston, IL 60208, USADepartment of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USADepartment of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USADepartment of Mechanical Engineering, Northwestern University, Evanston, IL 60208, USADepartment of Mechanical Engineering, Northwestern University, Evanston, IL 60208, USAPolyamide membranes, such as nanofiltration (NF) membranes, are widely used for water purification. However, the mechanisms of solute transport and solute rejection due to solute charge interactions with the membrane remain unclear at the molecular level. Here, we use molecular dynamics simulations to examine the transport of single-solute feeds through charged nanofiltration membranes with different membrane charge concentrations of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mi>COO</mi><mo>−</mo></msup></mrow></semantics></math></inline-formula> and NH<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mmultiscripts><mspace width="-0.166667em"></mspace><none></none><mo>+</mo><mprescripts></mprescripts><mn>2</mn><none></none></mmultiscripts></mrow></semantics></math></inline-formula> resulting from the deprotonation or protonation of polymeric end groups according to the pH level that the membrane experiences. The results show that <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mi>Na</mi><mo>+</mo></msup></mrow></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mi>Cl</mi><mo>−</mo></msup></mrow></semantics></math></inline-formula> solute ions are better rejected when the membrane has a higher concentration of negatively charged groups, corresponding to a higher pH, whereas <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mi>CaCl</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> is well rejected at all pH levels studied. These results are consistent with those of experiments performed at the same pH conditions as the simulation setup. Moreover, solute transport behavior depends on the membrane functional group distribution. When <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mi>COO</mi><mo>−</mo></msup></mrow></semantics></math></inline-formula> functional groups are concentrated at membrane feed surface, ion permeation into the membrane is reduced. Counter-ions tend to associate with charged functional groups while co-ions seem to pass by the charged groups more easily. In addition, steric effects play a role when ions of opposite charge cluster in pores of the membrane. This study reveals solute transport and rejection mechanisms related to membrane charge and provides insights into how membranes might be designed to achieve specific desired solute rejection.https://www.mdpi.com/2077-0375/15/6/184molecular dynamicssolute transportwater filtrationnanofiltration |
| spellingShingle | Suwei Liu Zihao Foo John H. Lienhard Sinan Keten Richard M. Lueptow Membrane Charge Effects on Solute Transport in Nanofiltration: Experiments and Molecular Dynamics Simulations Membranes molecular dynamics solute transport water filtration nanofiltration |
| title | Membrane Charge Effects on Solute Transport in Nanofiltration: Experiments and Molecular Dynamics Simulations |
| title_full | Membrane Charge Effects on Solute Transport in Nanofiltration: Experiments and Molecular Dynamics Simulations |
| title_fullStr | Membrane Charge Effects on Solute Transport in Nanofiltration: Experiments and Molecular Dynamics Simulations |
| title_full_unstemmed | Membrane Charge Effects on Solute Transport in Nanofiltration: Experiments and Molecular Dynamics Simulations |
| title_short | Membrane Charge Effects on Solute Transport in Nanofiltration: Experiments and Molecular Dynamics Simulations |
| title_sort | membrane charge effects on solute transport in nanofiltration experiments and molecular dynamics simulations |
| topic | molecular dynamics solute transport water filtration nanofiltration |
| url | https://www.mdpi.com/2077-0375/15/6/184 |
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