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1.
Dalton Trans ; 50(36): 12419-12423, 2021 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-34545879

RESUMO

Intercalation of Cu into layered polychalcogenide La2O2S2 was demonstrated to be viable both under solvothermal conditions at 200 °C and mechanical ball milling at ambient temperature. This result evidences the soft-chemical nature of metal intercalation into layered polychalcogenides driven by the redox reactivity of anion-anion bonds.

2.
Nat Commun ; 12(1): 3605, 2021 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-34127660

RESUMO

Designing and synthesising new metastable compounds is a major challenge of today's material science. While exploration of metastable oxides has seen decades-long advancement thanks to the topochemical deintercalation of oxygen as recently spotlighted with the discovery of nickelate superconductor, such unique synthetic pathway has not yet been found for chalcogenide compounds. Here we combine an original soft chemistry approach, structure prediction calculations and advanced electron microscopy techniques to demonstrate the topochemical deintercalation/reintercalation of sulfur in a layered oxychalcogenide leading to the design of novel metastable phases. We demonstrate that La2O2S2 may react with monovalent metals to produce sulfur-deintercalated metastable phases La2O2S1.5 and oA-La2O2S whose lamellar structures were predicted thanks to an evolutionary structure-prediction algorithm. This study paves the way to unexplored topochemistry of mobile chalcogen anions.

3.
J Phys Chem Lett ; 11(20): 8861-8866, 2020 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-33016707

RESUMO

The never-elucidated crystal structure of metastable iron disulfide FeS2 resulting from the full deintercalation of Li in Li2FeS2 has been cracked thanks to crystal structure prediction searches based on an evolutionary algorithm combined with first-principles calculations accounting for experimental observations. Besides the newly layered C2/m polymorph of iron disulfide, two-dimensional dynamically stable FeS2 phases are proposed that contain sulfides and/or persulfide S2 motifs.

4.
Chem Commun (Camb) ; 56(11): 1645-1648, 2020 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-31939974

RESUMO

We unveil the structure and investigate the visible light water-splitting of the photocatalyst α-LaOInS2, the second polymorph in this composition. This remarkable oxysulfide exhibits rare mixed anion InS5O octahedra leading to both O-2p and S-3p hybridized with indium states in the vicinity of the Fermi level. Ab initio structure prediction shows the stability of such heteroleptic environments and points to other hypothetical polymorphs.

5.
Inorg Chem ; 58(22): 15004-15007, 2019 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-31651150

RESUMO

Reduction of the size of a particle down to a few tens of nanometers or below may drastically affect its physical properties. That is well-known for quantum dots. Conversely, many works consider the chemical composition of nanoparticles as invariant upon reduction of their dimension. Here we demonstrate that the chemical composition of a transition-metal oxide, namely, nickel oxide, is drastically affected by its nanostructuration.

6.
Chem Commun (Camb) ; 55(44): 6189-6192, 2019 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-31049515

RESUMO

We demonstrate here the low temperature topochemical insertion of transition elements (Fe, Ni, and Cu) in precursors containing pre-formed (Sn)2- (n = 2 and 3) oligomers. Indeed, this soft chemistry route opens the door to the easy, orientated synthesis of low dimensional transition metal compounds provided that the elemental metal can retrocede electron(s) to empty antibonding sulfur σ* levels.

7.
Angew Chem Int Ed Engl ; 57(41): 13618-13623, 2018 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-30133113

RESUMO

Layered transition metal compounds represent a major playground to explore unconventional electric or magnetic properties. In that framework, topochemical approaches that mostly preserve the topology of layered reactants have been intensively investigated to tune properties and/or design new materials. Topochemical reactions often involve the insertion or deinsertion of a chemical element accompanied by a change of oxidation state of the cations only. Conversely, cases where anions play the role of redox centers are very scarce. Here we show that the insertion of copper into two dimensional precursors containing chalcogen dimers (Q2 )2- (Q=S, Se) can produce layered materials with extended (CuQ) sheets. The reality of this topochemical reaction is demonstrated here for different pristine materials, namely La2 O2 S2 , Ba2 F2 S2 , and LaSe2 . Therefore, this work opens up a new synthetic strategy to design layered transition metal compounds from precursors containing polyanionic redox centers.

8.
Nat Commun ; 8(1): 782, 2017 10 04.
Artigo em Inglês | MEDLINE | ID: mdl-28978909

RESUMO

Strong spin-orbit coupling lifts the degeneracy of t 2g orbitals in 5d transition-metal systems, leaving a Kramers doublet and quartet with effective angular momentum of J eff = 1/2 and 3/2, respectively. These spin-orbit entangled states can host exotic quantum phases such as topological Mott state, unconventional superconductivity, and quantum spin liquid. The lacunar spinel GaTa4Se8 was theoretically predicted to form the molecular J eff = 3/2 ground state. Experimental verification of its existence is an important first step to exploring the consequences of the J eff = 3/2 state. Here, we report direct experimental evidence of the J eff = 3/2 state in GaTa4Se8 by means of excitation spectra of resonant inelastic X-ray scattering at the Ta L3 and L2 edges. We find that the excitations involving the J eff = 1/2 molecular orbital are absent only at the Ta L2 edge, manifesting the realization of the molecular J eff = 3/2 ground state in GaTa4Se8.The strong interaction between electron spin and orbital degrees of freedom in 5d oxides can lead to exotic electronic ground states. Here the authors use resonant inelastic X-ray scattering to demonstrate that the theoretically proposed J eff = 3/2 state is realised in GaTa4Se8.

9.
Inorg Chem ; 56(14): 7922-7927, 2017 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-28665603

RESUMO

Nickel carbodiimide (NiCN2) was synthesized using a two-step precipitation-decomposition route leading to a brown powder with gypsum-flower-like morphology and a large specific surface area (75 m2/g). This layered material crystallizes in the 2H structure type of delafossite (space group P63/mmc), which is built upon infinite 2/∞[NiN2] layers connected by linear carbodiimide ([N═C═N]2-) bridges. An X-ray diffraction Rietveld refinement and thermal analyses pointed out some nickel deficiencies in the material, and band structure calculations carried out on the defect compound predicted p-type conductivity in relation to a slight amount of N2-. This p-type conductivity was demonstrated by electrochemical impedance spectroscopy measurements, and a flat band potential of 0.90 V vs SCE at pH 9.4 was measured. This value, which is more positive than those of CuGaO2 and CuCrO2 delafossite oxides and NiO, prompted us to test NiCN2 nanoparticles as a photocathode in p-type dye-sensitized solar cells.

10.
Inorg Chem ; 56(11): 6208-6213, 2017 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-28530099

RESUMO

An original concept for the property tuning of semiconductors is demonstrated by the synthesis of a p-type zinc oxide (ZnO)-like metal-organic framework (MOF), (ZnC2O3H2)n, which can be regarded as a possible alternative for ZnO, a natural n-type semiconductor. When small oxygen-rich organic linkers are introduced to the Zn-O system, oxygen vacancies and a deep valence-band maximum, the two obstacles for generating p-type behavior in ZnO, are restrained and raised, respectively. Further studies of this material on the doping and photoluminescence behaviors confirm its resemblance to metal oxides (MOs). This result answers the challenges of generating p-type behavior in an n-type-like system. This concept reveals that a new category of hybrid materials, with an embedded continuous metal-oxygen network, lies between the MOs and MOFs. It provides concrete support for the development of p-type hybrid semiconductors in the near future and, more importantly, the enrichment of tuning possibilities in inorganic semiconductors.

11.
Inorg Chem ; 55(15): 7729-33, 2016 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-27409456

RESUMO

Optical and electrical characteristics of solid materials are well-known to be intimately related to the presence of intrinsic or extrinsic defects. Hence, the control of defects in semiconductors is of great importance to achieve specific properties, for example, transparency and conductivity. Herein, a facile and controllable reduction method for modulating the defects is proposed and used for the case of p-type delafossite CuCrO2 nanoparticles. The optical absorption in the infrared region of the CuCrO2 material can then be fine-tuned via the continuous reduction of nonstoichiometric Cu(II), naturally stabilized in small amounts. This reduction modifies the concentration of positive charge carriers in the material, and thus the conductive and reflective properties, as well as the flat band potential. Indeed, this controllable reduction methodology provides a novel strategy to modulate the (opto-) electronic characteristics of semiconductors.

12.
Inorg Chem ; 55(6): 2923-8, 2016 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-26942451

RESUMO

The iron selenide compound Ba2F2Fe(1.5)Se3 was synthesized by a high-temperature ceramic method. The single-crystal X-ray structure determination revealed a layered-like structure built on [Ba2F2](2+) layers of the fluorite type and iron selenide layers [Fe(1.5)Se3](2-). These [Fe1.5Se3](2-) layers contain iron in two valence states, namely, Fe(II+) and Fe(III+) located in octahedral and tetrahedral sites, respectively. Magnetic measurements are consistent with a high-spin state for Fe(II+) and an intermediate-spin state for Fe(III+). Moreover, susceptibility and resistivity measurements demonstrate that Ba2F2Fe(1.5)Se3 is an antiferromagnetic insulator.

14.
Sci Rep ; 5: 12914, 2015 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-26333510

RESUMO

Owing to its high technological importance for optoelectronics, zinc oxide received much attention. In particular, the role of defects on its physical properties has been extensively studied as well as their thermodynamical stability. In particular, a large concentration of Zn vacancies in ZnO bulk materials is so far considered highly unstable. Here we report that the thermal decomposition of zinc peroxide produces wurtzite-type ZnO nanoparticles with an extraordinary large amount of zinc vacancies (>15%). These Zn vacancies segregate at the surface of the nanoparticles, as confirmed by ab initio calculations, to form a pseudo core-shell structure made of a dense ZnO sphere coated by a Zn free oxo-hydroxide mono layer. In others terms, oxygen terminated surfaces are privileged over zinc-terminated surfaces for passivation reasons what accounts for the Zn off-stoichiometry observed in ultra-fine powdered samples. Such Zn-deficient Zn1-xO nanoparticles exhibit an unprecedented photoluminescence signature suggesting that the core-shell-like edifice drastically influences the electronic structure of ZnO. This nanostructuration could be at the origin of the recent stabilisation of p-type charge carriers in nitrogen-doped ZnO nanoparticles.

15.
Phys Rev Lett ; 113(13): 137602, 2014 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-25302917

RESUMO

We report here the discovery of multiferroicity and large magnetoelectric coupling in the type I orbital order system GeV4S8. Our study demonstrates that this clustered compound displays a para-ferroelectric transition at 32 K. This transition originates from an orbital ordering which reorganizes the charge within the transition metal clusters. Below the antiferromagnetic transition at 17 K, the application of a magnetic field significantly affects the ferroelectric polarization, revealing thus a large magnetoelectric coupling. Our study suggests that the application of a magnetic field induces a metamagnetic transition which significantly affects the ferroelectric polarization thanks to an exchange striction phenomenon.

16.
Nano Lett ; 13(8): 3648-53, 2013 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-23826620

RESUMO

We study the Mott insulator compound GaTa4Se8 in which we previously discovered an electric-field-induced resistive transition. We show that the resistive switching is associated to the appearance of metallic and super-insulating nanodomains by means of scanning tunneling microscopy/spectroscopy (STM/STS). Moreover, we show that local electronic transitions can be controlled at the nanoscale at room temperature using the electric field of the STM tip. This opens the way for possible applications in resistive random access memories (RRAM) devices.

17.
Adv Mater ; 25(23): 3222-6, 2013 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-23649904

RESUMO

A striking universality in the electric-field-driven resistive switching is shown in three prototypical narrow-gap Mott systems. This model, based on key theoretical features of the Mott phenomenon, reproduces the general behavior of this resistive switching and demonstrates that it can be associated with a dynamically directed avalanche. This model predicts non-trivial accumulation and relaxation times that are verified experimentally.

18.
J Am Chem Soc ; 134(1): 464-70, 2012 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-22092170

RESUMO

Zinc oxide is considered as a very promising material for optoelectronics. However, to date, the difficulty in producing stable p-type ZnO is a bottleneck, which hinders the advent of ZnO-based devices. In that context, nitrogen-doped zinc oxide receives much attention. However, numerous reviews report the controversial character of p-type conductivity in N-doped ZnO, and recent theoretical contributions explain that N-doping alone cannot lead to p-typeness in Zn-rich ZnO. We report here that the ammonolysis at low temperature of ZnO(2) yields pure wurtzite-type N-doped ZnO nanoparticles with an extraordinarily large amount of Zn vacancies (up to 20%). Electrochemical and transient spectroscopy studies demonstrate that these Zn-poor nanoparticles exhibit a p-type conductivity that is stable over more than 2 years under ambient conditions.

20.
J Am Chem Soc ; 132(16): 5704-10, 2010 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-20356073

RESUMO

The lacunar spinel compounds GaTi(4-x)V(x)S(8) (0 < x < 4), consisting of Ti(4-x)V(x) tetrahedral clusters, were prepared and their structures were determined by powder X-ray diffraction. The electronic structures of GaTi(4-x)V(x)S(8) (x = 0, 1, 2, 3) were examined by density functional calculations, and the electrical resistivity and magnetic susceptibility of these compounds were measured. Our calculations predict that GaTi(3)VS(8) is a ferromagnetic half-metal, and this prediction was confirmed by magnetotransport experiments performed on polycrystalline samples of GaTi(3)VS(8). The latter reveal a large negative magnetoresistance (up to 22% at 2 K), which is consistent with the intergrain tunnelling magnetoresistance expected for powder samples of a ferromagnetic half-metal and indicates the presence of high spin polarization greater than 53% in GaTi(3)VS(8).

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