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1. Green synthesis of reduced Ti ₃ C ₂ T _x MXene nanosheets with enhanced conductivity, oxidation stability, and SERS activity

   https://doi.org/10.1039/C9TC06984D  

   Limbu, Tej B. ; Chitara, Basant ; Orlando, Jason D. ; Garcia Cervantes, Martha Y. ; Kumari, Shalini ; Li, Qi ; Tang, Yongan ; Yan, Fei ( April 2020 , Journal of Materials Chemistry C)

   Transition metal carbides (MXenes) are an emerging family of highly conductive two-dimensional materials with additional functional properties introduced by surface terminations. Further modification of the surface terminations makes MXenes even more appealing for practical applications. Herein, we report a facile and environmentally benign synthesis of reduced Ti 3 C 2 T x MXene (r-Ti 3 C 2 T x ) via a simple treatment with l -ascorbic acid at room temperature. r-Ti 3 C 2 T x shows a six-fold increase in electrical conductivity, from 471 ± 49 for regular Ti 3 C 2 T x to 2819 ± 306more »S m −1 for the reduced version. Additionally, we show an enhanced oxidation stability of r-Ti 3 C 2 T x as compared to regular Ti 3 C 2 T x . An examination of the surface-enhanced Raman scattering (SERS) activity reveals that the SERS enhancement factor of r-Ti 3 C 2 T x is an order of magnitude higher than that of regular Ti 3 C 2 T x . The improved SERS activity of r-Ti 3 C 2 T x is attributed to the charge transfer interaction between the MXene surface and probe molecules, re-enforced by an increased electronic density of states (DOS) at the Fermi level of r-Ti 3 C 2 T x . The findings of this study suggest that reduced MXene could be a superior choice over regular MXene, especially for the applications that employ high electronic conductivity, such as electrode materials for batteries and supercapacitors, photodetectors, and SERS-based sensors.« less
2. One-step hydrothermal synthesis of porous Ti ₃ C ₂ T _z MXene/rGO gels for supercapacitor applications

   https://doi.org/10.1039/D1NR02114A  

   Saha, Sanjit ; Arole, Kailash ; Radovic, Miladin ; Lutkenhaus, Jodie L. ; Green, Micah J. ( October 2021 , Nanoscale)

   Titanium carbide/reduced graphene oxide (Ti 3 C 2 T z /rGO) gels were prepared by a one-step hydrothermal process. The gels show a highly porous structure with a surface area of ∼224 m 2 g −1 and average pore diameter of ∼3.6 nm. The content of GO and Ti 3 C 2 T z nanosheets in the reaction precursor was varied to yield different microstructures. The supercapacitor performance of Ti 3 C 2 T z /rGO gels varied significantly with composition. Specific capacitance initially increased with increasing Ti 3 C 2 T z content, but at high Ti 3 Cmore »2 T z content gels cannot be formed. Also, the retention of capacitance decreased with increasing Ti 3 C 2 T z content. Ti 3 C 2 T z /rGO gel electrodes exhibit enhanced supercapacitor properties with high potential window (1.5 V) and large specific capacitance (920 F g −1 ) in comparison to pure rGO and Ti 3 C 2 T z . The synergistic effect of EDLC from rGO and redox capacitance from Ti 3 C 2 T z was the reason for the enhanced supercapacitor performance. A symmetric two-electrode supercapacitor cell was constructed with Ti 3 C 2 T z /rGO, which showed very high areal capacitance (158 mF cm −2 ), large energy density (∼31.5 μW h cm −2 corresponding to a power density of ∼370 μW cm −2 ), and long stability (∼93% retention) after 10 000 cycles.« less
3. Experimental and computational investigations of TiIrB: a new ternary boride with Ti _1+x Rh _2−x+y Ir _3−y B ₃ -type structure

   https://doi.org/10.1515/znb-2021-0121  

   Scheifers, Jan P. ; Gibson, Kate A. ; Fokwa, Boniface P. ( October 2021 , Zeitschrift für Naturforschung B)

   Abstract A new ternary phase, TiIrB, was synthesized by arc-melting of the elements and characterized by powder X-ray diffraction. The compound crystallizes in the orthorhombic Ti 1+ x Rh 2− x + y Ir 3− y B 3 structure type, space group Pbam (no. 55) with the lattice parameters a  = 8.655(2), b  = 15.020(2), and c  = 3.2271(4) Å. Density Functional Theory (DFT) calculations were carried out to understand the electronic structure, including a Bader charge analysis. The charge distribution of TiIrB in the Ti 1+ x Rh 2− x + y Ir 3− y B 3 -type phase has been evaluatedmore »for the first time, and the results indicate that more electron density is transferred to the boron atoms in the zigzag B 4 units than to isolated boron atoms.« less
4. Synthesis of colloidal MnAs _x Sb _1−x nanoparticles: compositional inhomogeneity and magnetic consequences

   https://doi.org/10.1039/D1TC02479E  

   Hettiarachchi, Malsha A. ; Su’a, Tepora ; Abdelhamid, Ehab ; Pokhrel, Shiva ; Nadgorny, Boris ; Brock, Stephanie L. ( October 2021 , Journal of Materials Chemistry C)

   The ternary manganese pnictide phases, MnAs 1− x Sb x , are of interest for magnetic refrigeration and waste heat recovery due to their magnetocaloric properties, maximized at the Curie temperature ( T C ), which varies from 580–240 K, depending on composition. Nanoparticles potentially enable application in microelectronics (cooling) or graded composites that can operate over a wide temperature range, but manganese pnictides are synthetically challenging to realize as discrete nanoparticles and their fundamental magnetic properties have not been extensively studied. Accordingly, colloidal synthesis methods were employed to target discrete MnAs x Sb 1− x nanoparticles ( x =more »0.1–0.9) by arrested precipitation reactions of Mn 2 (CO) 10 with (C 6 H 5 ) 3 AsO and (C 6 H 5 ) 3 Sb in coordinating solvents. The MnAs x Sb 1− x particles are spherical in morphology with average diameters 10–13 nm (standard deviations <20% based on transmission electron microscopy analysis). X-Ray fluorescence spectroscopy measurements on ensembles showed that all phases had an excess of Sb relative to the targeted composition, whereas energy dispersive spectroscopic mapping data of single particles revealed that the nanoparticles are inhomogeneous, adopting a core–shell structure, with the amorphous shell rich in Mn and O (and sometimes Sb) while the crystalline core is rich in Mn, As, and Sb. Magnetization measurements of the nanoparticle ensemble demonstrated the presence of both ferromagnetic and paramagnetic phases. By combining the magnetization measurements with precision chemical mapping and simple modeling, we were able to unambiguously attribute ferromagnetism to the MnAs x Sb 1− x crystalline core, whereas paramagnetism was attributed to the amorphous shell. Magnetization measurements at variable temperatures were used to determine the superparamagnetic transition of the nanoparticles, although for some compositions and particle sizes the blocking temperature exceeded room temperature. Preliminary magnetic studies also revealed a conventional dependence between core size and coercivity, in spite of variable compositions of the nanoparticles, an unexpected result.« less
5. High stability SrTi _1−x Fe _x O _3−δ electrodes for oxygen reduction and oxygen evolution reactions

   https://doi.org/10.1039/c9ta07548h  

   Zhang, Shan-Lin ; Cox, Dalton ; Yang, Hao ; Park, Beom-Kyeong ; Li, Cheng-Xin ; Li, Chang-Jiu ; Barnett, Scott A. ( September 2019 , Journal of Materials Chemistry A)

   Sr(Ti 1−x Fe x )O 3−δ (STF) has recently been explored as an oxygen electrode for solid oxide electrochemical cells (SOCs). Model thin film electrode studies show oxygen surface exchange rates that generally improve with increasing Fe content when x < 0.5, and are comparable to the best Co-containing perovskite electrode materials. Recent results on porous electrodes with the specific composition Sr(Ti 0.3 Fe 0.7 )O 3−δ show excellent electrode performance and stability, but other compositions have not been tested. Here we report results for porous electrodes with a range of compositions from x = 0.5 to 0.9. The polarizationmore »resistance decreases with increasing Fe content up to x = 0.7, but increases for further increases in x . This results from the interaction of two effects – the oxygen solid state diffusion coefficient increases with increasing x , but the electrode surface area and surface oxygen exchange rate decrease due to increased sinterability and Sr surface segregation for the Fe-rich compositions. Symmetric cells showed no degradation during 1000 h life tests at 700 °C even at a current density of 1.5 A cm −2 , showing that all the STF electrode compositions worked stably in both fuel cell mode and electrolysis modes. The excellent stability may be explained by X-ray Photoelectron Spectroscopy (XPS) results showing that the amount of surface segregated Sr did not change during the long-term testing, and by relatively low polarization resistances that help avoid electrode delamination.« less