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Barsoum, Michel W.

Publications and source records attributed to Barsoum, Michel W..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Ten Years of Progress in the Synthesis and Development of MXenes

Since their discovery in 2011, the number of 2D transition metal carbides and nitrides (MXenes) has steadily increased. Currently more than 40 MXene compositions exist. The ultimate number is far greater and in time they may develop into the largest family of 2D materials known. MXenes’ unique properties, such as their metal-like electrical conductivity reaching ≈20 000 S cm –1 , render them quite useful in a large number of applications, including energy storage, optoelectronic, biomedical, communications, and environmental. The number of MXene papers and patents published has been growing quickly. The first MXene generation is synthesized using selective etching of metal layers from the MAX phases, layered transition metal carbides and carbonitrides using hydrofluoric acid. Since then, multiple synthesis approaches have been developed, including selective etching in a mixture of fluoride salts and various acids, non-aqueous etchants, halogens, and molten salts, allowing for the synthesis of new MXenes with better control over their surface chemistries. In this paper, a brief historical overview of the first 10 years of MXene research and a perspective on their synthesis and future development are provided. The fact that their production is readily scalable in aqueous environments, with high yields bodes well for their commercialization.

2D materials↗
DOE OSTI2019

Atomically Layered and Ordered Rare-Earth i -MAX Phases: A New Class of Magnetic Quaternary Compounds

In 2017, we discovered quaternary i -MAX phases—atomically layered solids, where M is an early transition metal, A is an A group element, and X is C—with a (M 1 2/3 M 2 1/3 ) 2 AC chemistry, where the M 1 and M 2 atoms are in-plane ordered. Herein, we report the discovery of a class of magnetic i -MAX phases in which bilayers of a quasi-2D magnetic frustrated triangular lattice overlay a Mo honeycomb arrangement and an Al Kagomé lattice. The chemistry of this family is (Mo 2/3 RE 1/3 ) 2 AlC, and the rare-earth, RE, elements are Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. Here, the magnetic properties were characterized and found to display a plethora of ground states, resulting from an interplay of competing magnetic interactions in the presence of magnetocrystalline anisotropy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Compositions comprising free-standing two-dimensional nanocrystals

The present invention is directed to compositions comprising at least one layer or at least two layers, each layer comprising a substantially two-dimensional array of crystal cells, having first and second surfaces, each crystal cell having the empirical formula of Mn+1Xn, where M, X, and n are described in the specification, and devices incorporating these compositions.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Compositions comprising free-standing two-dimensional nanocrystals

The present invention is directed to methods of transferring urea from an aqueous solution comprising urea to a MXene composition, the method comprising contacting the aqueous solution comprising urea with the MXene composition for a time sufficient to form an intercalated MXene composition comprising urea.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

In this study, the use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improved ion accessibility to redox-active sites. A macroporous Ti 3 C 2 T x MXene film delivered up to 210 F g –1 at scan rates of 10 V s –1 , surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ~1,500 F cm –3 reaching the previously unmatched volumetric performance of RuO 2 .

25 ENERGY STORAGE↗
DOE OSTI2016

Effects of neutron irradiation of Ti 3 SiC 2 and Ti 3 AlC 2 in the 121–1085 °C temperature range

Herein we report on the formation of defects in response to neutron irradiation of polycrystalline Ti 3 SiC 2 and Ti 3 AlC 2 samples exposed to doses of 0.14±0.01, 1.6±0.1, and 3.4±0.1 displacements per atom (dpa) at irradiation temperatures of 121±12, 735±6 and 1085±68 °C. After irradiation to 0.14 dpa at 121 °C and 735 °C, black spots are observed in both Ti 3 SiC 2 and Ti 3 AlC 2 . After irradiation to 1.6 and 3.4 dpa at 735 °C, basal dislocation loops, with a Burgers vector of b = ½ [0001] are observed in Ti 3 SiC 2 , with loop diameters of 21±6 and 30±8 nm for 1.6 dpa and 3.4 dpa, respectively. In Ti3AlC2, larger dislocation loops, 75±34 nm in diameter are observed after 3.4 dpa at 735 °C, in addition to stacking faults. Impurity particles of TiC, as well as stacking fault TiC platelets in the MAX phases, are seen to form extensive dislocation loops under all conditions. Voids are observed at grain boundaries and within stacking faults after 3.4 dpa irradiation, with extensive void formation in the TiC regions at 1085 °C. Remarkably, denuded zones on the order of 1 µm are observed in Ti 3 SiC 2 after irradiation to 3.4 dpa at 735 °C. Small grains, 3-5 µm in diameter, are damage free after irradiation at 1085 °C at this dose. The presence of the A-layer in the MAX phases is seen to provide enhanced irradiation tolerance. Based on these results, and up to 3.41 dpa, Ti 3 SiC 2 remains a promising candidate for high temperature nuclear applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

MAX Phases for the Nuclear Industry: Possibilities and Pitfalls

By now it is well-established that the layered, machinable, hexagonal carbides and nitrides, with the general formula, M{sub n+1}AX{sub n}, (MAX) where n = 1 to 3, M is an early transition metal, A is an A-group (mostly groups 13 and 14) element and X is either C and/or N - sometimes referred to as polycrystalline nanolaminates because every basal plane is a potential deformation or delamination plane - combine some of the best attributes of metals and ceramics. Like metals, they are electrically and thermally conductive, most readily machinable (manual hack saw will suffice) not susceptible to thermal shock, plastic at high temperatures, and exceptionally damage tolerant. Like ceramics, some of them are elastically quite rigid, lightweight, and maintain their strengths to high temperatures. The ternaries Ti{sub 3}SiC{sub 2} and Ti{sub 2}AlC are also creep, fatigue and oxidation resistant. The impetus for this work was our conjecture - proven herein - that the presence of the pure A-layers in the MAX phases would result in extraordinary damage tolerance to neutron. After irradiation to 0.14 dpa at 121 deg. C and 735 deg. C, black spots are observed in both ternaries. After irradiation to higher doses, at 735 deg. C, basal dislocation loops, with a Burgers vector of b = 1/2 [0001] are observed in TAC with loop diameters of the order of the order of 25 nm. In TAC larger dislocation loops (75±34 nm) are observed after 3.4 dpa at 735 deg. C, in addition to stacking faults. In sharp contrast to the MAX phases, the TiC impurity particles in the former, form extensive dislocation loops at all conditions. Voids are observed at grain boundaries and within stacking faults after 3.4 dpa irradiation, with extensive void formation in the TiC regions at 1085 deg. C. Most remarkably, defect free, denuded zones, of the order of 1 μm, were observed after irradiation to 3.4 dpa at 735 deg. C. Small grains, 3-5 μm in diameter were totally damage free after irradiation at 1085 deg. C to this dose. When these results are compared to those of TiC, there is little doubt that the A-layers in the MAX phases, provide enhanced neutron irradiation tolerance. Based on these, and other results that will be touched upon, it is reasonable to conclude that Ti{sub 3}SiC{sub 2} is quite a promising candidate for high (> 500 deg. C) temperature nuclear applications. At lower temperatures anisotropic swelling results in microcracking. (authors)

36 MATERIALS SCIENCE↗
DOE OSTI2016

Ion-Exchange and Cation Solvation Reactions in Ti 3 C 2 MXene

Ti 3 C 2 and other two-dimensional transition metal carbides known as MXenes are currently being explored for many applications involving intercalated ions, from electrochemical energy storage, to contaminant sorption from water, to selected ion sieving. We report here a systematic investigation of ion exchange in Ti 3 C 2 MXene and its hydration/dehydration behavior. We have investigated the effects of the presence of LiCl during the chemical etching of the MAX phase Ti 3 AlC 2 into MXene Ti 3 C 2 T x (T stands for surface termination) and found that the resulting MXene has Li + cations in the interlayer space. We successfully exchanged the Li + cations with K + , Na + , Rb + , Mg 2+ , and Ca 2+ (supported by X-ray photoelectron and energy-dispersive spectroscopy) and found that the exchanged material expands on the unit-cell level in response to changes in humidity, with the nature of expansion dependent on the intercalated cation, similar to behavior of clay minerals; stepwise expansions of the basal spacing were observed, with changes consistent with the size of the H 2 O molecule. Thermogravimetric analysis of the dehydration behavior of these materials shows that the amounts of H 2 O contained at ambient humidity correlates simply with the hydration enthalpy of the intercalated cation, and that the diffusion of the exiting H 2 O proceeds with kinetics similar to clays. Furthermore, these results have implications for understanding, controlling, and exploiting structural changes and H 2 O sorption in MXene films and powders utilized in applications involving ions, such as electrochemical capacitors, sensors, reverse osmosis membranes, or contaminant sorbents.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Control of electronic properties of 2D carbides (MXenes) by manipulating their transition metal layers

In this paper, a transition from metallic to semiconducting-like behavior has been demonstrated in two-dimensional (2D) transition metal carbides by replacing titanium with molybdenum in the outer transition metal (M) layers of M 3 C 2 and M 4 C 3 MXenes. The MXene structure consists of n + 1 layers of near-close packed M layers with C or N occupying the octahedral site between them in an [MX] n M arrangement. Recently, two new families of ordered 2D double transition metal carbides MXenes were discovered, M' 2 M"C 2 and M' 2 M" 2 C 3 – where M' and M" are two different early transition metals, such as Mo, Cr, Ta, Nb, V, and Ti. The M' atoms only occupy the outer layers and the M" atoms fill the middle layers. In other words, M' atomic layers sandwich the middle M"–C layers. Using X-ray atomic pair distribution function (PDF) analysis on Mo 2 TiC 2 and Mo 2 Ti 2 C 3 MXenes, we present the first quantitative analysis of structures of these novel materials and experimentally confirm that Mo atoms are in the outer layers of the [MC] n M structures. The electronic properties of these Mo-containing MXenes are compared with their Ti 3 C 2 counterparts, and are found to be no longer metallic-like conductors; instead the resistance increases mildly with decreasing temperatures. Density functional theory (DFT) calculations suggest that OH terminated Mo–Ti MXenes are semiconductors with narrow band gaps. Measurements of the temperature dependencies of conductivities and magnetoresistances have confirmed that Mo 2 TiC 2 T x exhibits semiconductor-like transport behavior, while Ti 3 C 2 T x is a metal. Finally, this finding opens new avenues for the control of the electronic and optical applications of MXenes and for exploring new applications, in which semiconducting properties are required.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Synthesis and characterization of 2D molybdenum carbide (MXene)

Large scale synthesis and delamination of 2D Mo 2 CT x (where T is a surface termination group) has been achieved by selectively etching gallium from the recently discovered nanolaminated, ternary transition metal carbide Mo 2 Ga 2 C. Different synthesis and delamination routes result in different flake morphologies. The resistivity of free-standing Mo 2 CT x films increases by an order of magnitude as the temperature is reduced from 300 to 10 K, suggesting semiconductor-like behavior of this MXene, in contrast to Ti 3 C 2 T x which exhibits metallic behavior. At 10 K, the magnetoresistance is positive. Additionally, changes in electronic transport are observed upon annealing of the films. When 2 μm thick films are tested as electrodes in supercapacitors, capacitances as high as 700 F cm –3 in a 1 m sulfuric acid electrolyte and high capacity retention for at least 10,000 cycles at 10 A g –1 are obtained. Free-standing Mo 2 CT x films, with ≈8 wt% carbon nanotubes, perform well when tested as an electrode material for Li-ions, especially at high rates. In conclusion, at 20 and 131 C cycling rates, stable reversible capacities of 250 and 76 mAh g –1 , respectively, are achieved for over 1000 cycles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

A detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented in this work for select MXenes—a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Thus we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti 3 C 2 T x , Ti 2 CT x , Ti 3 CNTx, Nb 2 CT x and Nb 4 C 3 T x , where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, single bondO, single bondOH and single bondF, in addition to OH-terminations relatively strongly bonded to H 2 O molecules, was confirmed. Moreover, from XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Effect of neutron irradiation on defect evolution in Ti 3 SiC 2 and Ti 2 AlC

Here, we report on the characterization of defects formed in polycrystalline Ti 3 SiC 2 and Ti 2 AlC samples exposed to neutron irradiation – up to 0.1 displacements per atom (dpa) at 350 ± 40 °C or 695 ± 25 °C, and up to 0.4 dpa at 350 ± 40 °C. Black spots are observed in both Ti 3 SiC 2 and Ti 2 AlC after irradiation to both 0.1 and 0.4 dpa at 350 °C. After irradiation to 0.1 dpa at 695 °C, small basal dislocation loops, with a Burgers vector of b = 1/2 [0001] are observed in both materials. At 9 ± 3 and 10 ± 5 nm, the loop diameters in the Ti 3 SiC 2 and Ti 2 AlC samples, respectively, were comparable. At 1 × 10 23 loops/m 3 , the dislocation loop density in Ti 2 AlC was ≈1.5 orders of magnitude greater than in Ti 3 SiC 2 , at 3 x 10 21 loops/m3. After irradiation at 350 °C, extensive microcracking was observed in Ti 2 AlC, but not in Ti 3 SiC 2 . The room temperature electrical resistivities increased as a function of neutron dose for all samples tested, and appear to saturate in the case of Ti 3 SiC 2 . The MAX phases are unequivocally more neutron radiation tolerant than the impurity phases TiC and Al 2 O 3 . Based on these results, Ti 3 SiC 2 appears to be a more promising MAX phase candidate for high temperature nuclear applications than Ti 2 AlC.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Two-Dimensional Nb-Based M 4 C 3 Solid Solutions (MXenes)

Two new two-dimensional Nb 4 C 3 -based solid solutions (MXenes), (Nb 0.8 ,Ti 0.2 ) 4 C 3 T x and (Nb 0.8 ,Zr 0.2 ) 4 C 3 T x (where T is a surface termination) were synthesizedas confirmed by X-ray diffractionfrom their corresponding MAX phase precursors (Nb 0.8 ,Ti 0.2 ) 4 AlC 3 and (Nb 0.8 ,Zr 0.2 ) 4 AlC 3 . In our report we discuss Zr-containing MXene. We also studied intercalation of Li ions into these two compositions, and Nb 4 C 3 T x in order to determine the potential of those materials for energy storage applications. Lithiation and delithiation peaks at 2.26 and 2.35 V, respectively, appeared in the case of Nb 4 C 3 T x , but were not present in Nb 2 CT x . After 20 cycles at a rate of C/4, the specific capacities of (Nb 0.8 ,Ti 0.2 ) 4 C 3 T x and (Nb 0.8 ,Ti 0.2 ) 4 C 3 T x were 158 and 132 mAh/g, respectively, both slightly lower than the capacity of Nb 4 C 3 T x .

36 MATERIALS SCIENCE↗