Structure and Dynamics of Aqueous Electrolytes Confined in 2D-TiO2/Ti3C2T2 MXene Heterostructures

Ganeshan, Karthik; Shin, Yun Kyung; Osti, Naresh C.; Sun, Yangyunli; Prenger, Kaitlyn; Naguib, Michael; Tyagi, Madhusudan; Mamontov, Eugene; Jiang, De-en; van Duin, Adri C. T.

doi:10.1021/acsami.0c17536

Title: Structure and Dynamics of Aqueous Electrolytes Confined in 2D-TiO₂/Ti₃C₂T₂ MXene Heterostructures

Journal Article · Fri Dec 18 00:00:00 EST 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c17536· OSTI ID:1824958

^[1];

^[2]; Sun, Yangyunli ^[3];

^[4];

^[4]; Tyagi, Madhusudan ^[5];

^[2];

^[3];

^[1]

Pennsylvania State Univ., University Park, PA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of California, Riverside, CA (United States)
Tulane Univ., New Orleans, LA (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)

The synthesis of heterostructures of different two-dimensional (2D) materials offers an approach to combine advantages of different materials constituting the heterostructure and ultimately enhance their performance for applications such as electrochemical energy storage, achieving high energy, and high-power densities. Understanding the behavior of ions and solvents in confinement between these dissimilar layers is critical to understand their performance and control. Considering aqueous electrolytes, we explore the heterostructure of 2D lepidocrocite-type TiO₂ (2D-TiO₂) and hydroxylated or O-terminated Ti₃C₂ MXene using ReaxFF molecular dynamics simulations and elastic/quasielastic neutron scattering techniques. Simulating a bilayer water intercalation, we find that the extent of interlayer hydration is impacted most by the surface terminations on the MXene and is marginally affected by 2D-TiO₂. However, the introduction of 2D-TiO₂ decreases the water self-diffusion due to the notch sites (i.e., surface oxygen ridges) entrapping water molecules. Intercalating alkali cations into the heterostructures, we find that Li⁺ is predominantly adsorbed at the 2D-TiO₂ surface instead of the MXenes with the preferential occupation of the notch sites. In contrast, Na+ forms a planar solvation with water, while K⁺ is adsorbed both at the O-terminated MXene and 2D-TiO₂. This behavior is altered when OH-terminated MXene is involved—the repulsion from the protons on the MXene surface forces the K⁺ ions to be adsorbed exclusively to 2D-TiO₂, while Na⁺ retains some of its solvation in the water layer due to its smaller size. In OH-terminated MXenes, we see a consistent transfer of protons from the MXene surface toward 2D-TiO₂, implying a greater capacity to store protons in the heterostructures. Of the three cations simulated, Na⁺ hinders the proton migration the least and Li⁺ the most because of its position near the 2D-TiO₂ surface. Furthermore, 2D-TiO₂/MXene heterostructures are likely to exhibit a higher energy density but lower power density, especially with Na⁺ intercalation.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1824958

Journal Information:: ACS Applied Materials and Interfaces, Vol. 12, Issue 52; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (67)

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
Self-Assembly of Transition Metal Oxide Nanostructures on MXene Nanosheets for Fast and Stable Lithium Storage Liu, Yi-Tao; Zhang, Peng; Sun, Ning Advanced Materials, Vol. 30, Issue 23 https://doi.org/10.1002/adma.201707334	journal	April 2018
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
Exfoliation and Restacking of Lepidocrocite-type Layered Titanates Studied by Small-Angle X-ray Scattering Besselink, Rogier; Stawski, Tomasz M.; Castricum, Hessel L. The Journal of Physical Chemistry C, Vol. 114, Issue 49 https://doi.org/10.1021/jp108687q	journal	November 2010
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
Mantid—Data analysis and visualization package for neutron scattering and $μ$ SR experiments Arnold, O.; Bilheux, J. C.; Borreguero, J. M. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764 https://doi.org/10.1016/j.nima.2014.07.029	journal	November 2014
Fe ₃ O ₄ @Ti ₃ C ₂ MXene hybrids with ultrahigh volumetric capacity as an anode material for lithium-ion batteries Wang, Yesheng; Li, Yanyan; Qiu, Zhipeng Journal of Materials Chemistry A, Vol. 6, Issue 24 https://doi.org/10.1039/C8TA00122G	journal	January 2018
Flexible MXene/Graphene Films for Ultrafast Supercapacitors with Outstanding Volumetric Capacitance Yan, Jun; Ren, Chang E.; Maleski, Kathleen Advanced Functional Materials, Vol. 27, Issue 30 https://doi.org/10.1002/adfm.201701264	journal	June 2017
Effect of surface termination on ion intercalation selectivity of bilayer Ti 3 C 2 T 2 (T = F, O and OH) MXene Berdiyorov, Golibjon R.; Mahmoud, Khaled A. Applied Surface Science, Vol. 416 https://doi.org/10.1016/j.apsusc.2017.04.195	journal	September 2017
Proton Redox and Transport in MXene-Confined Water Sun, Yangyunli; Zhan, Cheng; Kent, Paul R. C. ACS Applied Materials & Interfaces, Vol. 12, Issue 1 https://doi.org/10.1021/acsami.9b18139	journal	December 2019
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Nanostructures and lithium electrochemical reactivity of lithium titanites and titanium oxides: A review Yang, Zhenguo; Choi, Daiwon; Kerisit, Sebastien Journal of Power Sources, Vol. 192, Issue 2, p. 588-598 https://doi.org/10.1016/j.jpowsour.2009.02.038	journal	July 2009
Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene Butler, Sheneve Z.; Hollen, Shawna M.; Cao, Linyou ACS Nano, Vol. 7, Issue 4, p. 2898-2926 https://doi.org/10.1021/nn400280c	journal	March 2013
Exfoliated 2D Lepidocrocite Titanium Oxide Nanosheets for High Sulfur Content Cathodes with Highly Stable Li–S Battery Performance Patil, Sharad B.; Kim, Hyeon Jin; Lim, Hyung-Kyu ACS Energy Letters, Vol. 3, Issue 2 https://doi.org/10.1021/acsenergylett.7b01202	journal	January 2018
Charge equilibration for molecular dynamics simulations Rappe, Anthony K.; Goddard, William A. The Journal of Physical Chemistry, Vol. 95, Issue 8 https://doi.org/10.1021/j100161a070	journal	April 1991
Synthesis of Water Soluble Graphene Si, Yongchao; Samulski, Edward T. Nano Letters, Vol. 8, Issue 6 https://doi.org/10.1021/nl080604h	journal	June 2008
ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation Chenoweth, Kimberly; van Duin, Adri C. T.; Goddard, William A. The Journal of Physical Chemistry A, Vol. 112, Issue 5 https://doi.org/10.1021/jp709896w	journal	February 2008
Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide Lukatskaya, M. R.; Mashtalir, O.; Ren, C. E. Science, Vol. 341, Issue 6153 https://doi.org/10.1126/science.1241488	journal	September 2013
Computational Screening of MXene Electrodes for Pseudocapacitive Energy Storage Zhan, Cheng; Sun, Weiwei; Kent, Paul R. C. The Journal of Physical Chemistry C, Vol. 123, Issue 1 https://doi.org/10.1021/acs.jpcc.8b11608	journal	December 2018
Nanoengineering of 2D MXene‐Based Materials for Energy Storage Applications Nan, Jianxiao; Guo, Xin; Xiao, Jun Small https://doi.org/10.1002/smll.201902085	journal	July 2019
Novel electronic properties of a new MoS 2 /TiO 2 heterostructure and potential applications in solar cells and photocatalysis Li, Yanhua; Cai, Congzhong; Gu, Yonghong Applied Surface Science, Vol. 414 https://doi.org/10.1016/j.apsusc.2017.04.001	journal	August 2017
2D materials and van der Waals heterostructures Novoselov, K. S.; Mishchenko, A.; Carvalho, A. Science, Vol. 353, Issue 6298 https://doi.org/10.1126/science.aac9439	journal	July 2016
Stacked-Layer Heterostructure Films of 2D Thiophene Nanosheets and Graphene for High-Rate All-Solid-State Pseudocapacitors with Enhanced Volumetric Capacitance Wu, Zhong-Shuai; Zheng, Yijun; Zheng, Shuanghao Advanced Materials, Vol. 29, Issue 3 https://doi.org/10.1002/adma.201602960	journal	November 2016
Two-dimensional heterostructures for energy storage Pomerantseva, Ekaterina; Gogotsi, Yury Nature Energy, Vol. 2, Issue 7 https://doi.org/10.1038/nenergy.2017.89	journal	June 2017
Rutile-TiO ₂ Nanocoating for a High-Rate Li ₄ Ti ₅ O ₁₂ Anode of a Lithium-Ion Battery Wang, Yong-Qing; Gu, Lin; Guo, Yu-Guo Journal of the American Chemical Society, Vol. 134, Issue 18 https://doi.org/10.1021/ja301266w	journal	April 2012
Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance Ghidiu, Michael; Lukatskaya, Maria R.; Zhao, Meng-Qiang Nature, Vol. 516, Issue 7529 https://doi.org/10.1038/nature13970	journal	November 2014
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Characteristic features of water dynamics in restricted geometries investigated with quasi-elastic neutron scattering Osti, N. C.; Coté, A.; Mamontov, E. Chemical Physics, Vol. 465-466 https://doi.org/10.1016/j.chemphys.2015.11.008	journal	February 2016
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Chemical functionalization of graphene and its applications Kuila, Tapas; Bose, Saswata; Mishra, Ananta Kumar Progress in Materials Science, Vol. 57, Issue 7 https://doi.org/10.1016/j.pmatsci.2012.03.002	journal	September 2012
A time-of-flight backscattering spectrometer at the Spallation Neutron Source, BASIS Mamontov, E.; Herwig, K. W. Review of Scientific Instruments, Vol. 82, Issue 8 https://doi.org/10.1063/1.3626214	journal	August 2011
Insights into Li ⁺ , Na ⁺ , and K ⁺ Intercalation in Lepidocrocite-Type Layered TiO ₂ Structures Reeves, Kyle G.; Ma, Jiwei; Fukunishi, Mika ACS Applied Energy Materials, Vol. 1, Issue 5 https://doi.org/10.1021/acsaem.8b00170	journal	April 2018
Novel electronic properties of 2D MoS ₂ /TiO ₂ van der Waals heterostructure Li, Yanhua; Cai, Congzhong; Sun, Baoguang Semiconductor Science and Technology, Vol. 32, Issue 10 https://doi.org/10.1088/1361-6641/aa8796	journal	September 2017
NMR reveals the surface functionalisation of Ti ₃ C ₂ MXene Hope, Michael A.; Forse, Alexander C.; Griffith, Kent J. Physical Chemistry Chemical Physics, Vol. 18, Issue 7 https://doi.org/10.1039/C6CP00330C	journal	January 2016
Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries Poizot, P.; Laruelle, S.; Grugeon, S. Nature, Vol. 407, Issue 6803, p. 496-499 https://doi.org/10.1038/35035045	journal	September 2000
Two-dimensional MXene Ti3C2 produced by exfoliation of Ti3AlC2 Feng, Aihu; Yu, Yun; Wang, Yong Materials & Design, Vol. 114 https://doi.org/10.1016/j.matdes.2016.10.053	journal	January 2017
MXene/Si@SiO _x @C Layer-by-Layer Superstructure with Autoadjustable Function for Superior Stable Lithium Storage Zhang, Yelong; Mu, Zijie; Lai, Jianping ACS Nano https://doi.org/10.1021/acsnano.8b08821	journal	February 2019
DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6 https://doi.org/10.6028/jres.114.025	journal	November 2009
Determining in situ phases of a nanoparticle catalyst via grand canonical Monte Carlo simulations with the ReaxFF potential Senftle, Thomas P.; van Duin, Adri C. T.; Janik, Michael J. Catalysis Communications, Vol. 52 https://doi.org/10.1016/j.catcom.2013.12.001	journal	July 2014
Multimodality of Structural, Electrical, and Gravimetric Responses of Intercalated MXenes to Water Muckley, Eric S.; Naguib, Michael; Wang, Hsiu-Wen ACS Nano, Vol. 11, Issue 11 https://doi.org/10.1021/acsnano.7b05264	journal	September 2017
Tracking ion intercalation into layered Ti ₃ C ₂ MXene films across length scales Gao, Qiang; Sun, Weiwei; Ilani-Kashkouli, Poorandokht Energy & Environmental Science, Vol. 13, Issue 8 https://doi.org/10.1039/D0EE01580F	journal	January 2020
The ReaxFF reactive force-field: development, applications and future directions Senftle, Thomas P.; Hong, Sungwook; Islam, Md Mahbubul npj Computational Materials, Vol. 2, Issue 1 https://doi.org/10.1038/npjcompumats.2015.11	journal	March 2016
Development of a high-performance anode for lithium ion batteries using novel ordered mesoporous tungsten oxide materials with high electrical conductivity Yoon, Songhun; Jo, Changshin; Noh, Soon Young Physical Chemistry Chemical Physics, Vol. 13, Issue 23 https://doi.org/10.1039/c1cp20940j	journal	January 2011
MoS ₂ -on-MXene Heterostructures as Highly Reversible Anode Materials for Lithium-Ion Batteries Chen, Chi; Xie, Xiuqiang; Anasori, Babak Angewandte Chemie, Vol. 130, Issue 7 https://doi.org/10.1002/ange.201710616	journal	January 2018
Battery Performance and Photocatalytic Activity of Mesoporous Anatase TiO2 Nanospheres/Graphene Composites by Template-Free Self-Assembly Li, Na; Liu, Gang; Zhen, Chao Advanced Functional Materials, Vol. 21, Issue 9 https://doi.org/10.1002/adfm.201002295	journal	March 2011
Two-Dimensional Nanocrystals Produced by Exfoliation of Ti₃AlC₂ Naguib, Michael; Kurtoglu, Murat; Presser, Volker Advanced Materials, Vol. 23, Issue 37, p. 4248-4253 https://doi.org/10.1002/adma.201102306	journal	August 2011
Sn ⁴⁺ Ion Decorated Highly Conductive Ti ₃ C ₂ MXene: Promising Lithium-Ion Anodes with Enhanced Volumetric Capacity and Cyclic Performance Luo, Jianmin; Tao, Xinyong; Zhang, Jun ACS Nano, Vol. 10, Issue 2 https://doi.org/10.1021/acsnano.5b07333	journal	January 2016
Revealing the Pseudo‐Intercalation Charge Storage Mechanism of MXenes in Acidic Electrolyte Mu, Xinpeng; Wang, Dashuai; Du, Fei Advanced Functional Materials, Vol. 29, Issue 29 https://doi.org/10.1002/adfm.201902953	journal	May 2019
Elastic Deformations in 2D van der waals Heterostructures and their Impact on Optoelectronic Properties: Predictions from a Multiscale Computational Approach Kumar, Hemant; Er, Dequan; Dong, Liang Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep10872	journal	June 2015
The high-flux backscattering spectrometer at the NIST Center for Neutron Research Meyer, A.; Dimeo, R. M.; Gehring, P. M. Review of Scientific Instruments, Vol. 74, Issue 5 https://doi.org/10.1063/1.1568557	journal	May 2003
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Surface Structure and Reactivity of Anatase TiO ₂ Crystals with Dominant {001} Facets Selçuk, Sencer; Selloni, Annabella The Journal of Physical Chemistry C, Vol. 117, Issue 12 https://doi.org/10.1021/jp402100v	journal	March 2013
ReaxFF: A Reactive Force Field for Hydrocarbons van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois The Journal of Physical Chemistry A, Vol. 105, Issue 41 https://doi.org/10.1021/jp004368u	journal	October 2001
Atomic layer deposition of SnO 2 on MXene for Li-ion battery anodes Ahmed, Bilal; Anjum, Dalaver H.; Gogotsi, Yury Nano Energy, Vol. 34 https://doi.org/10.1016/j.nanoen.2017.02.043	journal	April 2017
Hydrolysis of 2D Transition-Metal Carbides (MXenes) in Colloidal Solutions Huang, Shuohan; Mochalin, Vadym N. Inorganic Chemistry, Vol. 58, Issue 3 https://doi.org/10.1021/acs.inorgchem.8b02890	journal	January 2019
Electronics based on two-dimensional materials Fiori, Gianluca; Bonaccorso, Francesco; Iannaccone, Giuseppe Nature Nanotechnology, Vol. 9, Issue 10 https://doi.org/10.1038/nnano.2014.207	journal	October 2014
ReaxFF Reactive Force-Field Study of Molybdenum Disulfide (MoS ₂ ) Ostadhossein, Alireza; Rahnamoun, Ali; Wang, Yuanxi The Journal of Physical Chemistry Letters, Vol. 8, Issue 3 https://doi.org/10.1021/acs.jpclett.6b02902	journal	January 2017
MXene encapsulated titanium oxide nanospheres for ultra-stable and fast sodium storage Guo, Xin; Zhang, Jinqiang; Song, Jianjun Energy Storage Materials, Vol. 14 https://doi.org/10.1016/j.ensm.2018.05.010	journal	September 2018
Multidimensional materials and device architectures for future hybrid energy storage Lukatskaya, Maria R.; Dunn, Bruce; Gogotsi, Yury Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12647	journal	September 2016
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
Two-dimensional flexible nanoelectronics Akinwande, Deji; Petrone, Nicholas; Hone, James Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6678	journal	December 2014
MXene: a promising transition metal carbide anode for lithium-ion batteries Naguib, Michael; Come, Jérémy; Dyatkin, Boris Electrochemistry Communications, Vol. 16, Issue 1, p. 61-64 https://doi.org/10.1016/j.elecom.2012.01.002	journal	March 2012
2D TiO2 nanosheets for ultrasensitive humidity sensing application benefited by abundant surface oxygen vacancy defects Gong, Miaomiao; Li, Yushu; Guo, Yanan Sensors and Actuators B: Chemical, Vol. 262 https://doi.org/10.1016/j.snb.2018.01.187	journal	June 2018
Reversible and fast Na-ion storage in MoO2/MoSe2 heterostructures for high energy-high power Na-ion capacitors Zhao, Xu; Wang, Hong-En; Yang, Ying Energy Storage Materials, Vol. 12 https://doi.org/10.1016/j.ensm.2017.12.015	journal	May 2018
Significant improvement in Mn2O3 transition metal oxide electrical conductivity via high pressure Hong, Fang; Yue, Binbin; Hirao, Naohisa Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/srep44078	journal	March 2017
Influence of metal ions intercalation on the vibrational dynamics of water confined between MXene layers Osti, Naresh C.; Naguib, Michael; Ganeshan, Karthik Physical Review Materials, Vol. 1, Issue 6 https://doi.org/10.1103/PhysRevMaterials.1.065406	journal	November 2017
Effect of Metal Ion Intercalation on the Structure of MXene and Water Dynamics on its Internal Surfaces Osti, Naresh C.; Naguib, Michael; Ostadhossein, Alireza ACS Applied Materials & Interfaces, Vol. 8, Issue 14 https://doi.org/10.1021/acsami.6b01490	journal	March 2016

Similar Records

Confinement effects on the solvation structure of solvated alkaline metal cations in a single-digit 1T-MoS₂ nanochannel: A first-principles study

Journal Article · Fri Apr 23 00:00:00 EDT 2021 · Journal of Chemical Physics · OSTI ID:1824958

Zhan, Cheng; Sun, Yangyunli; Aydin, Fikret; +2 more

Interfacial charge transfer and interaction in the MXene/TiO₂ heterostructures

Journal Article · Thu May 27 00:00:00 EDT 2021 · Physical Review Materials · OSTI ID:1824958

Xu, Lihua; Wu, Tao; Kent, Paul R.C.; +1 more

Ion-Exchange and Cation Solvation Reactions in Ti₃C₂ MXene

Journal Article · Fri Apr 29 00:00:00 EDT 2016 · Chemistry of Materials · OSTI ID:1824958

Ghidiu, Michael; Halim, Joseph; Kota, Sankalp; +3 more

Related Subjects

25 ENERGY STORAGE
heterostructure
MXene
2D-TiO2
confined electrolyte
energy storage materials
ReaxFF molecular dynamics
layered materials
molecules
two dimensional materials
cations

Title: Structure and Dynamics of Aqueous Electrolytes Confined in 2D-TiO2/Ti3C2T2 MXene Heterostructures

Citation Formats

References (67)

Similar Records

Related Subjects

Title: Structure and Dynamics of Aqueous Electrolytes Confined in 2D-TiO₂/Ti₃C₂T₂ MXene Heterostructures