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Electrocaloric (EC) refrigeration, is accepted as an auspicious method to develop eco-friendly cooling devices. Here, the investigations on the EC response and energy storage performance of heterovalent-doped Ba(Sn, Ti)O3 relaxor ferroelectrics are carried out. Doping of aliovalent Mn or Nb elements into Ti site would regulate both the EC and energy storage behaviors. An enhanced EC temperature change up to 1.31 K, and a maximal recoverable energy storage density of 0.24 J cm− 3 with the efficiency as high as 87.11 %, can be observed under 70 kV cm− 1 in 0.5 % acceptor-doped Ba(Sn, Ti)O3 ceramics. It is found that the local internal stress, the local charge fluctuation, and the oxygen deficiencies would benefit the electrical behaviors of this system. These results would shed light on the effect of the heterovalent substitution on the electrical properties of lead-free BaTiO3 system and provide a novel and simple route to further improve the EC response and energy storage performance.

Titanium nitride (TiN) exhibits extremely high wear resistance and corrosion resistance, leading to a broad range of applications. Despite the extensive theoretical efforts on the structural stability of TiN under pressure, a few experimental observations of the pressure-induced phase transition through x-ray diffraction are still in debate. Here, the Raman spectra of TiN under pressure are studied in a diamond anvil cell up to 36 GPa. The discontinuity in the pressure dependent phonon frequencies suggests a phase transition at around 5 GPa with the bonding between Ti and N hardly changing. The phase transition is ascribed to an isostructural transition or a vacancy filling mechanism.

Although either surfactants or amines have been investigated to direct the crystal growth of metal chalcogenides, the synergic effect of organic amines and surfactants to control the crystal growth has not been explored. In this report, several organic bases (hydrazine monohydrate, ethylenediamine (en), 1,2-propanediamine (1,2-dap), and 1,3-propanediamine (1,3-dap)) have been employed as structure-directing agents (SDAs) to prepare four novel chalcogenides (Mn3Ge2S7(NH3)4 (1), [Mn(en)2(H2O)][Mn(en)2MnGe3Se9] (2), (1,2-dapH)2{[Mn(1,2-dap)2]Ge2Se7} (3), and (1,3-dapH)(puH)MnGeSe4(4) (pu = propyleneurea) under surfactant media (PEG-400). These as-prepared new crystalline materials provide diverse metal coordination geometries, including MnS3N tetrahedra, MnGe2Se7 trimer, and MnGe3Se10 T2 cluster. Compounds 1-3 have been fully characterized by single-crystal X-ray diffraction (XRD), powder XRD, UV-vis spectra, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Moreover, magnetic measurements for compound 1 showed an obvious antiferromagnetic transition at ~9 K. Our research not only enriches the structural chemistry of the transitional-metal/14/16 chalcogenides but also allows us to better understand the synergic effect of organic amines and surfactants on the crystallization of metal chalcogenides.

Vacancy engineering can effectively modulate the optical and electronic properties of metal oxides. Here, we demonstrate that high-pressure could be a clean strategy to tune the vacancies in oxides with a high cationic vacancy content. By combining in situ synchrotron x-ray diffraction, Raman scattering, and charge transport measurements in a diamond anvil cell, we systematically study the structure and electrical properties of TiO with ∼16% ordered vacancies up to 50.2 GPa at room temperature. The monoclinic TiO transforms to the cubic phase at ∼37.8 GPa. After decompression to ambient conditions, the cubic phase survives. The vacancies are partially filled and become disordered with a concentration of approximately 12.5%. The charge transport of TiO at high pressure exhibits a metal-insulator transition, which originates from the ordered to disordered transition of vacancies under pressure. Molecular dynamics simulations suggest that the vacancies enhance the mobility of atoms in the lattice under pressure and lead to the pressure-induced amorphization and recrystallization.Vacancy engineering can effectively modulate the optical and electronic properties of metal oxides. Here, we demonstrate that high-pressure could be a clean strategy to tune the vacancies in oxides with a high cationic vacancy content. By combining in situ synchrotron x-ray diffraction, Raman scattering, and charge transport measurements in a diamond anvil cell, we systematically study the structure and electrical properties of TiO with ∼16% ordered vacancies up to 50.2 GPa at room temperature. The monoclinic TiO transforms to the cubic phase at ∼37.8 GPa. After decompression to ambient conditions, the cubic phase survives. The vacancies are partially filled and become disordered with a concentration of approximately 12.5%. The charge transport of TiO at high pressure exhibits a metal-insulator transition, which originates from the ordered to disordered transition of vacancies under pressure. Molecular dynamics simulations suggest that the vacancies enhance the mobility of atoms in the lattice under press...

Nanoparticles (∼20 nm) of tetragonal (P42/mnm) cobalt fluoride (CoF2) has been synthesized by precipitation using cobalt nitrate and ammonium fluoride solution at room temperature, followed by annealing at 400 °C under argon atmosphere. The morphology and structure have been studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). The electrochemical lithiation of CoF2 and its structural and valence changes during conversion have been investigated. Electrochemical measurements revealed a discharge specific capacity close to theoretical specific capacity of 553 mAh g−1 and charge specific capacities ranging from 250 to 450 mAh g−1 in the first cycle, depending on the type of conductive carbon addictive used. Lithiation of CoF2 occurs without any intercalation, but via conversion reaction CoF2 + 2Li+ + 2e− → Co(0) + 2LiF. During lithiation, CoF2 is fully reduced to Co(0) and breaks down into smaller particles of ∼2 nm. Upon recharging, CoFx is formed instead of CoF2. XPS and EELS studies show that only the surface of the electrode is reconverted back to CoFx during recharging. In addition, recharging to form CoFx commences at the interface between the cobalt and lithium fluoride. These results offer the experimental evidence explaining the lack of cycle stability of metal fluorides that undergo a conversion reaction with lithium such as cobalt fluoride. In addition, they also provide insight into the reactions during conversion and reconversion. Finally, it is shown that the morphology of the conductive carbon addictives used in electrode fabrication plays a crucial role in determining the capacity retention ability for materials that undergo a conversion reaction with lithium.

Although surfactants have been widely used to tailor the size, shape, and surface properties of nanocrystals and control the pore size and phases of mesoporous frameworks, the use of surfactants as reaction media to grow chalcogenide crystals is unprecedented. In addition, compared with ionic liquids, surfactants are much cheaper and can have multifunctional properties such as acidic, basic, neutral, cationic, anionic, or even block. These features suggest that surfactants could be promising reaction platforms for the development of novel chalcogenide crystals. In this work, we used chalcogenidoarsenates as a model system to demonstrate our strategy. By using three different surfactants as reaction media, we obtained a series of novel thioarsenates ranging from a zero-dimensional (0D) cluster to a three-dimensional (3D) framework, namely, [NH(4)](8)[Mn(2)As(4)S(16)] (1), [Mn(NH(3))(6)][Mn(2)As(2)S(8)(N(2)H(4))(2)] (2), [enH][Cu(3)As(2)S(5)] (3), and [NH(4)][MnAs(3)S(6)] (4). The band gaps (estimated from the steep absorption edges) were found to be 2.31 eV for 1 (0D), 2.46 eV for 2 (1D), 1.91 eV for 3 (2D), and 2.08 eV for 4 (3D). The magnetic study of 4 indicated weak antiferromagnetic behavior. Our strategy of growing crystalline materials in surfactants could offer exciting opportunities for preparing novel crystalline materials with diverse structures and interesting properties.

Effects of different amines on the formation of manganese chalcogenidogermanates under PEG-thermal conditions are investigated.

In this report, three new metal-organic frameworks (MOFs), [Co3(μ3-OH)(HBTC)(BTC)2Co(HBTC)]·(HTEA)3·H2O (NTU-Z30), [Co(BTC)]·HTEA·H2O (NTU-Z31), [Co3(BTC)4]·(HTEA)4 (NTU-Z32), where H3BTC = 1,3,5-benzenetricarboxylic acid, TEA = triethylamine, and NTU = Nanyang Technological University, have been successfully synthesized under surfactant media and have been carefully characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, and IR spectromtry. NTU-Z30 has an unusual trimeric [Co3(μ3-OH)(COO)7] secondary building unit (SBU), which is different from the well-known trimeric [Co3O(COO)6] SBU. The topology studies indicate that NTU-Z30 and NTU-Z32 possess two new topologies, 3,3,6,7-c net and 2,8-c net, respectively, while NTU-Z31 has a known topology rtl type (3,6-c net). Magnetic analyses show that all three materials have weak antiferromagnetic behavior. Furthermore, NTU-Z30 has been selected as the heterogeneous catalyst for the aerobic epoxidation of alkene, and our results show that this material exhibits excellent catalytic activity as well as good stability. Our success in growing new crystalline cobalt 1,3,5-benzenetricarboxylate MOFs under surfactant media could pave a new road to preparing new diverse crystalline inorganic materials through a surfactant-thermal method.

Many commonly used electrical resistive switching devices are based on films of metal-oxide-metal ``sandwiches.'' Now scientists have observed ultrafast and reversible resistive switching in a thin-film device composed of a metallic platinum layer and two ultrathin layers of insulating oxides, LaAlO${}_{3}$ and SrTiO${}_{3}$, and revealed its origin in the oxides' charge-carrying oxygen vacancies.

Crystals of new thioarsenates are prepared using three different surfactants as reaction media.

We report that electrode engineering, particularly tailoring the metal work function, measurement configuration and geometric shape, has significant effects on the bipolar resistive switching (RS) in lateral memory devices based on self-doped SrTiO3 (STO) single crystals. Metals with different work functions (Ti and Pt) and their combinations are used to control the junction transport (either ohmic or Schottky-like). We find that the electric bias is effective in manipulating the concentration of oxygen vacancies at the metal/STO interface, influencing the RS characteristics. Furthermore, we show that the geometric shapes of electrodes (e.g., rectangular, circular, or triangular) affect the electric field distribution at the metal/oxide interface, thus plays an important role in RS. These systematic results suggest that electrode engineering should be deemed as a powerful approach toward controlling and improving the characteristics of RS memories. Published version

Solid oxide electrolyser cells (SOECs) have been considered effective to produce hydrogen at a high conversion efficiency through high temperature electrolysis (HTE) process and has a potential to scale up to a large-scale economy hydrogen source. The crucial issue for the SOEC moving into practical applications is stability. In this paper, investigation was conducted with the focus on the anode degradation using SOEC cells with strontium doped lanthanum manganite (LSM) anode and strontium doped lanthanum ferro-cobaltites (LSCF) anode. The results showed a more stable performance in LSM cells than LSCF cells when testing at 750ºC anode degradation and anode delamination contributed most of performance drop. The LSM cell is thus more suitable for HTE than the LSCF cell due to its better bonding between the electrolyte and anode.