Tailoring Electronic and Optical Properties of MXenes through Forming Solid Solutions

Han, Meikang; Maleski, Kathleen; Shuck, Christopher Eugene; Yang, Yizhou; Glazar, James T.; Foucher, Alexandre C.; Hantanasirisakul, Kanit; Sarycheva, Asia; Frey, Nathan C.; May, Steven J.; Shenoy, Vivek B.; Stach, Eric A.; Gogotsi, Yury

doi:10.1021/jacs.0c07395

Tailoring Electronic and Optical Properties of MXenes through Forming Solid Solutions

Journal Article · Tue Oct 27 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c07395· OSTI ID:1774152

^[1]; ^[2]; ^[2]; Yang, Yizhou ^[2]; Glazar, James T. ^[3]; ^[3]; ^[2]; Sarycheva, Asia ^[2]; ^[3]; May, Steven J. ^[2]; Shenoy, Vivek B. ^[3]; ^[3]; ^[2]

Drexel Univ., Philadelphia, PA (United States); Drexel University
Drexel Univ., Philadelphia, PA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)

Alloying is a long-established strategy to tailor properties of metals for specific applications, thus retaining or enhancing the principal elemental characteristics while offering additional functionality from the added elements. We propose a similar approach to the control of properties of two-dimensional transition metal carbides known as MXenes. MXenes (M_n+1X_n) have two sites for compositional variation: elemental substitution on both the metal (M) and carbon/nitrogen (X) sites presents promising routes for tailoring the chemical, optical, electronic, or mechanical properties of MXenes. Herein, we systematically investigated three interrelated binary solid-solution MXene systems based on Ti, Nb, and/or V at the M-site in a M₂XT_x structure (Ti_2-yNb_yCT_x, Ti_2-yV_yCT_x, and V_2-yNb_yCT_x, where T_x stands for surface terminations) showing the evolution of electronic and optical properties as a function of composition. All three MXene systems show unlimited solubility and random distribution of metal elements in the metal sublattice. Optically, the MXene systems are tailorable in a nonlinear fashion, with absorption peaks from ultraviolet to near-infrared wavelength. The macroscopic electrical conductivity of solid solution MXenes can be controllably varied over 3 orders of magnitude at room temperature and 6 orders of magnitude from 10 to 300 K. Here, this work greatly increases the number of nonstoichiometric MXenes reported to date and opens avenues for controlling physical properties of different MXenes with a limitless number of compositions possible through M-site solid solutions.

View Accepted Manuscript (DOE)

Research Organization:: Drexel Univ., Philadelphia, PA (United States)

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

Grant/Contract Number:: SC0018618; AC02-06CH11357

OSTI ID:: 1774152

Alternate ID(s):: OSTI ID: 1718966

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 45 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (42)

MAX Phases Barsoum, Michel W. Wiley‐VCH Verlag GmbH & Co https://doi.org/10.1002/9783527654581	book	January 2013
Scalable Synthesis of Ti ₃ C ₂ T _x MXene Shuck, Christopher E.; Sarycheva, Asia; Anayee, Mark Advanced Engineering Materials, Vol. 22, Issue 3 https://doi.org/10.1002/adem.201901241	journal	March 2020
Electrochromic Effect in Titanium Carbide MXene Thin Films Produced by Dip‐Coating Salles, Pol; Pinto, David; Hantanasirisakul, Kanit Advanced Functional Materials, Vol. 29, Issue 17 https://doi.org/10.1002/adfm.201809223	journal	February 2019
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
High-Performance Hydrogen Evolution from MoS _{2(1- x )} P _x Solid Solution Ye, Ruquan; del Angel-Vicente, Paz; Liu, Yuanyue Advanced Materials, Vol. 28, Issue 7 https://doi.org/10.1002/adma.201504866	journal	December 2015
Preparation of (Vx, Ti1−x)2C MXenes and their performance as anode materials for LIBs Wang, Ying; Zheng, Wei; Zhang, Peigen Journal of Materials Science, Vol. 54, Issue 18 https://doi.org/10.1007/s10853-019-03756-6	journal	June 2019
The alloy theoretic automated toolkit: A user guide van de Walle, A.; Asta, M.; Ceder, G. Calphad, Vol. 26, Issue 4 https://doi.org/10.1016/S0364-5916(02)80006-2	journal	December 2002
Vacancy-mediated lithium adsorption and diffusion on MXene Wu, Hao; Guo, Zhonglu; Zhou, Jian Applied Surface Science, Vol. 488 https://doi.org/10.1016/j.apsusc.2019.05.311	journal	September 2019
Thermodynamic modelling of multicomponent cubic Nb, Ti and V carbides/carbonitrides Frisk, Karin Calphad, Vol. 32, Issue 2 https://doi.org/10.1016/j.calphad.2007.11.007	journal	June 2008
BoltzTraP2, a program for interpolating band structures and calculating semi-classical transport coefficients Madsen, Georg K. H.; Carrete, Jesús; Verstraete, Matthieu J. Computer Physics Communications, Vol. 231 https://doi.org/10.1016/j.cpc.2018.05.010	journal	October 2018
A thermodynamic description of the C–Ti–V system over the whole composition and temperature ranges Zhang, Weibin; Peng, Yingbiao; Du, Yong International Journal of Refractory Metals and Hard Materials, Vol. 48 https://doi.org/10.1016/j.ijrmhm.2014.10.002	journal	January 2015
Alloying effects on structural, magnetic, and electrical/thermal transport properties in MAX-phase Cr2−MGeC (M= Ti, V, Mn, Fe, and Mo) Lin, Shuai; Huang, Yanan; Zu, Lin Journal of Alloys and Compounds, Vol. 680 https://doi.org/10.1016/j.jallcom.2016.04.197	journal	September 2016
Tailoring of the thermal expansion of Cr2(Alx,Ge1−x)C phases Cabioch, Thierry; Eklund, Per; Mauchamp, Vincent Journal of the European Ceramic Society, Vol. 33, Issue 4 https://doi.org/10.1016/j.jeurceramsoc.2012.10.008	journal	April 2013
Strengthening of Ti2AlC by substituting Ti with V Meng, F. L.; Zhou, Y. C.; Wang, J. Y. Scripta Materialia, Vol. 53, Issue 12 https://doi.org/10.1016/j.scriptamat.2005.08.030	journal	December 2005
On the Chemical Diversity of the MAX Phases Sokol, Maxim; Natu, Varun; Kota, Sankalp Trends in Chemistry, Vol. 1, Issue 2 https://doi.org/10.1016/j.trechm.2019.02.016	journal	May 2019
EELS of Niobium and Stoichiometric Niobium-Oxide Phases—Part I: Plasmon and Near-Edges Fine Structure Bach, David; Schneider, Reinhard; Gerthsen, Dagmar Microscopy and Microanalysis, Vol. 15, Issue 6 https://doi.org/10.1017/S143192760999105X	journal	October 2009
Raman Spectroscopy Analysis of the Structure and Surface Chemistry of Ti ₃ C ₂ T _x MXene Sarycheva, Asia; Gogotsi, Yury Chemistry of Materials, Vol. 32, Issue 8 https://doi.org/10.1021/acs.chemmater.0c00359	journal	April 2020
Synthesis and Surface Chemistry of 2D TiVC Solid-Solution MXenes Yazdanparast, Sanaz; Soltanmohammad, Sina; Fash-White, Annika ACS Applied Materials & Interfaces, Vol. 12, Issue 17 https://doi.org/10.1021/acsami.0c03181	journal	April 2020
Beyond Ti ₃ C ₂ T _x : MXenes for Electromagnetic Interference Shielding Han, Meikang; Shuck, Christopher Eugene; Rakhmanov, Roman ACS Nano, Vol. 14, Issue 4 https://doi.org/10.1021/acsnano.0c01312	journal	March 2020
The Rise of MXenes Gogotsi, Yury; Anasori, Babak ACS Nano, Vol. 13, Issue 8 https://doi.org/10.1021/acsnano.9b06394	journal	July 2019
Synthesis of Mo 4 VAlC 4 MAX Phase and Two-Dimensional Mo 4 VC 4 MXene with Five Atomic Layers of Transition Metals Deysher, Grayson; Shuck, Christopher Eugene; Hantanasirisakul, Kanit ACS Nano, Vol. 14, Issue 1 https://doi.org/10.1021/acsnano.9b07708	journal	December 2019
Growth of Alloy MoS_2xSe_2(1–x) Nanosheets with Fully Tunable Chemical Compositions and Optical Properties Li, Honglai; Duan, Xidong; Wu, Xueping Journal of the American Chemical Society, Vol. 136, Issue 10, p. 3756-3759 https://doi.org/10.1021/ja500069b	journal	February 2014
Preparation of Luminescent AgInS ₂ −AgGaS ₂ Solid Solution Nanoparticles and Their Optical Properties Uematsu, Taro; Doi, Toshihiro; Torimoto, Tsukasa The Journal of Physical Chemistry Letters, Vol. 1, Issue 22 https://doi.org/10.1021/jz101295w	journal	October 2010
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
High-entropy high-hardness metal carbides discovered by entropy descriptors Sarker, Pranab; Harrington, Tyler; Toher, Cormac Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-07160-7	journal	November 2018
Influences from solvents on charge storage in titanium carbide MXenes Wang, Xuehang; Mathis, Tyler S.; Li, Ke Nature Energy, Vol. 4, Issue 3 https://doi.org/10.1038/s41560-019-0339-9	journal	March 2019
Enhanced strength and ductility in a high-entropy alloy via ordered oxygen complexes Lei, Zhifeng; Liu, Xiongjun; Wu, Yuan Nature, Vol. 563, Issue 7732 https://doi.org/10.1038/s41586-018-0685-y	journal	November 2018
Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction Zhang, Jinqiang; Zhao, Yufei; Guo, Xin Nature Catalysis, Vol. 1, Issue 12 https://doi.org/10.1038/s41929-018-0195-1	journal	December 2018
Two-dimensional molybdenum carbides: potential thermoelectric materials of the MXene family Khazaei, Mohammad; Arai, Masao; Sasaki, Taizo Phys. Chem. Chem. Phys., Vol. 16, Issue 17 https://doi.org/10.1039/C4CP00467A	journal	January 2014
Control of electronic properties of 2D carbides (MXenes) by manipulating their transition metal layers Anasori, Babak; Shi, Chenyang; Moon, Eun Ju Nanoscale Horizons, Vol. 1, Issue 3 https://doi.org/10.1039/C5NH00125K	journal	January 2016
Coincident modulation of lattice and electron thermal transport performance in MXenes via surface functionalization Guo, Zhonglu; Miao, Naihua; Zhou, Jian Physical Chemistry Chemical Physics, Vol. 20, Issue 29 https://doi.org/10.1039/C8CP02564A	journal	January 2018
In situ formed ultrafine NbTi nanocrystals from a NbTiC solid-solution MXene for hydrogen storage in MgH ₂ Wang, Zeyi; Zhang, Xuelian; Ren, Zhuanghe Journal of Materials Chemistry A, Vol. 7, Issue 23 https://doi.org/10.1039/C9TA03665B	journal	January 2019
Synthesis and electrochemical properties of 2D molybdenum vanadium carbides – solid solution MXenes Pinto, David; Anasori, Babak; Avireddy, Hemesh Journal of Materials Chemistry A, Vol. 8, Issue 18 https://doi.org/10.1039/D0TA01798A	journal	January 2020
Multielemental single–atom-thick A layers in nanolaminated V ₂ (Sn, A ) C ( A = Fe, Co, Ni, Mn) for tailoring magnetic properties Li, Youbing; Lu, Jun; Li, Mian Proceedings of the National Academy of Sciences, Vol. 117, Issue 2 https://doi.org/10.1073/pnas.1916256117	journal	December 2019
Ordering of (Cr,V) Layers in Nanolamellar (Cr _0.5 V _0.5 ) _{n +1} AlC _n Compounds Caspi, El'ad N.; Chartier, Patrick; Porcher, Florence Materials Research Letters, Vol. 3, Issue 2 https://doi.org/10.1080/21663831.2014.975294	journal	December 2014
Valence state, hybridization and electronic band structure in the charge ordered AlV ₂ O ₄ Kalavathi, S.; Amirthapandian, S.; Chandra, Sharat Journal of Physics: Condensed Matter, Vol. 26, Issue 1 https://doi.org/10.1088/0953-8984/26/1/015601	journal	November 2013
Ti 2p X-ray absorption in titanium dioxides (TiO ₂ ): the influence of the cation site environment Crocombette, J. P.; Jollet, F. Journal of Physics: Condensed Matter, Vol. 6, Issue 49 https://doi.org/10.1088/0953-8984/6/49/022	journal	December 1994
Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes Yang, Yizhou; Hantanasirisakul, Kanit; Frey, Nathan C. 2D Materials, Vol. 7, Issue 2 https://doi.org/10.1088/2053-1583/ab68e7	journal	February 2020
Two-Dimensional Nb-Based M ₄ C ₃ Solid Solutions (MXenes) Yang, Jian; Naguib, Michael; Ghidiu, Michael Journal of the American Ceramic Society, Vol. 99, Issue 2 https://doi.org/10.1111/jace.13922	journal	October 2015
Synthesis and physical properties of (Zr _{1− x} ,Ti _x ) ₃ AlC ₂ MAX phases Zapata-Solvas, Eugenio; Hadi, Mohammad A.; Horlait, Denis Journal of the American Ceramic Society, Vol. 100, Issue 8 https://doi.org/10.1111/jace.14870	journal	April 2017
2D titanium carbide (MXene) for wireless communication Sarycheva, Asia; Polemi, Alessia; Liu, Yuqiao Science Advances, Vol. 4, Issue 9 https://doi.org/10.1126/sciadv.aau0920	journal	September 2018
The C-Nb-Ti system (Carbon - Niobium - Titanium) Bandyopadhyay, D.; Sharma, R.; Chakraborti, N. Journal of Phase Equilibria, Vol. 21, Issue 1 https://doi.org/10.1361/105497100770340480	journal	January 2000

Cited By (1)

2D transition metal carbides (MXenes) in metal and ceramic matrix composites Wyatt, Brian C.; Nemani, Srinivasa Kartik; Anasori, Babak Nano Convergence, Vol. 8, Issue 1 https://doi.org/10.1186/s40580-021-00266-7	journal	June 2021

Similar Records

Shifts in valence states in bimetallic MXenes revealed by electron energy-loss spectroscopy (EELS)

Journal Article · Sun Jan 30 23:00:00 EST 2022 · 2D Materials · OSTI ID:1979455

Tunable electrochromic behavior of titanium-based MXenes

Journal Article · Wed Jun 10 00:00:00 EDT 2020 · Nanoscale · OSTI ID:1803426

Related Subjects

Electrical conductivity
36 MATERIALS SCIENCE
Chemical structure
Elements
Metal
Two dimensional materials

Tailoring Electronic and Optical Properties of MXenes through Forming Solid Solutions

Citation Formats

References (42)

Cited By (1)

Similar Records

Related Subjects