Structure and Dispersion of Free and Grafted Polymer in Nanoparticle Organic Hybrid Materials-Based Solutions by Small-Angle Neutron Scattering

Haque, Md. Ashraful; Feric, Tony G.; Hamilton, Sara T.; Park, Ah-Hyung Alissa; Dadmun, Mark D.

doi:10.1021/acs.jpcc.0c10790

Structure and Dispersion of Free and Grafted Polymer in Nanoparticle Organic Hybrid Materials-Based Solutions by Small-Angle Neutron Scattering

Journal Article · Mon Mar 01 00:00:00 EST 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c10790· OSTI ID:1808451

Haque, Md. Ashraful ^[1]; Feric, Tony G. ^[2]; Hamilton, Sara T. ^[2]; Park, Ah-Hyung Alissa ^[2]; ^[3]

Univ. of Tennessee, Knoxville, TN (United States); Columbia University
Columbia Univ., New York, NY (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Liquid-like Nanoscale Organic Hybrid Materials or NOHMs consisting of polymer grafted nanoparticles have shown great promise in applications, such as electrochemistry and gas separation, due to their enhanced conductivity, tunability, and negligible vapor pressure. Recently, NOHMs are considered to be used as novel electrolytes in Redox Flow Batteries (RFBs). However, to employ NOHMs in redox flow batteries as electrolytes, it is important to understand the conformation and dispersion of NOHMs in the electrochemical milieu. In this work, we report the use of small-angle neutron scattering to probe the structure and dispersion of Jeffamine M2070 polymer grafted to a SiO₂ nanoparticle in an aqueous solution with and without the presence of a supporting electrolyte. Our results indicate that, in the aqueous environment, there exists a large amount of free polymer in the solution that is not grafted to the functionalized nanoparticles. These protonated free polymers, dispersed in the aqueous solvent, may also strongly interact with the grafted polymer layer and greatly affect the neat structure of NOHMs. Thus, there also exist polymers identified as “interacting” polymers to distinguish them from tethered or truly free polymers in the fluid system. The presence of supporting electrolyte shows a greater effect on the structure of NOHMs-based fluid as it not only alters the structure of the free polymer but also hinders the interaction of the polymer with the functionalized nanoparticles. Moreover, the change in the interaction of the Jeffamine M2070 with the functionalized nanoparticles due to the addition of supporting electrolyte has revealed a drastic change in the viscosities of NOHM solutions. Overall, the dispersion of the free polymer, the interaction of the interacting polymer with grafted polymer, and the change in conformation of free polymer and grafted layers with the addition of supporting electrolyte provide valuable insight into the overall scenario of the electrochemical environment of NOHMs. These results can be applied to fine-tune the structure of liquid-like NOHMs and will aid in a better understanding of their performance as potential electrolytes in RFBs.

View Accepted Manuscript (DOE)

Research Organization:: Case Western Reserve Univ., Cleveland, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019409

OSTI ID:: 1808451

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 9 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Redox-Flow Batteries: From Metals to Organic Redox-Active Materials Winsberg, Jan; Hagemann, Tino; Janoschka, Tobias Angewandte Chemie International Edition, Vol. 56, Issue 3 https://doi.org/10.1002/anie.201604925	journal	November 2016
Effects of the core of liquid-like SiO2 nanoparticle organic hybrid materials on CO2 capture Yang, Ruilu; Fan, Wendi; Zheng, Yaping Journal of Materials Science, Vol. 53, Issue 7 https://doi.org/10.1007/s10853-017-1772-4	journal	December 2017
The structure factor and the transport properties of dense fluids having molecules with square well potential, a possible generalization Sharma, R. V.; Sharma, K. C. Physica A: Statistical Mechanics and its Applications, Vol. 89, Issue 1 https://doi.org/10.1016/0378-4371(77)90151-0	journal	October 1977
Effect of water on the physical properties and carbon dioxide capture capacities of liquid-like Nanoparticle Organic Hybrid Materials and their corresponding polymers Petit, Camille; Bhatnagar, Sonali; Park, Ah-Hyung Alissa Journal of Colloid and Interface Science, Vol. 407 https://doi.org/10.1016/j.jcis.2013.05.065	journal	October 2013
The Electrolyte Frontier: A Manifesto Amanchukwu, Chibueze V. Joule, Vol. 4, Issue 2 https://doi.org/10.1016/j.joule.2019.12.009	journal	February 2020
Recent developments in organic redox flow batteries: A critical review Leung, P.; Shah, A. A.; Sanz, L. Journal of Power Sources, Vol. 360 https://doi.org/10.1016/j.jpowsour.2017.05.057	journal	August 2017
Hybrid Hairy Nanoparticle Electrolytes Stabilizing Lithium Metal Batteries Choudhury, Snehashis; Agrawal, Akanksha; Wei, Shuya Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.6b00029	journal	March 2016
Metal-Free Deep Eutectic Solvents: Preparation, Physical Properties, and Significance Gurkan, Burcu; Squire, Henry; Pentzer, Emily The Journal of Physical Chemistry Letters, Vol. 10, Issue 24 https://doi.org/10.1021/acs.jpclett.9b01980	journal	November 2019
Spectroscopic Investigation of Entropic Canopy–Canopy Interactions of Nanoparticle Organic Hybrid Materials Choi, Soyoung; Moon, Seokyoon; Park, Youngjune Langmuir, Vol. 36, Issue 32 https://doi.org/10.1021/acs.langmuir.0c01784	journal	July 2020
Interfacial and Bulk Nanostructure of Liquid Polymer Nanocomposites McDonald, Samila; Wood, Jared A.; FitzGerald, Paul A. Langmuir, Vol. 31, Issue 12 https://doi.org/10.1021/acs.langmuir.5b00255	journal	March 2015
Relative Size of the Polymer and Nanoparticle Controls Polymer Diffusion in All-Polymer Nanocomposites Martin, Halie J.; White, B. Tyler; Yuan, Guangcui Macromolecules, Vol. 52, Issue 7 https://doi.org/10.1021/acs.macromol.8b02596	journal	March 2019
Spectroscopic Investigation of Thermochemical Depolymerization of Lignin Model Compounds in the Presence of Novel Liquidlike Nanoparticle Organic Hybrid Solvents for Efficient Biomass Valorization Moon, Seokyoon; Lee, Yunseok; Choi, Soyoung Organic Process Research & Development, Vol. 22, Issue 12 https://doi.org/10.1021/acs.oprd.8b00282	journal	October 2018
Materials and Systems for Organic Redox Flow Batteries: Status and Challenges Wei, Xiaoliang; Pan, Wenxiao; Duan, Wentao ACS Energy Letters, Vol. 2, Issue 9 https://doi.org/10.1021/acsenergylett.7b00650	journal	August 2017
Large-Scale Diffusion of Entangled Polymers along Nanochannels Lange, Frank; Judeinstein, Patrick; Franz, Cornelius ACS Macro Letters, Vol. 4, Issue 5 https://doi.org/10.1021/acsmacrolett.5b00213	journal	April 2015
Polymer Chain Behavior in Polymer Nanocomposites with Attractive Interactions Jouault, Nicolas; Crawford, Michael K.; Chi, Changzai ACS Macro Letters, Vol. 5, Issue 4 https://doi.org/10.1021/acsmacrolett.6b00164	journal	March 2016
Local Structure and Relaxation Dynamics in the Brush of Polymer-Grafted Silica Nanoparticles Wei, Yuan; Xu, Yifan; Faraone, Antonio ACS Macro Letters, Vol. 7, Issue 6 https://doi.org/10.1021/acsmacrolett.8b00223	journal	May 2018
Location of Imbibed Solvent in Polymer-Grafted Nanoparticle Membranes Buenning, Eileen; Jestin, Jacques; Huang, Yucheng ACS Macro Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acsmacrolett.8b00472	journal	August 2018
Flow Batteries: Current Status and Trends Soloveichik, Grigorii L. Chemical Reviews, Vol. 115, Issue 20 https://doi.org/10.1021/cr500720t	journal	September 2015
Effect of SO ₂ on CO ₂ Capture Using Liquid-like Nanoparticle Organic Hybrid Materials Lin, Kun-Yi Andrew; Petit, Camille; Park, Ah-Hyung Alissa Energy & Fuels, Vol. 27, Issue 8 https://doi.org/10.1021/ef400374q	journal	June 2013
Effects of Bonding Types and Functional Groups on CO ₂ Capture using Novel Multiphase Systems of Liquid-like Nanoparticle Organic Hybrid Materials Lin, Kun-Yi Andrew; Park, Ah-Hyung Alissa Environmental Science & Technology, Vol. 45, Issue 15 https://doi.org/10.1021/es200146g	journal	August 2011
CO ₂ Capture Capacity and Swelling Measurements of Liquid-like Nanoparticle Organic Hybrid Materials via Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy Park, Youngjune; Shin, Dolly; Jang, Young Nam Journal of Chemical & Engineering Data, Vol. 57, Issue 1 https://doi.org/10.1021/je200623b	journal	October 2011
Spectroscopic Investigation of the Canopy Configurations in Nanoparticle Organic Hybrid Materials of Various Grafting Densities during CO ₂ Capture Petit, Camille; Park, Youngjune; Lin, Kun-Yi Andrew The Journal of Physical Chemistry C, Vol. 116, Issue 1 https://doi.org/10.1021/jp210391c	journal	December 2011
Design and Characterization of Liquidlike POSS-Based Hybrid Nanomaterials Synthesized via Ionic Bonding and Their Interactions with CO ₂ Petit, Camille; Lin, Kun-Yi Andrew; Park, Ah-Hyung Alissa Langmuir, Vol. 29, Issue 39 https://doi.org/10.1021/la4007923	journal	September 2013
Polymer-Grafted-Nanoparticles Nanocomposites: Dispersion, Grafted Chain Conformation, and Rheological Behavior Chevigny, Chloé; Dalmas, Florent; Di Cola, Emanuela Macromolecules, Vol. 44, Issue 1 https://doi.org/10.1021/ma101332s	journal	January 2011
Macromolecular Diffusion in a Crowded Polymer Nanocomposite Gam, Sangah; Meth, Jeffrey S.; Zane, Steve G. Macromolecules, Vol. 44, Issue 9 https://doi.org/10.1021/ma102463q	journal	May 2011
Nanocomposite Materials with Controlled Anisotropic Reinforcement Triggered by Magnetic Self-Assembly Robbes, Anne-Sophie; Cousin, Fabrice; Meneau, Florian Macromolecules, Vol. 44, Issue 22 https://doi.org/10.1021/ma201096u	journal	November 2011
Direct Measurements of Polymer Brush Conformation Using Small-Angle Neutron Scattering (SANS) from Highly Grafted Iron Oxide Nanoparticles in Homopolymer Melts Hore, Michael J. A.; Ford, Jamie; Ohno, Kohji Macromolecules, Vol. 46, Issue 23 https://doi.org/10.1021/ma401975a	journal	November 2013
Hierarchical Canopy Dynamics of Electrolyte-Doped Nanoscale Ionic Materials Jespersen, Michael L.; Mirau, Peter A.; von Meerwall, Ernst D. Macromolecules, Vol. 46, Issue 24 https://doi.org/10.1021/ma402002a	journal	December 2013
Canopy Dynamics in Nanoscale Ionic Materials Jespersen, Michael L.; Mirau, Peter A.; Meerwall, Ernst von ACS Nano, Vol. 4, Issue 7 https://doi.org/10.1021/nn100112h	journal	June 2010
Thermal stability, swelling behavior and CO ₂ absorption properties of Nanoscale Ionic Materials (NIMs) Andrew Lin, Kun-Yi; Park, Youngjune; Petit, Camille RSC Adv., Vol. 4, Issue 110 https://doi.org/10.1039/C4RA10722E	journal	January 2014
Nonaqueous redox-flow batteries: organic solvents, supporting electrolytes, and redox pairs Gong, Ke; Fang, Qianrong; Gu, Shuang Energy & Environmental Science, Vol. 8, Issue 12, p. 3515-3530 https://doi.org/10.1039/C5EE02341F	journal	January 2015
A highly conductive, non-flammable polymer–nanoparticle hybrid electrolyte Agrawal, Akanksha; Choudhury, Snehashis; Archer, Lynden A. RSC Advances, Vol. 5, Issue 27 https://doi.org/10.1039/C5RA01031D	journal	January 2015
Molecular engineering of organic electroactive materials for redox flow batteries Ding, Yu; Zhang, Changkun; Zhang, Leyuan Chemical Society Reviews, Vol. 47, Issue 1 https://doi.org/10.1039/C7CS00569E	journal	January 2018
Investigation of CO2 capture mechanisms of liquid-like nanoparticle organic hybrid materials via structural characterization Park, Youngjune; Decatur, John; Lin, Kun-Yi Andrew Physical Chemistry Chemical Physics, Vol. 13, Issue 40 https://doi.org/10.1039/c1cp22631b	journal	January 2011
Effect of canopy structures and their steric interactions on CO2 sorption behavior of liquid-like nanoparticle organic hybrid materials Park, Youngjune; Petit, Camille; Han, Patrick RSC Advances, Vol. 4, Issue 17 https://doi.org/10.1039/c3ra46801a	journal	January 2014
A new interpretation of the sticky hard sphere model Menon, S. V. G.; Manohar, C.; Rao, K. Srinivasa The Journal of Chemical Physics, Vol. 95, Issue 12 https://doi.org/10.1063/1.461199	journal	December 1991
Electrochemical Characterization of Bromine Reduction to Tribromide in Individual Nitrobenzene-in-Water Emulsion Droplets Chang, L.; Bard, A. J. Journal of The Electrochemical Society, Vol. 167, Issue 6 https://doi.org/10.1149/1945-7111/ab80ab	journal	January 2020
Electrochemical Behavior of Copper Ion Complexed with Nanoparticle Organic Hybrid Materials Cantillo, Nelly M.; Bruce, Maria; Hamilton, Sara T. Journal of The Electrochemical Society, Vol. 167, Issue 11 https://doi.org/10.1149/1945-7111/aba158	journal	July 2020
An Investigation of the Ionic Conductivity and Species Crossover of Lithiated Nafion 117 in Nonaqueous Electrolytes Su, Liang; Darling, Robert M.; Gallagher, Kevin G. Journal of The Electrochemical Society, Vol. 163, Issue 1 https://doi.org/10.1149/2.03211601jes	journal	December 2015
Stability Analysis of Electrodeposition across a Structured Electrolyte with Immobilized Anions Tikekar, Mukul D.; Archer, Lynden A.; Koch, Donald L. Journal of The Electrochemical Society, Vol. 161, Issue 6 https://doi.org/10.1149/2.085405jes	journal	January 2014
Avoiding Pitfalls in the Determination of Reliable Electrochemical Kinetics Parameters for the Cu ²⁺ → Cu ¹⁺ Reduction Reaction in Deep Eutectic Solvents Shen, Dai; Steinberg, Katherine; Akolkar, Rohan Journal of The Electrochemical Society, Vol. 165, Issue 14 https://doi.org/10.1149/2.1011814jes	journal	January 2018
Flow Batteries Nguyen, Trung; Savinell, Robert F. The Electrochemical Society Interface, Vol. 19, Issue 3 https://doi.org/10.1149/2.F06103if	journal	January 2010
Recent Advances in Anhydrous Solvents for CO2 Capture: Ionic Liquids, Switchable Solvents, and Nanoparticle Organic Hybrid Materials Park, Youngjune; Lin, Kun-Yi Andrew; Park, Ah-Hyung Alissa Frontiers in Energy Research, Vol. 3 https://doi.org/10.3389/fenrg.2015.00042	journal	October 2015

Similar Records

Insights into the Assembly and Conformation of Nanoparticle Organic Hybrid Materials (NOHMs) in Solution with Varying Grafting Type

Journal Article · Tue Mar 12 20:00:00 EDT 2024 · ACS Applied Polymer Materials · OSTI ID:2333622

Impacts of Bond Type and Grafting Density on the Thermal, Structural, and Transport Behaviors of Nanoparticle Organic Hybrid Materials–Based Electrolytes

Journal Article · Wed Jun 29 20:00:00 EDT 2022 · Advanced Functional Materials · OSTI ID:1899079

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

Journal Article · Sun Aug 08 20:00:00 EDT 2021 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry · OSTI ID:1865376

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Layers
Nanoparticles
Polymer solutions
Polymers
Scattering

Structure and Dispersion of Free and Grafted Polymer in Nanoparticle Organic Hybrid Materials-Based Solutions by Small-Angle Neutron Scattering

Citation Formats

References (43)

Similar Records

Related Subjects