Ultrafast Intercalation Enabled by Strong Solvent–Host Interactions: Understanding Solvent Effect at the Atomic Level

Zhu, Yue; Ji, Yujin; Ju, Zhengyu; Yu, Kang; Ferreira, Paulo J.; Liu, Yuanyue; Yu, Guihua

doi:10.1002/anie.201908982

Ultrafast Intercalation Enabled by Strong Solvent–Host Interactions: Understanding Solvent Effect at the Atomic Level

Journal Article · Tue Sep 24 00:00:00 EDT 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201908982· OSTI ID:1774913

Zhu, Yue ^[1]; Ji, Yujin ^[2]; Ju, Zhengyu ^[2]; Yu, Kang ^[3]; Ferreira, Paulo J. ^[4]; Liu, Yuanyue ^[2]; ^[2]

Univ. of Texas, Austin, TX (United States); The University of Texas at Austin
Univ. of Texas, Austin, TX (United States)
Univ. of Texas, Austin, TX (United States); International Iberian Nanotechnology Lab., Braga (Portugal)
International Iberian Nanotechnology Lab., Braga (Portugal); Univ. of Lisbon (Portugal)

Solvents play an essential role in many areas of chemistry and is the cornerstone of understanding reactivity in solution-phase reactions. Solvent effects have been widely observed in intercalation reactions; however, understanding of the influence of solvents on the thermodynamics and kinetics remains largely elusive in intercalation chemistry. Now, the solvent-dependent kinetics of ferrocene intercalation into a layered vanadyl phosphate (VOPO₄∙2 H₂O) host is presented, with a special focus on primary alcohols. From methanol to 1-hexnaol, the intercalation rate peaks in 1-propanol (80 times faster than the slowest case in methanol). Similar kinetics of exfoliation are also found in these solvents without ferrocene. Here, the correlation between intercalation and exfoliation is understood at atomic level by DFT calculations, which reveal the role of pre-intercalated solvent molecules play in intralayer interactions, interlayer expansion, and layer sliding.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Texas, Austin, TX (United States)

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

Grant/Contract Number:: SC0019019

OSTI ID:: 1774913

Alternate ID(s):: OSTI ID: 1570508

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 48 Vol. 58; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

Engineering 2D Nanofluidic Li‐Ion Transport Channels for Superior Electrochemical Energy Storage Yan, Chunshuang; Lv, Chade; Zhu, Yue Advanced Materials, Vol. 29, Issue 46 https://doi.org/10.1002/adma.201703909	journal	October 2017
Graphene-Graphene Interactions: Friction, Superlubricity, and Exfoliation Sinclair, Robert C.; Suter, James L.; Coveney, Peter V. Advanced Materials, Vol. 30, Issue 13 https://doi.org/10.1002/adma.201705791	journal	February 2018
Structural Engineering of 2D Nanomaterials for Energy Storage and Catalysis Zhu, Yue; Peng, Lele; Fang, Zhiwei Advanced Materials, Vol. 30, Issue 15 https://doi.org/10.1002/adma.201706347	journal	February 2018
Two-Dimensional Materials for Beyond-Lithium-Ion Batteries Peng, Lele; Zhu, Yue; Chen, Dahong Advanced Energy Materials, Vol. 6, Issue 11 https://doi.org/10.1002/aenm.201600025	journal	March 2016
Conditions for Reversible Na Intercalation in Graphite: Theoretical Studies on the Interplay Among Guest Ions, Solvent, and Graphite Host Yoon, Gabin; Kim, Haegyeom; Park, Inchul Advanced Energy Materials, Vol. 7, Issue 2 https://doi.org/10.1002/aenm.201601519	journal	September 2016
Holey 2D Nanomaterials for Electrochemical Energy Storage Peng, Lele; Fang, Zhiwei; Zhu, Yue Advanced Energy Materials, Vol. 8, Issue 9 https://doi.org/10.1002/aenm.201702179	journal	December 2017
Heterogeneous Molten Salt Design Strategy toward Coupling Cobalt-Cobalt Oxide and Carbon for Efficient Energy Conversion and Storage Yan, Chunshuang; Zhu, Yue; Fang, Zhiwei Advanced Energy Materials, Vol. 8, Issue 23 https://doi.org/10.1002/aenm.201800762	journal	June 2018
Solid-State Kinetic Models: Basics and Mathematical Fundamentals Khawam, Ammar; Flanagan, Douglas R. ChemInform, Vol. 37, Issue 47 https://doi.org/10.1002/chin.200647223	journal	November 2006
2D Materials with Nanoconfined Fluids for Electrochemical Energy Storage Augustyn, Veronica; Gogotsi, Yury Joule, Vol. 1, Issue 3 https://doi.org/10.1016/j.joule.2017.09.008	journal	November 2017
Ultrafast Solvent-Assisted Sodium Ion Intercalation into Highly Crystalline Few-Layered Graphene Cohn, Adam P.; Share, Keith; Carter, Rachel Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b04187	journal	December 2015
Intercalation Pseudocapacitance in Ultrathin VOPO ₄ Nanosheets: Toward High-Rate Alkali-Ion-Based Electrochemical Energy Storage Zhu, Yue; Peng, Lele; Chen, Dahong Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b04610	journal	December 2015
Effective Interlayer Engineering of Two-Dimensional VOPO ₄ Nanosheets via Controlled Organic Intercalation for Improving Alkali Ion Storage Peng, Lele; Zhu, Yue; Peng, Xu Nano Letters, Vol. 17, Issue 10 https://doi.org/10.1021/acs.nanolett.7b02958	journal	September 2017
Solvent-Dependent Intercalation and Molecular Configurations in Metallocene-Layered Crystal Superlattices Zhu, Yue; Qian, Yumin; Ju, Zhengyu Nano Letters, Vol. 18, Issue 9 https://doi.org/10.1021/acs.nanolett.8b03030	journal	August 2018
Two-Dimensional Holey Nanoarchitectures Created by Confined Self-Assembly of Nanoparticles via Block Copolymers: From Synthesis to Energy Storage Property Peng, Lele; Fang, Zhiwei; Li, Jing ACS Nano, Vol. 12, Issue 1 https://doi.org/10.1021/acsnano.7b08186	journal	December 2017
Significantly Improving Lithium-Ion Transport via Conjugated Anion Intercalation in Inorganic Layered Hosts Yan, Chunshuang; Fang, Zhiwei; Lv, Chade ACS Nano, Vol. 12, Issue 8 https://doi.org/10.1021/acsnano.8b04614	journal	July 2018
Thin-Layered Sheets of VOHPO ₄ ·0.5H ₂ O Prepared from VOPO ₄ ·2H ₂ O by Intercalation−Exfoliation−Reduction in Alcohol Yamamoto, Naoki; Hiyoshi, Norihito; Okuhara, Toshio Chemistry of Materials, Vol. 14, Issue 9 https://doi.org/10.1021/cm020292y	journal	September 2002
Preparation and Probable Structure of Layered Complexes of Vanadyl Phosphate with 1-Alkanols and 1,ω-Alkanediols Beneš, Ludvík; Melánová, Klára; Zima, Vítězslav Inorganic Chemistry, Vol. 36, Issue 13 https://doi.org/10.1021/ic970073s	journal	June 1997
Understanding the Stabilization of Liquid-Phase-Exfoliated Graphene in Polar Solvents: Molecular Dynamics Simulations and Kinetic Theory of Colloid Aggregation Shih, Chih-Jen; Lin, Shangchao; Strano, Michael S. Journal of the American Chemical Society, Vol. 132, Issue 41 https://doi.org/10.1021/ja1064284	journal	October 2010
Kinetic Study of the Intercalation of Cobaltocene by Layered Metal Dichalcogenides with Time-Resolved in Situ X-ray Powder Diffraction Evans, John S. O.; Price, Stephen J.; Wong, Heng-Vee Journal of the American Chemical Society, Vol. 120, Issue 42 https://doi.org/10.1021/ja9819099	journal	October 1998
Solid-State Kinetic Models: Basics and Mathematical Fundamentals Khawam, Ammar; Flanagan, Douglas R. The Journal of Physical Chemistry B, Vol. 110, Issue 35 https://doi.org/10.1021/jp062746a	journal	September 2006
Non-oxidative intercalation and exfoliation of graphite by Brønsted acids Kovtyukhova, Nina I.; Wang, Yuanxi; Berkdemir, Ayse Nature Chemistry, Vol. 6, Issue 11 https://doi.org/10.1038/nchem.2054	journal	September 2014
Two-dimensional vanadyl phosphate ultrathin nanosheets for high energy density and flexible pseudocapacitors Wu, Changzheng; Lu, Xiuli; Peng, Lele Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3431	journal	September 2013
Intercalation in two-dimensional transition metal chalcogenides Jung, Yeonwoong; Zhou, Yu; Cha, Judy J. Inorganic Chemistry Frontiers, Vol. 3, Issue 4 https://doi.org/10.1039/C5QI00242G	journal	January 2016
An advanced high-energy sodium ion full battery based on nanostructured Na ₂ Ti ₃ O ₇ /VOPO ₄ layered materials Li, Hongsen; Peng, Lele; Zhu, Yue Energy & Environmental Science, Vol. 9, Issue 11 https://doi.org/10.1039/C6EE00794E	journal	January 2016
The chemical sensitivity of X-ray spectroscopy: high energy resolution XANES versus X-ray emission spectroscopy of substituted ferrocenes Atkins, Andrew J.; Bauer, Matthias; Jacob, Christoph R. Physical Chemistry Chemical Physics, Vol. 15, Issue 21 https://doi.org/10.1039/c3cp50999k	journal	January 2013
The crystal and molecular structure of oxovanadium(V) orthophosphate dihydrate, VOPO4,2H2O Tietze, Hr Australian Journal of Chemistry, Vol. 34, Issue 10 https://doi.org/10.1071/CH9812035	journal	January 1981
Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals Liu, Yuanyue; Merinov, Boris V.; Goddard, William A. Proceedings of the National Academy of Sciences, Vol. 113, Issue 14 https://doi.org/10.1073/pnas.1602473113	journal	March 2016
Intercalation compounds of graphite Dresselhaus, M. S.; Dresselhaus, G. Advances in Physics, Vol. 51, Issue 1 https://doi.org/10.1080/00018730110113644	journal	January 2002
Intercalation compounds of graphite Dresselhaus, M. S.; Dresselhaus, G. Advances in Physics, Vol. 30, Issue 2 https://doi.org/10.1080/00018738100101367	journal	April 1981
Probing enhanced lithium-ion transport kinetics in 2D holey nanoarchitectured electrodes Zhang, Xiao; Bruck, Andrea M.; Zhu, Yue Nano Futures, Vol. 2, Issue 3 https://doi.org/10.1088/2399-1984/aada90	journal	August 2018
Liquid Exfoliation of Layered Materials Nicolosi, V.; Chhowalla, M.; Kanatzidis, M. G. Science, Vol. 340, Issue 6139, p. 1226419 https://doi.org/10.1126/science.1226419	journal	June 2013
Intercalation of Metallocenes in the Layered Transition-Metal Dichalcogenides Dines, M. B. Science, Vol. 188, Issue 4194 https://doi.org/10.1126/science.188.4194.1210	journal	June 1975
Inclusion Systems of Organic Molecules in Restacked Single-Layer Molybdenum Disulfide Divigalpitiya, W. M. R.; Frindt, R. F.; Morrison, S. R. Science, Vol. 246, Issue 4928 https://doi.org/10.1126/science.246.4928.369	journal	October 1989

Cited By (1)

Evaporation‐Induced Vertical Alignment Enabling Directional Ion Transport in a 2D‐Nanosheet‐Based Battery Electrode Zhu, Yue; Ju, Zhengyu; Zhang, Xiao Advanced Materials, Vol. 32, Issue 10 https://doi.org/10.1002/adma.201907941	journal	January 2020

Similar Records

Ultrafast Intercalation Enabled by Strong Solvent–Host Interactions: Understanding Solvent Effect at the Atomic Level

Journal Article · Mon Oct 14 20:00:00 EDT 2019 · Angewandte Chemie · OSTI ID:1570507

Synthesis, characterization, and intercalation of vanadyl phsophate modified with manganese

Journal Article · Mon May 01 00:00:00 EDT 1995 · Journal of Solid State Chemistry · OSTI ID:146485

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
exfoliation
solvent effects
solvent pre-intercalation
solvent–host interactions
ultrafast intercalation

Ultrafast Intercalation Enabled by Strong Solvent–Host Interactions: Understanding Solvent Effect at the Atomic Level

Citation Formats

References (33)

Cited By (1)

Similar Records

Related Subjects