High‐Entropy Carbonitride MAX Phases and Their Derivative MXenes

2021 ◽  
pp. 2103228
Author(s):  
Zhiguo Du ◽  
Cheng Wu ◽  
Yuchuan Chen ◽  
Qi Zhu ◽  
Yanglansen Cui ◽  
...  
Keyword(s):  
2019 ◽  
Vol 117 (2) ◽  
pp. 820-825 ◽  
Author(s):  
Youbing Li ◽  
Jun Lu ◽  
Mian Li ◽  
Keke Chang ◽  
Xianhu Zha ◽  
...  

Tailoring of individual single–atom-thick layers in nanolaminated materials offers atomic-level control over material properties. Nonetheless, multielement alloying in individual atomic layers in nanolaminates is largely unexplored. Here, we report 15 inherently nanolaminated V2(AxSn1-x)C (A = Fe, Co, Ni, Mn, and combinations thereof, with x ∼ 1/3) MAX phases synthesized by an alloy-guided reaction. The simultaneous occupancy of the 4 magnetic elements and Sn in the individual single–atom-thick A layers constitutes high-entropy MAX phase in which multielemental alloying exclusively occurs in the 2-dimensional (2D) A layers. V2(AxSn1-x)C exhibit distinct ferromagnetic behavior that can be compositionally tailored from the multielement A-layer alloying. Density functional theory and phase diagram calculations are performed to understand the structure stability of these MAX phases. This 2D multielemental alloying approach provides a structural design route to discover nanolaminated materials and expand their chemical and physical properties. In fact, the magnetic behavior of these multielemental MAX phases shows strong dependency on the combination of various elements.


2021 ◽  
Author(s):  
Srinivasa Kartik Nemani ◽  
BOWEN ZHANG ◽  
Brian C. Wyatt ◽  
Zachary D. Hood ◽  
Sukriti Manna ◽  
...  

<p>Two-dimensional (2D) transition metal carbides and nitrides, known as MXenes, are a fast-growing family of 2D materials. MXenes 2D flakes have <i>n </i>+ 1 (<i>n</i> = 1 – 4) atomic layers of transition metals interleaved by carbon/nitrogen layers, but to-date remain limited in composition to one or two transition metals. In this study, through the use of four transition metals, we report the synthesis of multi-principal element high-entropy M<sub>4</sub>C<sub>3</sub>T<i><sub>x</sub></i> MXenes. Specifically, we introduce two high-entropy MXenes, TiVNbMoC<sub>3</sub>T<i><sub>x</sub></i> and TiVCrMoC<sub>3</sub>T<i><sub>x</sub></i>, as well as their precursor TiVNbMoAlC<sub>3</sub> and TiVCrMoAlC<sub>3 </sub>high-entropy MAX phases. We used a combination of real and reciprocal space characterization (x-ray diffraction, x-ray photoelectron spectroscopy, energy dispersive x-ray spectroscopy, and scanning transmission electron microscopy) to establish the structure, phase purity, and equimolar distribution of the four transition metals in high-entropy MAX and MXene phases. We use first-principles calculations to compute the formation energies and explore synthesizability of these high-entropy MAX phases. We also show that when three transition metals are used instead of four, under similar synthesis conditions to those of the four-element MAX phase, two different MAX phases can be formed (<i>i.e.</i> no pure single-phase forms). This finding indicates the importance of configurational entropy in stabilizing the desired single-phase high-entropy MAX over multiphases of MAX, which is essential for the synthesis of phase-pure high-entropy MXenes. The synthesis of high-entropy MXenes significantly expand the compositional variety of the MXene family to further tune their properties, including electronic, magnetic, electrochemical, catalytic, high temperature stability, and mechanical properties. </p>


2021 ◽  
Author(s):  
Srinivasa Kartik Nemani ◽  
BOWEN ZHANG ◽  
Brian C. Wyatt ◽  
Zachary D. Hood ◽  
Sukriti Manna ◽  
...  

<p>Two-dimensional (2D) transition metal carbides and nitrides, known as MXenes, are a fast-growing family of 2D materials. MXenes 2D flakes have <i>n </i>+ 1 (<i>n</i> = 1 – 4) atomic layers of transition metals interleaved by carbon/nitrogen layers, but to-date remain limited in composition to one or two transition metals. In this study, through the use of four transition metals, we report the synthesis of multi-principal element high-entropy M<sub>4</sub>C<sub>3</sub>T<i><sub>x</sub></i> MXenes. Specifically, we introduce two high-entropy MXenes, TiVNbMoC<sub>3</sub>T<i><sub>x</sub></i> and TiVCrMoC<sub>3</sub>T<i><sub>x</sub></i>, as well as their precursor TiVNbMoAlC<sub>3</sub> and TiVCrMoAlC<sub>3 </sub>high-entropy MAX phases. We used a combination of real and reciprocal space characterization (x-ray diffraction, x-ray photoelectron spectroscopy, energy dispersive x-ray spectroscopy, and scanning transmission electron microscopy) to establish the structure, phase purity, and equimolar distribution of the four transition metals in high-entropy MAX and MXene phases. We use first-principles calculations to compute the formation energies and explore synthesizability of these high-entropy MAX phases. We also show that when three transition metals are used instead of four, under similar synthesis conditions to those of the four-element MAX phase, two different MAX phases can be formed (<i>i.e.</i> no pure single-phase forms). This finding indicates the importance of configurational entropy in stabilizing the desired single-phase high-entropy MAX over multiphases of MAX, which is essential for the synthesis of phase-pure high-entropy MXenes. The synthesis of high-entropy MXenes significantly expand the compositional variety of the MXene family to further tune their properties, including electronic, magnetic, electrochemical, catalytic, high temperature stability, and mechanical properties. </p>


2020 ◽  
Author(s):  
Junbo Wang ◽  
Yanyan Cui ◽  
Qingsong Wang ◽  
Kai Wang ◽  
Xiaohui Wang ◽  
...  

<p>Layered Li<i><sub>x</sub></i>MO<sub>2</sub> materials, a new class of high-entropy oxides, have been synthesized by nebulized spray pyrolysis. Specifically, the lattice structure of Li(Ni<sub>1/3</sub>Mn<sub>1/3</sub>Co<sub>1/3</sub>)O<sub>2</sub> (NCM111) cathode material has been replicated successfully while increasing the number of cations in equimolar proportions, thereby allowing transition to high-entropy oxide materials.</p>


2019 ◽  
Author(s):  
Jack Pedersen ◽  
Thomas Batchelor ◽  
Alexander Bagger ◽  
Jan Rossmeisl

Using the high-entropy alloys (HEAs) CoCuGaNiZn and AgAuCuPdPt as starting points we provide a framework for tuning the composition of disordered multi-metallic alloys to control the selectivity and activity of the reduction of carbon dioxide (CO2) to highly reduced compounds. By combining density functional theory (DFT) with supervised machine learning we predicted the CO and hydrogen (H) adsorption energies of all surface sites on the (111) surface of the two HEAs. This allowed an optimization for the HEA compositions with increased likelihood for sites with weak hydrogen adsorption{to suppress the formation of molecular hydrogen (H2) and with strong CO adsorption to favor the reduction of CO. This led to the discovery of several disordered alloy catalyst candidates for which selectivity towards highly reduced carbon compounds is expected, as well as insights into the rational design of disordered alloy catalysts for the CO2 and CO reduction reaction.


2019 ◽  
Author(s):  
Nirmal Kumar ◽  
Subramanian Nellaiappan ◽  
Ritesh Kumar ◽  
Kirtiman Deo Malviya ◽  
K. G. Pradeep ◽  
...  

<div>Renewable harvesting clean and hydrogen energy using the benefits of novel multicatalytic materials of high entropy alloy (HEA equimolar Cu-Ag-Au-Pt-Pd) from formic acid with minimum energy input has been achieved in the present investigation. The synthesis effect of pristine elements in the HEA drives the electro-oxidation reaction towards non-carbonaceous pathway . The atomistic simulation based on DFT rationalize the distinct lowering of the d-band center for the individual atoms in the HEA as compared to the pristine counterparts. This catalytic activity of the HEA has also been extended to methanol electro-oxidation to show the unique capability of the novel catalyst. The nanostructured HEA, properties using a combination of casting and cry omilling techniques can further be utilized as fuel cell anode in direct formic acid/methanol fuel cells (DFFE).<br></div>


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