Effects of Applied Potential and Water Intercalation on the Surface Chemistry of Ti2C and Mo2C MXenes

Fredrickson, Kurt D.; Anasori, Babak; Seh, Zhi Wei; Gogotsi, Yury; Vojvodic, Aleksandra

doi:10.1021/acs.jpcc.6b09109

Title: Effects of Applied Potential and Water Intercalation on the Surface Chemistry of Ti₂C and Mo₂C MXenes

Journal Article · Fri Dec 09 00:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b09109· OSTI ID:1360912

Fredrickson, Kurt D. ^[1]; Anasori, Babak ^[2]; Seh, Zhi Wei ^[3];

^[2];

^[4]

Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Drexel Univ., Philadelphia, PA (United States)
Agency for Science, Technology and Research (A*STAR) (Singapore)
Univ. of Pennsylvania, Philadelphia, PA (United States)

Here, two-dimensional transition metal carbides and nitrides, also known as MXenes, represent an attractive class of materials for a multitude of electrochemical and other applications. While single sheets of MXenes have been widely studied theoretically, there have been much fewer studies on layered bulk MXenes, which are more representative of multi- or few-layer MXenes used in actual applications. Herein, we investigate the structural and electronic effects of water intercalation, multiple functional groups and applied potential on layered bulk Ti₂C and Mo₂C MXenes using density functional theory. The out-of plane lattice parameter, c, was found to vary significantly with the functional group, and is greatly increased upon intercalation of water. Experimental results confirm the change in lattice constant due to addition or removal of intercalated water. Under zero applied potential, both Ti₂C and Mo₂C were found to be functionalized by one monolayer of O; bare MXenes were never found to be stable, regardless of the applied potential. Applying a potential changed the adsorbate coverage, changing the systems from O covered to H covered at negative potentials and, in some cases, giving rise to a metal–insulator transition. Understanding of the effects of surface functionalization and water intercalation of MXenes provides a better insight of their use for catalytic and electronic applications.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1360912

Journal Information:: Journal of Physical Chemistry. C, Vol. 120, Issue 50; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 92 works

Citation information provided by
Web of Science

References (44)

25th Anniversary Article: MXenes: A New Family of Two-Dimensional Materials Naguib, Michael; Mochalin, Vadym N.; Barsoum, Michel W. Advanced Materials, Vol. 26, Issue 7, p. 992-1005 https://doi.org/10.1002/adma.201304138	journal	December 2013
Recent advances in MXene: Preparation, properties, and applications Lei, Jin-Cheng; Zhang, Xu; Zhou, Zhen Frontiers of Physics, Vol. 10, Issue 3 https://doi.org/10.1007/s11467-015-0493-x	journal	June 2015
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
Two-Dimensional Transition Metal Carbides Naguib, Michael; Mashtalir, Olha; Carle, Joshua ACS Nano, Vol. 6, Issue 2 https://doi.org/10.1021/nn204153h	journal	January 2012
New Two-Dimensional Niobium and Vanadium Carbides as Promising Materials for Li-Ion Batteries Naguib, Michael; Halim, Joseph; Lu, Jun Journal of the American Chemical Society, Vol. 135, Issue 43 https://doi.org/10.1021/ja405735d	journal	October 2013
Synthesis of Two-Dimensional Materials by Selective Extraction Naguib, Michael; Gogotsi, Yury Accounts of Chemical Research, Vol. 48, Issue 1 https://doi.org/10.1021/ar500346b	journal	December 2014
Resolving the Structure of Ti ₃ C ₂ T _x MXenes through Multilevel Structural Modeling of the Atomic Pair Distribution Function Wang, Hsiu-Wen; Naguib, Michael; Page, Katharine Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b04250	journal	December 2015
Ti ₃ C ₂ MXene as a High Capacity Electrode Material for Metal (Li, Na, K, Ca) Ion Batteries Er, Dequan; Li, Junwen; Naguib, Michael ACS Applied Materials & Interfaces, Vol. 6, Issue 14 https://doi.org/10.1021/am501144q	journal	June 2014
What Nano Can Do for Energy Storage Gogotsi, Yury ACS Nano, Vol. 8, Issue 6 https://doi.org/10.1021/nn503164x	journal	May 2014
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
MXene: A New Family of Promising Hydrogen Storage Medium Hu, Qianku; Sun, Dandan; Wu, Qinghua The Journal of Physical Chemistry A, Vol. 117, Issue 51 https://doi.org/10.1021/jp409585v	journal	December 2013
MXene: a promising photocatalyst for water splitting Guo, Zhonglu; Zhou, Jian; Zhu, Linggang Journal of Materials Chemistry A, Vol. 4, Issue 29 https://doi.org/10.1039/C6TA04414J	journal	January 2016
Two-Dimensional Molybdenum Carbide (MXene) as an Efficient Electrocatalyst for Hydrogen Evolution Seh, Zhi Wei; Fredrickson, Kurt D.; Anasori, Babak ACS Energy Letters, Vol. 1, Issue 3 https://doi.org/10.1021/acsenergylett.6b00247	journal	August 2016
Intercalation and delamination of layered carbides and carbonitrides Mashtalir, Olha; Naguib, Michael; Mochalin, Vadym N. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2664	journal	April 2013
Interacting Carbon Nitride and Titanium Carbide Nanosheets for High-Performance Oxygen Evolution Ma, Tian Yi; Cao, Jian Liang; Jaroniec, Mietek Angewandte Chemie International Edition, Vol. 55, Issue 3 https://doi.org/10.1002/anie.201509758	journal	December 2015
Preparation of MXene-Cu2O nanocomposite and effect on thermal decomposition of ammonium perchlorate Gao, Yupeng; Wang, Libo; Li, Zhengyang Solid State Sciences, Vol. 35 https://doi.org/10.1016/j.solidstatesciences.2014.06.014	journal	September 2014
An extraordinarily stable catalyst: Pt NPs supported on two-dimensional Ti3C2X2 (X = OH, F) nanosheets for oxygen reduction reaction Xie, Xiaohong; Chen, Siguo; Ding, Wei Chemical Communications, Vol. 49, Issue 86 https://doi.org/10.1039/c3cc44428g	journal	January 2013
Synthesis of ruthenium nanoparticles deposited on graphene-like transition metal carbide as an effective catalyst for the hydrolysis of sodium borohydride Li, Xiaojing; Fan, Guangyin; Zeng, Chunmei International Journal of Hydrogen Energy, Vol. 39, Issue 27 https://doi.org/10.1016/j.ijhydene.2014.07.029	journal	September 2014
Role of Surface Structure on Li-Ion Energy Storage Capacity of Two-Dimensional Transition-Metal Carbides Xie, Yu; Naguib, Michael; Mochalin, Vadym N. Journal of the American Chemical Society, Vol. 136, Issue 17 https://doi.org/10.1021/ja501520b	journal	April 2014
X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes) Halim, Joseph; Cook, Kevin M.; Naguib, Michael Applied Surface Science, Vol. 362 https://doi.org/10.1016/j.apsusc.2015.11.089	journal	January 2016
Are MXenes Promising Anode Materials for Li Ion Batteries? Computational Studies on Electronic Properties and Li Storage Capability of Ti ₃ C ₂ and Ti ₃ C ₂ X ₂ (X = F, OH) Monolayer Tang, Qing; Zhou, Zhen; Shen, Panwen Journal of the American Chemical Society, Vol. 134, Issue 40 https://doi.org/10.1021/ja308463r	journal	September 2012
Structural and Electronic Properties and Stability of MX enes Ti ₂ C and Ti ₃ C ₂ Functionalized by Methoxy Groups Enyashin, Andrey N.; Ivanovskii, Alexander L. The Journal of Physical Chemistry C, Vol. 117, Issue 26 https://doi.org/10.1021/jp401820b	journal	June 2013
Novel Electronic and Magnetic Properties of Two-Dimensional Transition Metal Carbides and Nitrides Khazaei, Mohammad; Arai, Masao; Sasaki, Taizo Advanced Functional Materials, Vol. 23, Issue 17 https://doi.org/10.1002/adfm.201202502	journal	December 2012
Surface group modification and carrier transport properties of layered transition metal carbides (Ti ₂ CT _x , T: –OH, –F and –O) Lai, Shen; Jeon, Jaeho; Jang, Sung Kyu Nanoscale, Vol. 7, Issue 46 https://doi.org/10.1039/C5NR06513E	journal	January 2015
OH-terminated two-dimensional transition metal carbides and nitrides as ultralow work function materials Khazaei, Mohammad; Arai, Masao; Sasaki, Taizo Physical Review B, Vol. 92, Issue 7 https://doi.org/10.1103/PhysRevB.92.075411	journal	August 2015
Predicted Surface Composition and Thermodynamic Stability of MXenes in Solution Ashton, Michael; Mathew, Kiran; Hennig, Richard G. The Journal of Physical Chemistry C, Vol. 120, Issue 6 https://doi.org/10.1021/acs.jpcc.5b11887	journal	February 2016
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
Electronic structure of hexagonal Ti3AlC2 and Ti3AlN2 Ivanovskii, Alexander L.; Medvedeva, Nadezhda I. Mendeleev Communications, Vol. 9, Issue 1 https://doi.org/10.1070/MC1999v009n01ABEH001039	journal	January 1999
Electronic properties ofTi3SiC2-based solid solutions Medvedeva, N. I.; Novikov, D. L.; Ivanovsky, A. L. Physical Review B, Vol. 58, Issue 24 https://doi.org/10.1103/PhysRevB.58.16042	journal	December 1998
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
An object-oriented scripting interface to a legacy electronic structure code Bahn, S. R.; Jacobsen, K. W. Computing in Science & Engineering, Vol. 4, Issue 3 https://doi.org/10.1109/5992.998641	journal	January 2002
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation Wellendorff, Jess; Lundgaard, Keld T.; Møgelhøj, Andreas Physical Review B, Vol. 85, Issue 23 https://doi.org/10.1103/PhysRevB.85.235149	journal	June 2012
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism Vanderbilt, David Physical Review B, Vol. 41, Issue 11, p. 7892-7895 https://doi.org/10.1103/PhysRevB.41.7892	journal	April 1990
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Synthesis of two-dimensional molybdenum carbide, Mo 2 C, from the gallium based atomic laminate Mo 2 Ga 2 C Meshkian, Rahele; Näslund, Lars-Åke; Halim, Joseph Scripta Materialia, Vol. 108 https://doi.org/10.1016/j.scriptamat.2015.07.003	journal	November 2015
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
Hybrid density functional study of structural and electronic properties of functionalized Ti $_{n + 1} X_{n}$ ( $X = C$ , N) monolayers Xie, Yu; Kent, P. R. C. Physical Review B, Vol. 87, Issue 23 https://doi.org/10.1103/PhysRevB.87.235441	journal	June 2013
Oxygen adsorption and dissociation during the oxidation of monolayer Ti2C Gan, Li-Yong; Huang, Dan; Schwingenschlögl, Udo Journal of Materials Chemistry A, Vol. 1, Issue 43 https://doi.org/10.1039/c3ta12032e	journal	January 2013
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
Ion-Exchange and Cation Solvation Reactions in Ti ₃ C ₂ MXene Ghidiu, Michael; Halim, Joseph; Kota, Sankalp Chemistry of Materials, Vol. 28, Issue 10 https://doi.org/10.1021/acs.chemmater.6b01275	journal	May 2016
Synthesis and Characterization of 2D Molybdenum Carbide (MXene) Halim, Joseph; Kota, Sankalp; Lukatskaya, Maria R. Advanced Functional Materials, Vol. 26, Issue 18 https://doi.org/10.1002/adfm.201505328	journal	February 2016
The effect of hydrazine intercalation on the structure and capacitance of 2D titanium carbide (MXene) Mashtalir, O.; Lukatskaya, M. R.; Kolesnikov, A. I. Nanoscale, Vol. 8, Issue 17 https://doi.org/10.1039/C6NR01462C	journal	January 2016
Intriguing electronic properties of two-dimensional MoS ₂ /TM ₂ CO ₂ (TM = Ti, Zr, or Hf) hetero-bilayers: type-II semiconductors with tunable band gaps Li, Xinru; Dai, Ying; Ma, Yandong Nanotechnology, Vol. 26, Issue 13 https://doi.org/10.1088/0957-4484/26/13/135703	journal	March 2015
Probing the Mechanism of High Capacitance in 2D Titanium Carbide Using In Situ X-Ray Absorption Spectroscopy Lukatskaya, Maria R.; Bak, Seong-Min; Yu, Xiqian Advanced Energy Materials, Vol. 5, Issue 15 https://doi.org/10.1002/aenm.201500589	journal	May 2015

Cited By (8)

Synthesis and photocatalytic H ₂ ‐production activity of plasma‐treated Ti ₃ C ₂ T _x MXene modified graphitic carbon nitride Xu, Fang; Zhang, Dainan; Liao, Yulong Journal of the American Ceramic Society, Vol. 103, Issue 2 https://doi.org/10.1111/jace.16798	journal	September 2019
Surface and Interface Engineering: Molybdenum Carbide–Based Nanomaterials for Electrochemical Energy Conversion Ge, Riyue; Huo, Juanjuan; Sun, Mingjie Small https://doi.org/10.1002/smll.201903380	journal	September 2019
Recent Progress of MXene-Based Nanomaterials in Flexible Energy Storage and Electronic Devices Yang, Qi; Wang, Yukun; Li, Xinliang Energy & Environmental Materials, Vol. 1, Issue 4 https://doi.org/10.1002/eem2.12023	journal	December 2018
Engineering Multifunctional Collaborative Catalytic Interface Enabling Efficient Hydrogen Evolution in All pH Range and Seawater Wu, Xianhong; Zhou, Si; Wang, Zhiyu Advanced Energy Materials, Vol. 9, Issue 34 https://doi.org/10.1002/aenm.201901333	journal	July 2019
Oxidized Ti ₃ C ₂ MXene nanosheets for dye-sensitized solar cells Dall'Agnese, Chunxiang; Dall'Agnese, Yohan; Anasori, Babak New Journal of Chemistry, Vol. 42, Issue 20 https://doi.org/10.1039/c8nj03246g	journal	January 2018
Strong Surface‐Bound Sulfur in Carbon Nanotube Bridged Hierarchical Mo ₂ C‐Based MXene Nanosheets for Lithium–Sulfur Batteries Lv, Li‐Ping; Guo, Chao‐Fei; Sun, Weiwei Small https://doi.org/10.1002/smll.201804338	journal	December 2018
MXene‐Based Composites: Synthesis and Applications in Rechargeable Batteries and Supercapacitors Yang, Jian; Bao, Weizhai; Jaumaux, Pauline Advanced Materials Interfaces, Vol. 6, Issue 8 https://doi.org/10.1002/admi.201802004	journal	February 2019
A Robust, Freestanding MXene‐Sulfur Conductive Paper for Long‐Lifetime Li–S Batteries Tang, Huan; Li, Wenlong; Pan, Limei Advanced Functional Materials, Vol. 29, Issue 30 https://doi.org/10.1002/adfm.201901907	journal	May 2019

Similar Records

Tuning the Microenvironment of Water Confined in Ti ₃ C ₂ T _x MXene by Cation Intercalation

Journal Article · Wed Feb 14 00:00:00 EST 2024 · Journal of Physical Chemistry. C · OSTI ID:1360912

Lounasvuori, Mailis; Zhang, Teng; Gogotsi, Yury; +1 more

Probing the In Situ Pseudocapacitive Charge Storage in Ti₃C₂ MXene Thin Films with X-ray Reflectivity

Journal Article · Tue Aug 31 00:00:00 EDT 2021 · ACS Applied Materials and Interfaces · OSTI ID:1360912

Sobyra, Thomas B.; Mathis, Tyler S.; Gogotsi, Yury; +1 more

Influence of metal ions intercalation on the vibrational dynamics of water confined between MXene layers

Journal Article · Tue Nov 21 00:00:00 EST 2017 · Physical Review Materials · OSTI ID:1360912

Osti, Naresh C.; Naguib, Michael; Ganeshan, Karthik; +8 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Effects of Applied Potential and Water Intercalation on the Surface Chemistry of Ti2C and Mo2C MXenes

Citation Formats

References (44)

Cited By (8)

Similar Records

Related Subjects

Title: Effects of Applied Potential and Water Intercalation on the Surface Chemistry of Ti₂C and Mo₂C MXenes