Two-dimensional transition-metal-based carbides (or nitrides), so-called MXenes, that can be derived from the three-dimensional MAX phases, have attracted considerable attention throughout the past couple of years. The particular structure together with their hydrophilic and metallic nature make them promising candidates for a plethora of applications, such as sensors, electrodes, and catalysts. Obviously, the respective chemical and physical properties are highly dependent on the chemical composition, stoichiometry, and surface structure of the MXene. Here, we introduce a new member of the MXene family, V 4 C 3 T x (T representing the surface groups), based on the chemical exfoliation of the 413 MAX phase V 4 AlC 3 by treatment with aqueous hydrofluoric acid. X-ray powder diffraction data together with scale-bridging electron microscopy studies prove the successful removal of aluminum from the MAX phase structure. The electrocatalytic activity for the hydrogen evolution reaction of this new MXene is tested in acidic solution over the course of 100 cycles. Interestingly, we find a significant improvement of the catalytic performance over time (i.e., the overpotential required to achieve a current density of 10 mA cm −2 decreases by almost 200 mV) that we assign to the removal of an oxide species from the surface of the MXene, as shown by XPS measurements. Our study provides crucial experimental data of the electrocatalytic activity of MXenes together with the evolution of its surface structure that is also relevant for other transition-metal-based MXenes in the context of further potential applications. KEYWORDS: MAX phase, MXene, V 4 AlC 3 , V 4 C 3 T x , hydrogen evolution reaction, electrocatalysis, carbides
The 18-electron ternary intermetallic systems TiNiSn and TiCoSb are promising for applications as high-temperature thermoelectrics and comprise earth-abundant, and relatively nontoxic elements. Heusler and half-Heusler compounds are usually prepared by conventional solid state methods involving arc-melting and annealing at high temperatures for an extended period of time. Here, we report an energy-saving preparation route using a domestic microwave oven, reducing the reaction time significantly from more than a week to one minute. A microwave susceptor material rapidly heats the elemental starting materials inside an evacuated quartz tube resulting in near single phase compounds. The initial preparation is followed by a densification step involving hot-pressing, which reduces the amount of secondary phases, as verified by synchrotron X-ray diffraction, leading to the desired half-Heusler compounds, demonstrating that hot-pressing should be treated as part of the preparative process. For TiNiSn, high thermoelectric power factors of 2 mW/mK2 at temperatures in the 700 to 800 K range, and zT values of around 0.4 are found, with the microwave-prepared sample displaying somewhat superior properties to conventionally prepared half-Heuslers due to lower thermal conductivity. The TiCoSb sample shows a lower thermoelectric figure of merit when prepared using microwave methods because of a metallic second phase.
In this work, Ag(x)Te(y)-Sb(2)Te(3) heterostructured films are prepared by ligand exchange using hydrazine soluble metal chalcogenide. Because of the created interfacial barrier, cold carriers are more strongly scattered than hot ones and thereby an over 50% enhanced thermoelectric power factor (~2 μW/(cm·K(2))) is obtained at 150 °C. This shows the possibility of engineering multiphases to further improve thermoelectric performance beyond phonon scattering through a low-temperature solution processed route.
Half-Heusler thermoelectrics offer the possibility to choose from a variety of non-toxic and earth-abundant elements. TiNiSn is of particular interest and - with its relatively high electrical conductivity and Seebeck coefficient - allows for optimization of its thermoelectric figure of merit, reaching values of up to 1 in heavily-doped and/or phase-segregated systems. In this contribution, we used an energy- and time-efficient process involving solid-state preparation in a commercial microwave oven and a fast consolidation technique, Spark Plasma Sintering, to prepare a series of Ni-rich TiNi1+xSn with small deviations from the half-Heusler composition. Spark Plasma Sintering plays an important role in the process by being a part of the synthesis of the material rather than solely a densification technique. Synchrotron powder X-ray diffraction and microprobe data confirm the presence of a secondary TiNi2Sn full-Heusler phase within the half-Heusler matrix. We observe a clear correlation between the amount of full-Heusler phase and the lattice thermal conductivity of the samples, resulting in decreasing total thermal conductivity with increasing TiNi2Sn fraction. This trend shows that phonons are scattered effectively as a result of the microstructure of the materials with full-Heusler inclusions in the size range of microns to tens of microns. The best performing samples with around 5% of TiNi2Sn phase exhibit maximum figures of merit of almost 0.6 between 750 K and 800 K which is an increase of ca. 35% compared to the zT of the parent compound TiNiSn.
Engineering materials with specific physical properties have recently focused on the effect of nanoscopic inhomogeneities at the 10 nm scale. Such features are expected to scatter medium- and long-wavelength phonons thereby lowering the thermal conductivity of the system. Low thermal conductivity is a prerequisite for effective thermoelectric materials, and the challenge is to limit the transport of heat by phonons, without simultaneously decreasing charge transport. A solution-phase technique was devised for synthesis of thermoelectric "Zn(4)Sb(3)" nanocrystals as a precursor for phase segregation into ZnSb and a new Zn-Sb intermetallic phase, Zn(1+delta)Sb, in a peritectoid reaction. Our approach uses activated metal nanoparticles as precursors for the synthesis of this intermetallic compound. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. Both phases were identified and structurally characterized by automated electron diffraction tomography combined with precession electron diffraction. An ab initio structure solution based on electron diffraction data revealed two different phases. The new pseudo-hexagonal phase, Zn(1+delta)Sb, was identified and classified within the structural diversity of the Zn-Sb phase diagram.
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