Unraveling the Ion Adsorption Kinetics in Microporous Carbon Electrodes: A Multiscale Quantum-Continuum Simulation and Experimental Approach

Oyarzun, Diego I.; Zhan, Cheng; Hawks, Steven A.; Cerón, Maira R.; Kuo, Helen A.; Loeb, Colin K.; Aydin, Fikret; Pham, Tuan Anh; Stadermann, Michael; Campbell, Patrick G.

doi:10.1021/acsami.1c01640

Title: Unraveling the Ion Adsorption Kinetics in Microporous Carbon Electrodes: A Multiscale Quantum-Continuum Simulation and Experimental Approach

Journal Article · Wed May 12 00:00:00 EDT 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c01640· OSTI ID:1845217

^[1]; Zhan, Cheng ^[1];

^[1];

^[1]; Kuo, Helen A. ^[1]; Loeb, Colin K. ^[1];

^[1];

^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

With the understanding that sorption in porous carbon electrodes is crucial to many environmental and energy technologies, such as capacitive deionization (CDI), supercapacitor energy storage, and activated carbon filters. In each of these examples, a practical model that can describe ion electrosorption kinetics is highly desirable for accelerating material design. Here, we proposed a multiscale model to study the ion electrosorption kinetics in porous carbon electrodes by combining quantum mechanical simulations with continuum approaches. Our model integrates the Butler-Volmer (BV) equation for sorption kinetics and a continuously stirred tank reactor (CSTR) formulation with atomistic calculations of ion hydration and ion-pore interactions based on density functional theory (DFT). We validated our model experimentally by using ion mixtures in a flow-through electrode CDI device and developed an in-line UV absorption system to provide unprecedented resolution of individual ions in the separation process. We showed that the multiscale model captures unexpected experimental phenomena that cannot be explained by the traditional ion electrosorption theory. The proposed multiscale framework provides a viable approach for modeling separation processes in systems where pore sizes and ion hydration effects strongly influence the sorption kinetics, which can be leveraged to explore possible strategies for improving carbon-based and, more broadly, pore-based technologies

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; California Energy Commission

Grant/Contract Number:: AC52-07NA27344; ECP16-014; 18-ERD-024

OSTI ID:: 1845217

Report Number(s):: LLNL-JRNL-817159; 1026932

Journal Information:: ACS Applied Materials and Interfaces, Vol. 13, Issue 20; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (49)

Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Critical Knowledge Gaps in Mass Transport through Single-Digit Nanopores: A Review and Perspective Faucher, Samuel; Aluru, Narayana; Bazant, Martin Z. The Journal of Physical Chemistry C, Vol. 123, Issue 35 https://doi.org/10.1021/acs.jpcc.9b02178	journal	May 2019
Advanced carbon aerogels for energy applications Biener, Juergen; Stadermann, Michael; Suss, Matthew Energy & Environmental Science, Vol. 4, Issue 3, p. 656-667 https://doi.org/10.1039/c0ee00627k	journal	January 2011
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502 https://doi.org/10.1088/0953-8984/21/39/395502	journal	September 2009
Cation Selectivity in Capacitive Deionization: Elucidating the Role of Pore Size, Electrode Potential, and Ion Dehydration Cerón, Maira R.; Aydin, Fikret; Hawks, Steven A. ACS Applied Materials & Interfaces, Vol. 12, Issue 38 https://doi.org/10.1021/acsami.0c07903	journal	September 2020
Macroscopic 3D Nanographene with Dynamically Tunable Bulk Properties Biener, Juergen; Dasgupta, Subho; Shao, Lihua Advanced Materials, Vol. 24, Issue 37, p. 5083-5087 https://doi.org/10.1002/adma.201202289	journal	July 2012
Water desalination via capacitive deionization: what is it and what can we expect from it? Suss, M. E.; Porada, S.; Sun, X. Energy & Environmental Science, Vol. 8, Issue 8 https://doi.org/10.1039/C5EE00519A	journal	January 2015
Understanding Cation Selectivity in Carbon Nanopores with Hybrid First-Principles/Continuum Simulations: Implications for Water Desalination and Separation Technologies Zhan, Cheng; Aydin, Fikret; Schwegler, Eric ACS Applied Nano Materials, Vol. 3, Issue 10 https://doi.org/10.1021/acsanm.0c01842	journal	September 2020
Comments on “Comparison of energy consumption in desalination by capacitive deionization and reverse osmosis” Ramachandran, Ashwin; Oyarzun, Diego I.; Hawks, Steven A. Desalination, Vol. 461 https://doi.org/10.1016/j.desal.2019.03.010	journal	July 2019
Tafel Kinetics of Electrocatalytic Reactions: From Experiment to First-Principles Fang, Ya-Hui; Liu, Zhi-Pan ACS Catalysis, Vol. 4, Issue 12 https://doi.org/10.1021/cs501312v	journal	November 2014
Theoretical characterization of the “ridge” in the supercritical region in the fluid phase diagram of water Matsugami, Masaru; Yoshida, Norio; Hirata, Fumio The Journal of Chemical Physics, Vol. 140, Issue 10 https://doi.org/10.1063/1.4867974	journal	March 2014
Langmuir adsorption processes and ion transport under bias potential in capacitive deionisation cells Alexe-Ionescu, A. L.; Barbero, G.; Evangelista, L. R. Electrochimica Acta, Vol. 348 https://doi.org/10.1016/j.electacta.2020.136288	journal	July 2020
Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: Kinetic and isotherm study Yu, Qiang; Zhang, Ruiqi; Deng, Shubo Water Research, Vol. 43, Issue 4 https://doi.org/10.1016/j.watres.2008.12.001	journal	March 2009
Thermodynamics of Ion Separation by Electrosorption Hemmatifar, Ali; Ramachandran, Ashwin; Liu, Kang Environmental Science & Technology, Vol. 52, Issue 17 https://doi.org/10.1021/acs.est.8b02959	journal	August 2018
Using Ultramicroporous Carbon for the Selective Removal of Nitrate with Capacitive Deionization Hawks, Steven A.; Cerón, Maira R.; Oyarzun, Diego I. Environmental Science & Technology, Vol. 53, Issue 18 https://doi.org/10.1021/acs.est.9b01374	journal	June 2019
Water Desalination Using Capacitive Deionization with Microporous Carbon Electrodes Porada, S.; Weinstein, L.; Dash, R. ACS Applied Materials & Interfaces, Vol. 4, Issue 3 https://doi.org/10.1021/am201683j	journal	February 2012
Origins and Implications of Interfacial Capacitance Enhancements in C ₆₀ -Modified Graphene Supercapacitors Zhan, Cheng; Pham, Tuan Anh; Cerón, Maira R. ACS Applied Materials & Interfaces, Vol. 10, Issue 43 https://doi.org/10.1021/acsami.8b10349	journal	October 2018
Self similarities in desalination dynamics and performance using capacitive deionization Ramachandran, Ashwin; Hemmatifar, Ali; Hawks, Steven A. Water Research, Vol. 140 https://doi.org/10.1016/j.watres.2018.04.042	journal	September 2018
Water-ion permselectivity of narrow-diameter carbon nanotubes Li, Yuhao; Li, Zhongwu; Aydin, Fikret Science Advances, Vol. 6, Issue 38 https://doi.org/10.1126/sciadv.aba9966	journal	September 2020
Improved modeling of electrified interfaces using the effective screening medium method Hamada, Ikutaro; Sugino, Osamu; Bonnet, Nicéphore Physical Review B, Vol. 88, Issue 15 https://doi.org/10.1103/PhysRevB.88.155427	journal	October 2013
Pseudopotentials for high-throughput DFT calculations Garrity, Kevin F.; Bennett, Joseph W.; Rabe, Karin M. Computational Materials Science, Vol. 81 https://doi.org/10.1016/j.commatsci.2013.08.053	journal	January 2014
Intrapore energy barriers govern ion transport and selectivity of desalination membranes Zhou, Xuechen; Wang, Zhangxin; Epsztein, Razi Science Advances, Vol. 6, Issue 48 https://doi.org/10.1126/sciadv.abd9045	journal	November 2020
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 118, Issue 45 https://doi.org/10.1021/ja9621760	journal	January 1996
Accelerating charging dynamics in subnanometre pores Kondrat, Svyatoslav; Wu, Peng; Qiao, Rui Nature Materials, Vol. 13, Issue 4 https://doi.org/10.1038/nmat3916	journal	March 2014
Predicting and Enhancing the Ion Selectivity in Multi-Ion Capacitive Deionization Nordstrand, Johan; Dutta, Joydeep Langmuir, Vol. 36, Issue 29 https://doi.org/10.1021/acs.langmuir.0c00982	journal	June 2020
Nitrate removal from water using electrostatic regeneration of functionalized adsorbent Palko, James W.; Oyarzun, Diego I.; Ha, Byunghang Chemical Engineering Journal, Vol. 334 https://doi.org/10.1016/j.cej.2017.10.161	journal	February 2018
Kinetics of scandium ion sorption onto oxidized carbon nanotubes Pęgier, Mateusz; Kilian, Krzysztof; Pyrzynska, Krystyna Monatshefte für Chemie - Chemical Monthly, Vol. 150, Issue 9 https://doi.org/10.1007/s00706-019-02472-w	journal	August 2019
Effect of pore size and its dispersity on the energy storage in nanoporous supercapacitors Kondrat, S.; Pérez, C. R.; Presser, V. Energy & Environmental Science, Vol. 5, Issue 4 https://doi.org/10.1039/c2ee03092f	journal	January 2012
Nanofluidics coming of age Bocquet, Lydéric Nature Materials, Vol. 19, Issue 3 https://doi.org/10.1038/s41563-020-0625-8	journal	February 2020
Investigation on removal of hardness ions by capacitive deionization (CDI) for water softening applications Seo, Seok-Jun; Jeon, Hongrae; Lee, Jae Kwang Water Research, Vol. 44, Issue 7 https://doi.org/10.1016/j.watres.2009.10.020	journal	April 2010
Theory of membrane capacitive deionization including the effect of the electrode pore space Biesheuvel, P. M.; Zhao, R.; Porada, S. Journal of Colloid and Interface Science, Vol. 360, Issue 1 https://doi.org/10.1016/j.jcis.2011.04.049	journal	August 2011
Adsorption and capacitive regeneration of nitrate using inverted capacitive deionization with surfactant functionalized carbon electrodes Oyarzun, Diego I.; Hemmatifar, Ali; Palko, James W. Separation and Purification Technology, Vol. 194 https://doi.org/10.1016/j.seppur.2017.11.027	journal	April 2018
Sorption studies of uranium and thorium on activated carbon prepared from olive stones: Kinetic and thermodynamic aspects Kütahyalı, Ceren; Eral, Meral Journal of Nuclear Materials, Vol. 396, Issue 2-3 https://doi.org/10.1016/j.jnucmat.2009.11.018	journal	January 2010
Self-consistent description of a metal–water interface by the Kohn–Sham density functional theory and the three-dimensional reference interaction site model Kovalenko, Andriy; Hirata, Fumio The Journal of Chemical Physics, Vol. 110, Issue 20 https://doi.org/10.1063/1.478883	journal	May 1999
Consistency of carbon nanopore characteristics derived from adsorption of simple gases and 2D-NLDFT models. Advantages of using adsorption isotherms of oxygen (O2) at 77 K Jagiello, Jacek; Kenvin, Jeffrey Journal of Colloid and Interface Science, Vol. 542 https://doi.org/10.1016/j.jcis.2019.01.116	journal	April 2019
The OPLS [optimized potentials for liquid simulations] potential functions for proteins, energy minimizations for crystals of cyclic peptides and crambin Jorgensen, William L.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 110, Issue 6 https://doi.org/10.1021/ja00214a001	journal	March 1988
Van der Waals Density Functional for General Geometries Dion, M.; Rydberg, H.; Schröder, E. Physical Review Letters, Vol. 92, Issue 24 https://doi.org/10.1103/PhysRevLett.92.246401	journal	June 2004
Adsorption of basic dye onto palm kernel shell activated carbon: sorption equilibrium and kinetics studies Jumasiah, A.; Chuah, T. G.; Gimbon, J. Desalination, Vol. 186, Issue 1-3 https://doi.org/10.1016/j.desal.2005.05.015	journal	December 2005
Adsorption of toxic metal ions onto activated carbon Srivastava, Vimal Chandra; Mall, Indra Deo; Mishra, Indra Mani Chemical Engineering and Processing: Process Intensification, Vol. 47, Issue 8 https://doi.org/10.1016/j.cep.2007.04.006	journal	August 2008
High surface area carbon aerogel monoliths with hierarchical porosity Baumann, Theodore F.; Worsley, Marcus A.; Han, T. Yong-Jin Journal of Non-Crystalline Solids, Vol. 354, Issue 29, p. 3513-3515 https://doi.org/10.1016/j.jnoncrysol.2008.03.006	journal	July 2008
Modeling the influence of chemical reactions on the mechanisms of ionic transport in porous materials Samson, E.; Marchand, J.; Beaudoin, J. J. Cement and Concrete Research, Vol. 30, Issue 12 https://doi.org/10.1016/S0008-8846(00)00458-0	journal	December 2000
Dual gas analysis of microporous carbons using 2D-NLDFT heterogeneous surface model and combined adsorption data of N2 and CO2 Jagiello, Jacek; Ania, Conchi; Parra, Jose B. Carbon, Vol. 91 https://doi.org/10.1016/j.carbon.2015.05.004	journal	September 2015
Quantifying the flow efficiency in constant-current capacitive deionization Hawks, Steven A.; Knipe, Jennifer M.; Campbell, Patrick G. Water Research, Vol. 129 https://doi.org/10.1016/j.watres.2017.11.025	journal	February 2018
Adsorption of aromatic organic acids onto high area activated carbon cloth in relation to wastewater purification Ayranci, E.; Duman, O. Journal of Hazardous Materials, Vol. 136, Issue 3 https://doi.org/10.1016/j.jhazmat.2005.12.029	journal	August 2006
Specific ion effects at graphitic interfaces Zhan, Cheng; Cerón, Maira R.; Hawks, Steven A. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12854-7	journal	October 2019
High Energy Density Lithium-Sulfur Batteries: Challenges of Thick Sulfur Cathodes Lv, Dongping; Zheng, Jianming; Li, Qiuyan Advanced Energy Materials, Vol. 5, Issue 16, Article No. 1402290 https://doi.org/10.1002/aenm.201402290	journal	March 2015
Ion selectivity in capacitive deionization with functionalized electrode: Theory and experimental validation Oyarzun, Diego I.; Hemmatifar, Ali; Palko, James W. Water Research X, Vol. 1 https://doi.org/10.1016/j.wroa.2018.100008	journal	December 2018
Green conversion of crop residues into porous carbons and their application to efficiently remove polycyclic aromatic hydrocarbons from water: Sorption kinetics, isotherms and mechanism Cheng, Hu; Bian, Yongrong; Wang, Fang Bioresource Technology, Vol. 284 https://doi.org/10.1016/j.biortech.2019.03.104	journal	July 2019

Similar Records

Understanding resistances in capacitive deionization devices

Journal Article · Thu May 14 00:00:00 EDT 2020 · Environmental Science: Water Research & Technology · OSTI ID:1845217

Kuo, Helen A.; Ramachandran, Ashwin; Oyarzun, Diego I.; +5 more

Selectivity of nitrate and chloride ions in microporous carbons: the role of anisotropic hydration and applied potentials

Journal Article · Fri Sep 25 00:00:00 EDT 2020 · Nanoscale · OSTI ID:1845217

Aydin, Fikret; Cerón, Maira R.; Hawks, Steven A.; +5 more

Methanol fuel cell model: Anode

Journal Article · Mon Feb 01 00:00:00 EST 1999 · Journal of the Electrochemical Society · OSTI ID:1845217

Baxter, S F; Battaglia, V S; White, R E

Related Subjects

36 MATERIALS SCIENCE
97 MATHEMATICS AND COMPUTING
54 ENVIRONMENTAL SCIENCES
quantum mechanical simulation
continuum model
electrosorption
ion adsorption kinetics
capacitive deionization
Butler-Volmer equation

Title: Unraveling the Ion Adsorption Kinetics in Microporous Carbon Electrodes: A Multiscale Quantum-Continuum Simulation and Experimental Approach

Citation Formats

References (49)

Similar Records

Related Subjects