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Few hydride-ion conductors exhibit chemical stability and hydride-ion conductivity, which are essential properties in developing hydride-ion-driven electrochemical devices. Herein, we successfully synthesized a novel hydride-fluoride system, SrMgH4 − xFx, possessing high atmospheric stability and relatively high hydride-ion conductivity. The correlation between anion composition, structure, hydride-ion conductive properties, and atmospheric stability in the hydride-fluoride system was elucidated. The doping of fluoride ions at hydrogen sites resulted in high atmospheric stabilities while retaining hydride-ion conductivities of SrMgH2F2 and SrMgHF3 of 3.4 × 10− 4 and 1.4 × 10− 4 S cm− 1 at 400°C, respectively. For SrMgHF3, in particular, 84% ionic conductivity was retained after exposure to the atmosphere. Hydride-fluoride systems enable the balancing of the ionic conductivity and atmospheric stability by controlling the H/F ratio. Our findings provide insight for use in effective material design to expand the use of metal hydrides in practical solid electrolytes for use in hydride-ion-driven devices.

In recent years, lead halide perovskites have emerged as excellent photovoltaic materials for solar power generation. However, because they are toxic and chemically unstable in air, lead-free perovskites are also being investigated. In this study, the perovskite variant (CH3NH3)2SnI6 was studied. Polycrystalline films of (CH3NH3)2SnI6 were prepared using the thermal evaporation method. The films had a direct band gap of 1.81 eV with a strong absorption coefficient of ∼7 × 104 cm–1. In addition, the films were n-type with a carrier concentration of ∼2 × 1015 cm–3 and an electron mobility of ∼3 cm2 V–1 s–1. Moreover, the conductivity was increased by a factor of 4 under simulated solar illumination (100 mW cm–2). These results indicate that (CH3NH3)2SnI6 is a lead-free optical semiconductor suitable for solar cell applications.

Ruthenium is the most effective catalyst reported to date for ammonia synthesis under mild conditions, especially when an electron promoter is used. However, electron donation from the promoter has not been sufficient because the promoter contacts with Ru only through its surface. Here, we report a Laves phase intermetallic bulk catalyst, YRu2, which has higher electron density on Ru. This is derived from large electron transfer from Y to Ru, which is first confirmed by X-ray absorption fine structure measurements and theoretical calculations. In addition, YRu2 has high hydrogen solubilities leading to suppression of hydrogen poisoning, a common drawback of Ru-based catalysts. Consequently, YRu2 exhibits higher catalytic activity for ammonia synthesis over 300 times that with pure ruthenium. The present results suggest a simple concept for ammonia synthesis: Laves phase intermetallic compounds of Ru and more electropositive metals are more efficient catalysts than pure Ru because of the large electron pro...

We fabricated amorphous oxide semiconductor films, a-(Ga1–xZnx)Oy, at room temperature on glass, which have widely tunable band gaps (Eg) ranging from 3.47–4.12 eV. The highest electron Hall mobility ~ 7 cm2 V− 1 s− 1 was obtained for Eg = ~ 3.8 eV. Ultraviolet photoemission spectroscopy revealed that the increase in Eg with increasing the Ga content comes mostly from the deepening of the valence band maximum level while the conduction band minimum level remains almost unchanged. These characteristics are explained by their electronic structures. As these films can be fabricated at room temperature on plastic, this achievement extends the applications of flexible electronics to opto-electronic integrated circuits associated with deep ultraviolet region.

We report an air and water stable electride Y5Si3 and its catalytic activity for direct ammonia synthesis. It crystallizes in the Mn5Si3-type structure and confines 0.79/f.u. anionic electrons in the quasi-one-dimensional holes. These anionic electrons strongly hybridize with yttrium 4d electrons, giving rise to improved chemical stability. The ammonia synthesis rate using Ru(7.8 wt %)-loaded Y5Si3 was as high as 1.9 mmol/g/h under 0.1 MPa and at 400 °C with activation energy of ∼50 kJ/mol. Its strong electron-donating ability to Ru metal of Y5Si3 is considered to enhance nitrogen dissociation and reduce the activation energy of ammonia synthesis reaction. Catalytic activity was not suppressed even after Y5Si3, once dipped into water, was used as the catalyst promoter. These findings provide novel insights into the design of simple catalysts for ammonia synthesis.

Transparent bipolar semiconductors (TBSCs) are in demand for transparent electronics to serve as the basis for next generation optoelectronic devices. However, the poor carrier controllability in wide-bandgap materials makes the realization of a bipolar nature difficult. Only two materials, CuInO2 and SnO, have been reported as TBSCs. To satisfy demand for the coexistence of transparency and bipolarity, we propose a design concept with three strategies; choice of early transition metals (eTM) such as Y3+ and Zr4+ for improving controllability of carrier doping, design of chemical bonds to obtain an appropriate band structure for bipolar doping, and use of a forbidden band-edge transition to retain transparency. This approach is verified through a practical examination of a candidate material, tetragonal ZrOS, which is chosen by following the criteria. ZrOS exhibits an excellent controllability of the electrical conductivity (10–7–10–2 S cm–1), p- or n-type nature with ∼10–2 S cm–1 by Y or F doping, respec...

A simple and robust approach to visualization of continuous wave terahertz (CW-THz) light would open up opportunities to couple physical phenomena that occur at fundamentally different energy scales. Here we demonstrate how nanoscale cages of Ca12Al14O33 crystal enable conversion of CW-THz radiation to visible light. These crystallographic cages are partially occupied with weakly bonded oxygen ions and give rise to a narrow conduction band that can be populated with localized, yet mobile electrons. CW-THz light excites a nearly stand-alone rattling motion of the encaged oxygen species, which promotes electron transfer from them to the neighboring vacant cages. When the power of CW-THz light reaches tens of watts, the coupling between forced rattling in the confined space, electronic excitation and ionization of oxygen species, and corresponding recombination processes result in emission of bright visible light.

Processes of a new transparent amorphous oxide semiconductor (TAOS) as ETL and EIL were developed. Conventional processes can be applied for the deposition and structuring of the new TAOS, which enables to fabricate inverted OLEDs. The new TAOS materials make it possible to realize thicker ETL, potentially giving impacts not only on yield, but also on higher aperture ratio and cost reduction by omitting resin banks.

We examined the superconductivity of SnAs and the valence state of Sn in its lattice with an expectation that SnAs and related compounds with the NaCl-type structure might exhibit superconductivity...

Electrides are ionic crystals in which the anionic electrons are confined to interstitial subnanometer-sized spaces. At present, the reported electrides only consist of main-group elements. Here, w...

We investigate the band structure of the inverse perovskite ${\mathrm{Ca}}_{3}\mathrm{PbO}$, a candidate three-dimensional (3D) Dirac fermion material, through soft x-ray angle-resolved photoemission spectroscopy. Conelike band dispersions are observed for ${\mathrm{Ca}}_{3}\mathrm{PbO}$, in close agreement with the predictions of electronic structure calculations. We further demonstrate that chemical substitution of Bi for Pb is effective in tuning the Fermi level of ${\mathrm{Ca}}_{3}\mathrm{PbO}$ while leaving its electronic structure intact. Our study confirms that the inverse perovskite family provides a promising platform for the exploration of 3D Dirac fermion systems.

Efficient electron transfer between a cathode and an active organic layer is one key to realizing high-performance organic devices, which require electron injection/transport materials with very low work functions. We developed two wide-bandgap amorphous (a-) oxide semiconductors, a-calcium aluminate electride (a-C12A7:e) and a-zinc silicate (a-ZSO). A-ZSO exhibits a low work function of 3.5 eV and high electron mobility of 1 cm2/(V · s); furthermore, it also forms an ohmic contact with not only conventional cathode materials but also anode materials. A-C12A7:e has an exceptionally low work function of 3.0 eV and is used to enhance the electron injection property from a-ZSO to an emission layer. The inverted electron-only and organic light-emitting diode (OLED) devices fabricated with these two materials exhibit excellent performance compared with the normal type with LiF/Al. This approach provides a solution to the problem of fabricating oxide thin-film transistor-driven OLEDs with both large size and high stability.

Highly efficient inverted OLED was fabricated by using a newly developed new transparent amorphous oxide semiconductor (TAOS) for an electron transport layer. This new TAOS has high mobility (˜1cm2/Vs), low work function (˜3.5 eV), sufficient chemical stability and high transparency, and can form Ohmic contact with conventional electrodes (ITO, Al, etc.).

Transparent thin film of amorphous 12CaO·7Al2O3 electride, sputter-deposited at RT, having work function of 2.9 − 3.1 eV, was found to act as a good electron injection layer for OLED, and was adequate in combination with n-channel IGZO-TFTs.

The ionic crystal Ca2N is shown to be an electride in terms of [Ca2N]+·e−, with diffusive two-dimensional transport in dense electron layers. The physical properties of electrides — ionic crystals in which electrons behave as anions — significantly depend on the topology of the confining cavity for anionic electrons. Thus, an essential step towards practical electride applications is to discover new confinement spaces with unique topologies. Confined two-dimensional electron layers have previously been achieved by artificially fabricating hetero-interface structures usually of semiconducting materials. Here the authors extend the range of materials demonstrating such behaviour to an electride, dicalcium nitride (Ca2N). This compound has ideal properties for electron confinement: a layered structure with appropriate interlayer spacing and a chemistry that allows for loosely bound electron layers without electron trapping. By providing a new material image for electrides, this work should lead to a series of two-dimensional electrides with unique physical properties. Recent studies suggest that electrides—ionic crystals in which electrons serve as anions—are not exceptional materials but rather a generalized form, particularly under high pressure1,2,3. The topology of the cavities confining anionic electrons determines their physical properties4. At present, reported confining sites consist only of zero-dimensional cavities or weakly linked channels4. Here we report a layered-structure electride of dicalcium nitride, Ca2N, which possesses two-dimensionally confined anionic electrons whose concentration agrees well with that for the chemical formula of [Ca2N]+·e−. Two-dimensional transport characteristics are demonstrated by a high electron mobility (520 cm2 V−1 s−1) and long mean scattering time (0.6 picoseconds) with a mean free path of 0.12 micrometres. The quadratic temperature dependence of the resistivity up to 120 Kelvin indicates the presence of an electron–electron interaction. A striking anisotropic magnetoresistance behaviour with respect to the direction of magnetic field (negative for the field perpendicular to the conducting plane and positive for the field parallel to it) is observed, confirming diffusive two-dimensional transport in dense electron layers. Additionally, band calculations support confinement of anionic electrons within the interlayer space, and photoemission measurements confirm anisotropic low work functions of 3.5 and 2.6 electronvolts, revealing the loosely bound nature of the anionic electrons. We conclude that Ca2N is a two-dimensional electride in terms of [Ca2N]+·e−.

The air and water stable title electride is characterized by powder XRD, transport, magnetic, and thermodynamic measurements, PES, and DFT calculations.

We report an air and water stable electride Y5Si3 and its catalytic activity for direct ammonia synthesis. It crystallizes in the Mn5Si3-type structure and confines 0.79/f.u. anionic electrons in the quasi-one-dimensional holes. These anionic electrons strongly hybridize with yttrium 4d electrons, giving rise to improved chemical stability. The ammonia synthesis rate using Ru(7.8 wt %)-loaded Y5Si3 was as high as 1.9 mmol/g/h under 0.1 MPa and at 400 °C with activation energy of ∼50 kJ/mol. Its strong electron-donating ability to Ru metal of Y5Si3 is considered to enhance nitrogen dissociation and reduce the activation energy of ammonia synthesis reaction. Catalytic activity was not suppressed even after Y5Si3, once dipped into water, was used as the catalyst promoter. These findings provide novel insights into the design of simple catalysts for ammonia synthesis.

Polycrystalline β-PbO films were grown by pulsed laser deposition in atmospheres ranging from oxygen-poor (the oxygen pressure of 0.01 Pa) to oxygen-rich (13 Pa) conditions, and the oxygen chemical potential was further enhanced by ozone annealing to examine hole doping. It was found that each of the as-grown β-PbO films showed poor electrical conductivity, σ 7.1 × 102 S cm−1) but it is the result of the formation of an n-type PbO2 phase because oxygen chemical potential exceeded the phase boundary limit. The striking difference in carrier generation between PbO and SnO is discussed based on the electronic structures calculated by density functional theory.

Surface structures of stoichiometric and oxygen-deficient complex subnanoporous oxide 12CaO·7Al 2 O 3 (C12A7) are generated by simulating lattice rupture under the influence of an external strain. Extra-framework anions are found to serve as buffers, maintaining stability of the lattice cages in both elastic and inelastic stretching regimes. Modification of the local atomic structure in the near-surface region reduces the band gap in stoichiometric insulating C12A7. On the contrary, the band gap appears in the oxygen-deficient form of C12A7, which is metallic in the bulk. This is due to formation of the surface electron traps, which differ both in the type of the local atomic structure and stability of the electronic states. The implications of this electronic structure for the surface chemical and electron emission properties are discussed.

Single crystals of 12CaO·7Al2O3 (C12A7) have been grown by the Czochralski method with three different growth directions of , , and . Employment of a 2.0% oxygen-containing nitrogen atmosphere and use of an iridium crucible were the critical factors for obtaining the single crystal. The crystal exhibited orange color resulting from the incorporation of Ir4+ ions of ∼ 5 × 1017 cm− 3, presumably occupying at Ca2+ sites. High resolution X-ray diffraction analyses indicated that the C12A7 single crystal shows the tetragonal symmetry belonging to the space group I 4 ― 2 m .

Tin monosulfide (SnS) is a naturally p-type semiconductor with a layered crystal structure, but no reliable n-type SnS has been obtained by conventional aliovalent ion substitution. In this work, carrier polarity conversion to n-type was achieved by isovalent ion substitution for polycrystalline SnS thin films on glass substrates. Substituting Pb2+ for Sn2+ converted the majority carrier from hole to electron and the free electron density ranged from 1012 to 1015 cm−3 with the largest electron mobility of 7.0 cm2/(Vs). The n-type conduction was confirmed further by the position of the Fermi level (EF) based on photoemission spectroscopy and electrical characteristics of pn heterojunctions. Density functional theory calculations reveal that the Pb substitution invokes a geometrical size effect that enlarges the interlayer distance and subsequently reduces the formation energies of Sn and Pb interstitials, which results in the electron doping.

Polycrystalline layered Y2C with quasi-2D anionic electrons confined in the interlayer is prepared by melting stoichiometric amounts of Y shots and C granules under Ar.

Beta-BaZn2As2 is known to be a p-type semiconductor with the layered crystal structure similar to that of LaZnAsO, leading to the expectation that beta-BaZn2As2 and LaZnAsO have similar bandgaps; however, the bandgap of beta-BaZn2As2 (previously-reported value ~0.2 eV) is one order of magnitude smaller than that of LaZnAsO (1.5 eV). In this paper, the reliable bandgap value of beta-BaZn2As2 is determined to be 0.23 eV from the intrinsic region of the tem-perature dependence of electrical conductivity. The origins of this narrow bandgap are discussed based on the chemi-cal bonding nature probed by 6 keV hard X-ray photoemission spectroscopy, hybrid density functional calculations, and the ligand theory. One origin is the direct As-As hybridization between adjacent [ZnAs] layers, which leads to a secondary splitting of As 4p levels and raises the valence band maximum. The other is that the non-bonding Ba 5dx2-y2 orbitals form unexpectedly deep conduction band minimum (CBM) in beta-BaZn2As2 although the CBM of LaZnAsO is formed mainly of Zn 4s. These two origins provide a quantitative explanation for the bandgap difference between beta-BaZn2As2 and LaZnAsO.

Single crystals of nanoporous 12CaO·7Al2O3 (C12A7) as large as 27 mm in diameter, 120 mm in length, and 207 g in weight have been successfully grown by the Czochralski method. We found that a 2.0% oxygen-containing nitrogen atmosphere and an iridium crucible are the critical factors for success. The crystal ingot exhibited an orange color resulting from the incorporation of Ir4+ ions of ca. 5 × 1017 cm-3, which presumably occupy Ca2+ sites. X-ray diffraction analysis indicated that the ingot obtatined was a single crystal with few domains.

Microporous calcium aluminates with a common formula [Ca12Al14O33-δ]2δ+(2δe-), (0 < δ ≤ 1), represent a new family of electrides with conducting extraframework electrons encaged within the framework. Their enthalpies of oxidation to eliminate these electrons and obtain a stoichiometric Ca12Al14O33 compound, and formation enthalpies relative to the most stable annealed calcium aluminate Ca12Al14O33.46 (which contains excess oxygen probably as O- and O2- species), are studied by transposed temperature drop calorimetry and drop solution calorimetry in molten lead borate at 1080 K. The standard enthalpy of oxidation per O2 consumed is −579.4 ± 9.4 kJ/mol (or −144.8 ± 9.4 kJ per encaged electron). The enthalpies obtained for samples with variable amounts of electrons (and less than 33 oxygens per formula unit) are compared to that for oxidation of a stoichiometric Ca12Al14O33 sample to an oxygen-rich composition. The study supports the idea that the oxidation of the stoichiometric Ca12Al14O33 sample results in...

Thin film fabrication of crystalline 12CaO·7Al2O3 (C12A7) with zeolitic structure was examined, and their electrical and optical properties were measured. Polycrystalline thin films were prepared by post-annealing of amorphous films in oxygen atmosphere at temperatures above 800 °C. Choice of substrates was crucial for obtaining single-phase thin films. Although various oxide substrates (single crystals of Al2O3, Y-stabilized ZrO2, MgO and silica glass) were examined, single-phase films were obtained only for MgO substrates and the other substrates reacted with the CaO component in the films during post-annealing. The optical band gap of C12A7 was evaluated to be 5.9 eV. Hydride ions were incorporated into the film by a thermal treatment in a hydrogen atmosphere at 1200 °C. The resulting transparent thin films were converted into transparent persistent electronic conductors exhibiting an electrical conductivity 6.2×10−1 S cm−1 at 300 K by ultraviolet light illumination. This is the first example of transparent conductive thin film in which conductive areas can be patterned directly by light.

We removed ∼100% of clathrated oxygen ions from the crystallographic cages in a single crystal of 12CaO·7Al 2 O 3 , leading to the formation of high-density (∼2 × 10 21 cm – 3 ) electrons highly localized in the cages. The resulting electron forms a structure that we interpret as an F + center and migrates throughout the crystal by hopping to a neighboring cage with conductivity ∼100 siemens per centimeter, demonstrating that the encaged electron behaves as an anion. The electron anions couple antiferromagnetically with each other, forming a diamagnetic pair or singlet bipolaron. The resulting [Ca 24 Al 28 O 64 ] 4 + (4 e – ) may be regarded as a thermally and chemically stable single crystalline “electride.”

The variety of semiconductor materials has been extended in various directions, for example, to very wide bandgap materials such as oxide semiconductors as well as to amorphous semiconductors. Crystalline β-Ga2O3 is known as a transparent conducting oxide with an ultra-wide bandgap of ~4.9 eV, but amorphous (a-) Ga2Ox is just an electrical insulator because the combination of an ultra-wide bandgap and an amorphous structure has serious difficulties in attaining electronic conduction. This paper reports semiconducting a-Ga2Ox thin films deposited on glass at room temperature and their applications to thin-film transistors and Schottky diodes, accomplished by suppressing the formation of charge compensation defects. The film density is the most important parameter, and the film density is increased by enhancing the film growth rate by an order of magnitude. Additionally, as opposed to the cases of conventional oxide semiconductors, an appropriately high oxygen partial pressure must be chosen for a-Ga2Ox to reduce electron traps. These considerations produce semiconducting a-Ga2Ox thin films with an electron Hall mobility of ~8 cm2V−1 s−1, a carrier density Ne of ~2 × 1014 cm−3 and an ultra-wide bandgap of ~4.12 eV. An a-Ga2Ox thin-film transistor exhibited reasonable performance such as a saturation mobility of ~1.5 cm2 V−1 s−1 and an on/off ratio >107. Reversing the usual role of oxygen during deposition of semiconducting thin films makes it easier to produce bendable electronics. Crystalline gallium oxide is a large-bandgap semiconductor that can handle the strong electric fields used to supply power components. However, it usually turns into an insulator when produced as amorphous, flexible thin films. Now, Junghwan Kim from the Tokyo Institute of Technology in Japan and colleagues have found that high partial pressures of oxygen gas during rapid laser deposition transforms amorphous gallium oxide films into semiconductors. While most oxide films are manufactured under low-oxygen conditions, the researchers discovered their procedure suppresses the formation of electron-trapping defects that diminish conductivity. Prototype thin-film transistors and diodes demonstrated the potential for using amorphous gallium oxide for high-efficiency devices. Crystalline Ga2O3 is an ultra-wide bandgap oxide semiconductor, but electron conduction in amorphous Ga2Ox has never been attained to date. Here we succeeded in converting amorphous Ga2Ox to a semiconductor with the bandgap of ~4.12 eV and the electron mobility ~8 cm2 V−1 s−1. The key is to suppress charge compensation defects by increasing the film density and suppress formation of oxygen-poor and oxygen-excess defects. It produces thin-film transistors and Schottky diodes with high on currents and on/off ratios.

β-BaZn2As2 is known to be a p-type semiconductor with the layered crystal structure similar to that of LaZnAsO, leading to the expectation that β-BaZn2As2 and LaZnAsO have similar bandgaps; however, the bandgap of β-BaZn2As2 (previously reported value ~0.2 eV) is 1 order of magnitude smaller than that of LaZnAsO (1.5 eV). In this paper, the reliable bandgap value of β-BaZn2As2 is determined to be 0.23 eV from the intrinsic region of the temperature dependence of electrical conductivity. The origins of this narrow bandgap are discussed based on the chemical bonding nature probed by 6 keV hard X-ray photoemission spectroscopy, hybrid density functional calculations, and the ligand theory. One origin is the direct As-As hybridization between adjacent [ZnAs] layers, which leads to a secondary splitting of As 4p levels and raises the valence band maximum. The other is that the nonbonding Ba 5d(x(2)-y(2)) orbitals form an unexpectedly deep conduction band minimum (CBM) in β-BaZn2As2 although the CBM of LaZnAsO is formed mainly of Zn 4s. These two origins provide a quantitative explanation for the bandgap difference between β-BaZn2As2 and LaZnAsO.

Inorganic imides are useful for hydrogen storage and base-catalyzed reactions but are extremely unstable under ambient conditions, which hinders their practical use as functional materials. Here, we demonstrate that NH2(-) and H(-), as well as NH(2-), can be incorporated into the nanocages of the mayenite crystals, [Ca24Al28O64](4+)(e(-))4 and [Ca24Al28O64](4+)(O(2-))2, by ammonothermal treatment. We evaluated the reaction conditions and found that the anion exchange reaction proceeded at higher than 500 °C. Raman spectroscopy showed that the N-H band position of encaged NH(2-) was close to that of CaNH and MgNH crystals. We also studied the reaction pathways that yield NH2(-) and NH(2-) anions and their dynamic motions by (1)H NMR spectroscopy. Successive reactions of encaged e(-) and O(2-) ions with NH3 yielded NH2(-), NH(2-), and H(-) or OH(-), in which the O(2-) ion reacted more efficiently with NH3. The maximum NH(2-) concentration and content were ∼2.7 × 10(20) cm(-3) and ∼0.25 (wt %)NH, respectively. The short spin-lattice relaxation time found in (1)H NMR suggests that the incorporated NH2(-) and NH(2-) rotate or librate in the cage near room temperature. Stability tests showed that the encaged NH(2-) ions are chemically stable under ambient conditions and in organic solvents. These results are attributed to the encapsulation of active anions within subnanometer-sized cages composed of Ca-O-Al oxide frameworks. The encaged NH(2-) desorbed as NH3 at higher than 500 °C under vacuum (Ea = 172 kJ mol(-1)). It is thus expected that C12A7:NH(2-) will function as a reactive nitrogen source for nitrogen transfer reactions by in situ cage degradation.

The title compounds are prepared from mixtures of Rh or Ir, BaS or BaSe, Ge, and S or Se (h-BN capsule, 5 GPa, 1473 K, 2 h).

Structure and chemical features of layered compounds BaM2Ge4Ch6 (M = Rh, Ir; Ch = S, Se) synthesized under high-pressure and high-temperature method are systematically studied. These compounds crystallize in an orthorhombic phase with space group Pbca (No. 61). The remarkable structural feature is to have the M-Ge-Ch pyrite-type building units, stacking with Ba-Ch layers alternatively along c axis. It is very rare and novel that pyrite-type subunits as the building blocks in the layered compounds. Theoretical calculations and experimental results indicate that there are strongly polarized covalent bonds between Ge and Ch atoms, forming heteromolecule-like anions in these compounds. Moreover, Ge atoms in this structure exhibit unusual valence state (~ +1) due to the tetrahedral coordination environment of Ge atoms along with M and Ch atoms simultaneously., 24 pages, 12 figures, 5 tables

Single-phase, powdered InOF is prepared by thermal decomposition of InF3·3H2O under flowing O2 (360—440 °C, 2 h).

Activation of carbon dioxide is the most important step in its conversion into valuable chemicals. Surfaces of stable oxide with a low work function may be promising for this purpose. Here we report that the surfaces of the inorganic electride [Ca24Al28O64]4+(e−)4 activate and split carbon dioxide at room temperature. This behaviour is attributed to a high concentration of localized electrons in the near-surface region and a corrugation of the surface that can trap oxygen atoms and strained carbon monoxide and carbon dioxide molecules. The [Ca24Al28O64]4+(e−)4 surface exposed to carbon dioxide is studied using temperature-programmed desorption, and spectroscopic methods. The results of these measurements, corroborated with ab initio simulations, show that both carbon monoxide and carbon dioxide adsorb on the [Ca24Al28O64]4+(e−)4 surface at RT and above and adopt unusual configurations that result in desorption of molecular carbon monoxide and atomic oxygen upon heating., Effective activation and spitting of carbon dioxide are important steps in its conversion to valuable chemicals. Here the authors report an inorganic electride material with a high concentration of near-surface electrons that is capable of adsorbing and decomposing carbon dioxide.

A method for the synthesis of single-phase powdered InOF under ambient pressure has been developed. The method involves pyrolysis of a hydrate of InF3 in an O2 atmosphere of controlled humidity. Various intermediate phases were formed during the pyrolysis, and their structures and interconversions were analyzed. Combined results of optical absorption measurements and density functional calculations indicate that InOF is a direct band gap material with a band gap energy of ∼3.7 eV. Unlike In2O3, the electrical conductivity of polycrystalline InOF pellets can be controlled over ∼8 orders of magnitude from ∼10(-8) S cm(-1) to ∼2 S cm(-1) by thermal annealing, and the sample with the highest conductivity was a nearly degenerate n-type semiconductor with a relatively small carrier concentration of ∼10(18) cm(-3). The work function of InOF measured by ultraviolet photoelectron spectroscopy is ∼3.5 eV and is smaller by ∼1.5 eV than that of In2O3. This difference comes from a decrease in the electron affinity.

The nanocage compound crystal [Ca24Al28O64]4+(e-)4 (C12A7:e-) is a room-temperature-stable electride. Although bulk C12A7:e- exhibits metallic conduction, the surface of an as-prepared sample or one prepared by mechanical fracture in ultrahigh vacuum is almost insulating and exhibits distinct non-ohmic contact. We studied whether the intrinsic surface of this electride exhibits metallic conduction or not by examining various conditions for preparing the intrinsic surface. A combination of sputtering with thermal annealing led to the emergence of metallic conductivity in a specific condition. Suitably prepared surfaces revealed ohmic contact even in an ambient atmosphere. Atomic-resolution scanning tunneling microscopy (STM) images of the surfaces were consistent with a structural model in which the cage structure in the bulk C12A7:e- electride is conserved at the surface.

Room temperature-stable inorganic electride [Ca(24)Al(28)O(68)](4+)4e(-) was employed for a pinacol coupling reaction in aqueous media. Ca-Al-O gel formed by the destruction of the crystal structure of an electride by water media played a key role in transferring the electron to electrophilic aldehydes. Aromatic aldehydes reacted smoothly with moderate to high yields.

A room temperature (RT) stable electride was realized by thermally annealing an insulating 12CaO·7Al2O3 (C12A7) single crystal in a calcium metal vapor. Here we report a simple and direct method for synthesizing polycrystalline C12A7 electride (C12A7:e-); the solidification of a “melt” in a reducing atmosphere and the crystallization of a “glass” with an oxygen-deficient composition in a vacuum. The carbon-related anion (C22-) presumably serves as the template for the formation of the C12A7 phase in the solidification process and may be spontaneously released from the lattice during the cooling process, leaving mobile electrons in the lattice. Also the C22- ions accommodated in the glass may play a significant role in the formation of C12A7:e- during the crystallization. The polycrystalline C12A7:e- exhibits an electrical conductivity up to 5 S·cm-1 at 300 K, which corresponds to an electron concentration of ∼3 × 1019 cm-3 and a nearly equal mobility of ∼0.1 cm2·V-1·s-1 to that of the single crystalline C...

A new method to convert 12CaO7Al2O3 (C12A7) thin films to electronic conductor by hot Ar+ ion implantation has been developed and its mechanism is discussed. It was found that hot Ar+ ion implantation extruded free O2- ions in C12A7 films by kick-out effects at fluences higher than 1×1017 cm−2, which left electrons in the cages embedded in C12A7 crystal and produced high concentration F+-like centers (∼1.4×1021 cm−3). The resulting films show coloration and persistent electronic conduction with conductivities up to ∼1 Scm−1. On the other hand, fluences less than 1×1017 cm−2 kept the films transparent and insulating.

The use of ammonia as a hydrogen carrier has received much attention due to its high hydrogen content and liquid state under mild conditions, which could lead to fuel cell applications. This study demonstrates facile ammonia decomposition on ruthenium nanoparticles loaded on inorganic electride, C12A7:e−. A high turnover frequency (∼12 s−1 at 400 °C) and low activation energy (64 kJ mol−1) for recombinative N2 desorption were obtained for Ru/C12A7:e−. N2-temperature programmed desorption (N2-TPD) and kinetic analyses indicate that the high catalytic performance is due to the low work function of chemically stable C12A7:e−, which enables electron injection to the antibonding orbital of the Ru–N bond formed transiently through the reaction by raising the Fermi level of Ru metal.