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1.
Small ; 20(11): e2305307, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-37926775

RESUMEN

Herein, a facile strategy is illustrated to develop pyrolysis-free out-of-plane coordinated single atomic sites-based M-POP via a one-pot Friedel Craft acylation route followed by a post-synthetic metalation. The optimized geometry of the Co@BiPy-POP clearly reveals the presence of out-of-plane Co-single atomic sites in the porous backbone. This novel photopolymer Co@BiPy-POP shows extensive π-conjugations followed by impressive light harvesting ability and is utilized for photochemical CO2 fixation to value-added chemicals. A remarkable conversion of styrene epoxide (STE) to styrene carbonate (STC) (≈98%) is obtained under optimized photocatalytic conditions in the existence of promoter tert-butyl ammonium bromide (TBAB). Synchrotron-based X-ray adsorption spectroscopy (XAS) analysis reveals the single atom coordination sites along with the metal (Co) oxidation number of +2.16 in the porous network. Moreover, in situ diffuse reflectance spectroscopy (DRIFTS) and electron paramagnetic resonance (EPR) investigations provide valuable information on the evolution of key reaction intermediates. Comprehensivecomputational analysis also helps to understand the overall mechanistic pathway along with the interaction between the photocatalyst and reactants. Overall, this study presents a new concept of fabricating porous photopolymers based on a pyrolysis-free out-of-plane-coordination strategy and further explores the role of single atomic sites in carrying out feasible CO2 fixation reactions.

2.
J Am Chem Soc ; 145(1): 422-435, 2023 Jan 11.
Artículo en Inglés | MEDLINE | ID: mdl-36537351

RESUMEN

The development of an efficient photocatalyst for C2 product formation from CO2 is of urgent importance toward the deployment of solar-fuel production. Here, we report a template-free, cost-effective synthetic strategy to develop a carbazole-derived porous organic polymer (POP)-based composite catalyst. The composite catalyst is comprised of In2.77S4 and porous organic polymer (POP) and is held together by induced-polarity-driven electrostatic interaction. Utilizing the synergy of the catalytically active In centers and light-harvesting POPs, the catalyst showed 98.9% selectivity toward the generation of C2H4, with a formation rate of 67.65 µmol g-1 h-1. Two different oxidation states of the In2.77S4 spinel were exploited for the C-C coupling process, and this was investigated by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and density functional theory (DFT) calculations. The role of POP was elucidated via several photophysical and photoelectrochemical studies. The electron transfer was mapped by several correlated approaches, which assisted in establishing the Z-scheme mechanism. Furthermore, the mechanism of C2H4 formation was extensively investigated using density functional theory (DFT) calculations from multiple possible pathways.

3.
J Am Chem Soc ; 145(2): 1433-1440, 2023 Jan 18.
Artículo en Inglés | MEDLINE | ID: mdl-36580662

RESUMEN

The scientific community has found immense difficulty to focus on the generation of chiral intermetallics compared to the chiral molecular structure, probably due to the technical difficulty in producing them as no general controlled protocol is available. Herein, using a conventional metal flux technique, we have discovered a new ternary intermetallic Co3Ni3Ga8, substituting Co at the Ni sublattice in a highly symmetric Ni3Ga4 (Ia3̅d). Co3Ni3Ga8 crystallizes in the I4132 space group, a Sohncke type, and can host the chiral structure. To the best of our knowledge, this is the first report of a ternary intermetallic crystallizing in this space group. The chiral structure of Co3Ni3Ga8 is comprehensively mapped by various techniques such as single-crystal X-ray diffraction (XRD), synchrotron powder XRD, X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy (STEM) and theoretically studied using density functional theory. The discovery of this chiral compound can inspire the researchers to design hidden ternary chiral intermetallics to study the exotic electrical and magnetic properties.

4.
Small ; 19(45): e2303495, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37434340

RESUMEN

The development of robust electrocatalysts with low platinum content for acidic hydrogen evolution reaction (HER) is paramount for large scale commercialization of proton exchange membrane electrolyzers. Herein, a simple strategy is reported to synthesize a well anchored, low Pt containing Vulcan carbon catalyst using ZnO as a sacrificial template. Pt containing ZnO (PZ) is prepared by a simultaneous borohydride reduction. PZ is then loaded onto Vulcan carbon to produce a very low Pt content electrocatalyst, PZ@VC. PZ@VC with 2 wt.% Pt shows excellent performance for acidic HER in comparison to the commercial Pt/C (20 wt.%) catalyst. PZ@VC with a very low Pt loading shows significantly low η10 and η100 values (15 and 46 mV, respectively). PZ@VC on coating with Nafion (PZ@VC-N) shows further improvement in its performance (η10 of 7 mV, η100 of 28 mV) with ≈300 h of stability (≈10 mA cm-2 ) with only 4 µgPt cm-2 . PZ@VC-N shows a record high mass activity of 71 A mgPt -1 (32 times larger than Pt/C (20 wt.%) at 50 mV of overpotential. Post reaction characterizations reveal Pt nanoparticles are embedded onto VC with no traces of zinc, suggestive of a strong metal-support interaction leading to this high stability at low Pt loading.

5.
Angew Chem Int Ed Engl ; 62(9): e202216613, 2023 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-36537874

RESUMEN

We present surface reconstruction-induced C-C coupling whereby CO2 is converted into ethylene. The wurtzite phase of CuGaS2. undergoes in situ surface reconstruction, leading to the formation of a thin CuO layer over the pristine catalyst, which facilitates selective conversion of CO2 to ethylene (C2 H4 ). Upon illumination, the catalyst efficiently converts CO2 to C2 H4 with 75.1 % selectivity (92.7 % selectivity in terms of Relectron ) and a 20.6 µmol g-1 h-1 evolution rate. Subsequent spectroscopic and microscopic studies supported by theoretical analysis revealed operando-generated Cu2+ , with the assistance of existing Cu+ , functioning as an anchor for the generated *CO and thereby facilitating C-C coupling. This study demonstrates strain-induced in situ surface reconstruction leading to heterojunction formation, which finetunes the oxidation state of Cu and modulates the CO2 reduction reaction pathway to selective formation of ethylene.

6.
Angew Chem Int Ed Engl ; 62(50): e202311304, 2023 Dec 11.
Artículo en Inglés | MEDLINE | ID: mdl-37872849

RESUMEN

Herein, we have specifically designed two metalated porous organic polymers (Zn-POP and Co-POP) for syngas (CO+H2 ) production from gaseous CO2 . The variable H2 /CO ratio of syngas with the highest efficiency was produced in water medium (without an organic hole scavenger and photosensitizer) by utilizing the basic principle of Lewis acid/base chemistry. Also, we observed the formation of entirely different major products during photocatalytic CO2 reduction and water splitting with the help of the two catalysts, where CO (145.65 µmol g-1 h-1 ) and H2 (434.7 µmol g-1 h-1 ) production were preferentially obtained over Co-POP & Zn-POP, respectively. The higher electron density/better Lewis basic nature of Co-POP was investigated further using XPS, XANES, and NH3 -TPD studies, which considerably improve CO2 activation capacity. Moreover, the structure-activity relationship was confirmed via in situ DRIFTS and DFT studies, which demonstrated the formation of COOH* intermediate along with the thermodynamic feasibility of CO2 reduction over Co-POP while water splitting occurred preferentially over Zn-POP.

7.
J Am Chem Soc ; 144(26): 11859-11869, 2022 07 06.
Artículo en Inglés | MEDLINE | ID: mdl-35749229

RESUMEN

The well-known limitation of alkaline fuel cells is the slack kinetics of the cathodic half-cell reaction, the oxygen reduction reaction (ORR). Platinum, being the most active ORR catalyst, is still facing challenges due to its corrosive nature and sluggish kinetics. Many novel approaches for substituting Pt have been reported, which suffer from stability issues even after mighty modifications. Designing an extremely stable, but unexplored ordered intermetallic structure, Pd2Ge, and tuning the electronic environment of the active sites by site-selective Pt substitution to overcome the hurdle of alkaline ORR is the main motive of this paper. The substitution of platinum atoms at a specific Pd position leads to Pt0.2Pd1.8Ge demonstrating a half-wave potential (E1/2) of 0.95 V vs RHE, which outperforms the state-of-the-art catalyst 20% Pt/C. The mass activity (MA) of Pt0.2Pd1.8Ge is 320 mA/mgPt, which is almost 3.2 times better than that of Pt/C. E1/2 and MA remained unaltered even after 50,000 accelerated degradation test (ADT) cycles, which makes it a promising stable catalyst with its activity better than that of the state-of-the-art Pt/C. The undesired 2e- transfer ORR forming hydrogen peroxide (H2O2) is diminished in Pt0.2Pd1.8Ge as visible from the rotating ring-disk electrode (RRDE) experiment, spectroscopically visualized by in situ Fourier transform infrared (FTIR) spectroscopy and supported by computational studies. The effect of Pt substitution on Pd has been properly manifested by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The swinging of the oxidation state of atomic sites of Pt0.2Pd1.8Ge during the reaction is probed by in situ XAS, which efficiently enhances 4e- transfer, producing an extremely low percentage of H2O2.


Asunto(s)
Peróxido de Hidrógeno , Platino (Metal) , Catálisis , Electrones , Oxígeno/química , Platino (Metal)/química
8.
Chem Rec ; 22(5): e202100317, 2022 May.
Artículo en Inglés | MEDLINE | ID: mdl-35174953

RESUMEN

Rare Earth (re) based intermetallics are a fascinating class of inorganic compounds due to the presence of highly localized f-electrons. Among the ternary intermetallics, RETX3 (RE - Rare Earth, T - Transition metals, X - 13-15th elements of the main groups) is one of the most widely studied RE-based intermetallic families in terms of diverse crystal structures as well as physical properties. This perspective presents a brief account of different structural variations observed in this family of compounds. We have also discussed structure-property correlations in selected compounds in this series that show interesting physical properties such as spin-glass behavior, superconductivity, heavy fermion behavior, Kondo behavior, etc. The origin of different physical properties of these compounds is also discussed in brief by correlating their crystal structures.

9.
Inorg Chem ; 57(19): 12078-12092, 2018 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-30226372

RESUMEN

In this work we synthesized two novel isostructural twin hybrids Comp1: [H(C10H10N2)Cu2][PMo12O40] & Comp2: [H(C10H10N2)Cu2][PW12O40], based on the Keggin ions (PMo12O40-3 & PW12O40-3), Cu(I) cation, and 4,4'-bipyridine, by in situ hydrothermal reduction of Cu, facilitated through extensive standardizations of synthetic pH conditions. Both compounds crystallized in monoclinic P21/ c space group with similar lattice parameters and crystal structures. The structural similarity prompted us to explore comparative catalytic properties of the hybrids, to understand the relative role of the POM species in the activity. While characterization techniques like powder X-ray diffraction (XRD), single-crystal XRD, IR, adsorption studies, etc. confirmed the identical structural hierarchy in the twin polyoxometalate-based metal organic frameworks (POMOFs), critical analyses through X-ray photoelectron spectroscopy, X-ray absorption near-edge structure spectroscopy, and magnetic property studies elucidated the electronic and local structural properties of the two. The hybrids were highly active for heterogeneous catalysis of small-molecule oxidation, with Comp 2 showing better activity than Comp1, particularly for oxidation of ethylbenzene and cyclooctene. Comp2 also outperformed Comp1 in photocatalytic degradation of methylene blue, with higher conversion efficiency of 83% and one order higher apparent rate constant of 0.0139 min-1, which is comparable to that of the well-known photocatalyst, P25. Electrochemical pseudocapacitance studies revealed that these POMOFs are having the potential to act as good charge storage and conducting devices if their electrochemical stability can be improved.

10.
Inorg Chem ; 57(2): 590-601, 2018 Jan 16.
Artículo en Inglés | MEDLINE | ID: mdl-29272117

RESUMEN

A family of five different three-dimensional polyoxometalate (POM) based supramolecular hybrids were synthesized by a hydrothermal route under different pH using a hydrolyzable naphthalene diimide ligand. The mechanism of crystallographic phase variation of the POM-amino pyridine hybrids under different pH was studied through controlled experiments where the final hydrolyzed products were analyzed through NMR and single crystal X-ray diffraction. Different pH conditions led to variation in the extent of protonation and hydrolyzation of the ligand, yielding different phases. All of these were identified, and the structures of the supramolecular hybrids were characterized extensively. Mechanistic study proved that only the reaction conditions are responsible for the hydrolysis of the ligand and the in situ generated POM species do not have any role in it. Magnetic measurements confirmed the hexavalent oxidation states of the transition metal center (Mo) in the POM. Optical band gap measurements revealed that these hybrids are semiconducting in nature. Two of the compounds were studied for hydrogen peroxide mediated selective oxidation catalysis of small organic molecules and found to exhibit very good activity with high percentage of selectivity for the desired products of industrial importance.

11.
Inorg Chem ; 57(20): 12576-12587, 2018 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-30281284

RESUMEN

In this work, we have discovered the anisotropic near-zero thermal expansion (NZTE) behavior in a family of compounds REAg xGa4- x ( RE = La-Nd, Sm, Eu, and Yb). The compounds adopt the CeAl2Ga2 structure type and were obtained as single crystals in high yield by metal flux growth technique using gallium as active flux. Temperature-dependent single crystal X-ray diffraction suggests that all the compounds exhibit near zero thermal expansion along c direction in the temperature range of 100-450 K. Temperature-dependent X-ray absorption near-edge spectroscopic study confirmed ZTE behavior is due to the geometrical features associated within the crystal structure. The anisotropic NZTE behavior was further established by anisotropic magnetic measurements on selected single crystals. The atomic displacement parameters, apparent bond lengths, bond angles, and structural distortion with respect to the temperature reveal that geometric features associated with the structural distortion cause the anisotropic NZTE along c-direction. The preliminary magnetic studies suggest all the compounds are paramagnetic at room temperature except LaAgGa3. Electrical resistivity study reveals that compounds from this series are metallic in nature.

12.
Inorg Chem ; 56(14): 7582-7597, 2017 Jul 17.
Artículo en Inglés | MEDLINE | ID: mdl-28654276

RESUMEN

Over the last 3-4 decades, solid-state chemistry has emerged as the forefront of materials design and development. The field has revolutionized into a multidisciplinary subject and matured with a scope of new synthetic strategies, new challenges, and opportunities. Understanding the structure is very crucial in the design of appropriate materials for desired applications. Professor Mercouri G. Kanatzidis has encountered both challenges and opportunities during the course of the discovery of many novel materials. Throughout his scientific career, Mercouri and his group discovered several inorganic compounds and pioneered structure-property relationships. We, a few Ph.D. and postdoctoral students, celebrate his 60th birthday by providing a Viewpoint summarizing his contributions to inorganic solid-state chemistry. The topics discussed here are of significant interest to various scientific communities ranging from condensed matter to green energy production.

13.
Inorg Chem ; 55(11): 5603-11, 2016 Jun 06.
Artículo en Inglés | MEDLINE | ID: mdl-27187579

RESUMEN

We conceptually selected the compounds REPb3 (RE = Eu, Yb), which are unstable in air, and converted them to the stable materials in ambient conditions by the chemical processes of "nanoparticle formation" and "dimensional reduction". The nanoparticles and the bulk counterparts were synthesized by the solvothermal and high-frequency induction furnace heating methods, respectively. The reduction of the particle size led to the valence transition of the rare earth atom, which was monitored through magnetic susceptibility and X-ray absorption near edge spectroscopy (XANES) measurements. The stability was checked by X-ray diffraction and thermogravimetric analysis over a period of seven months in oxygen and argon atmospheres and confirmed by XANES. The nanoparticles showed outstanding stability toward aerial oxidation over a period of seven months compared to the bulk counterpart, as the latter one is more prone to the oxidation within a few days.

14.
Inorg Chem ; 55(2): 666-75, 2016 Jan 19.
Artículo en Inglés | MEDLINE | ID: mdl-26717270

RESUMEN

The compounds RECuGa3 (RE = La-Nd, Sm-Gd) were synthesized by various techniques. Preliminary X-ray diffraction (XRD) analyses at room temperature suggested that the compounds crystallize in the tetragonal system with either the centrosymmetric space group I4/mmm (BaAl4 type) or the non-centrosymmetric space group I4mm (BaNiSn3 type). Detailed single-crystal XRD, neutron diffraction, and synchrotron XRD studies of selected compounds confirmed the non-centrosymmetric BaNiSn3 structure type at room temperature with space group I4mm. Temperature-dependent single-crystal XRD, powder XRD, and synchrotron beamline measurements showed a structural transition between centro- and non-centrosymmetry followed by a phase transition to the Rb5Hg19 type (space group I4/m) above 400 K and another transition to the Cu3Au structure type (space group Pm3̅m) above 700 K. Combined single-crystal and synchrotron powder XRD studies of PrCuGa3 at high temperatures revealed structural transitions at higher temperatures, highlighting the closeness of the BaNiSn3 structure to other structure types not known to the RECuGa3 family. The crystal structure of RECuGa3 is composed of eight capped hexagonal prism cages [RE4Cu4Ga12] occupying one rare-earth atom in each ring, which are shared through the edge of Cu and Ga atoms along the ab plane, resulting in a three-dimensional network. Resistivity and magnetization measurements demonstrated that all of these compounds undergo magnetic ordering at temperatures between 1.8 and 80 K, apart from the Pr and La compounds: the former remains paramagnetic down to 0.3 K, while superconductivity was observed in the La compound at T = 1 K. It is not clear whether this is intrinsic or due to filamentary Ga present in the sample. The divalent nature of Eu in EuCuGa3 was confirmed by magnetization measurements and X-ray absorption near edge spectroscopy and is further supported by the crystal structure analysis.

15.
Inorg Chem ; 55(7): 3364-77, 2016 Apr 04.
Artículo en Inglés | MEDLINE | ID: mdl-26986739

RESUMEN

We have demonstrated engineering of the electronic band gap of the hybrid materials based on POMs (polyoxometalates), by controlling its structural complexity through variation in the conditions of synthesis. The pH- and temperature-dependent studies give a clear insight into how these experimental factors affect the overall hybrid structure and its properties. Our structural manipulations have been successful in effectively tuning the optical band gap and electronic band structure of this kind of hybrids, which can find many applications in the field of photovoltaic and semiconducting devices. We have also addressed a common crystallographic disorder observed in Keggin-ion (one type of heteropolyoxometalate [POMs])-based hybrid materials. Through a combination of crystallographic, spectroscopic, and theoretical analysis of four new POM-based hybrids synthesized with tactically varied reaction conditions, we trace the origin and nature of the disorder associated with it and the subtle local structural coordination involved in its core picture. While the crystallography yields a centrosymmetric structure with planar coordination of Si, our analysis with XPS, IR, and Raman spectroscopy reveals a tetrahedral coordination with broken inversion symmetry, corroborated by first-principles calculations.

16.
Inorg Chem ; 55(20): 10351-10360, 2016 Oct 17.
Artículo en Inglés | MEDLINE | ID: mdl-27676392

RESUMEN

Single crystals (SCs) of the compounds Eu3Ag2In9 and EuCu2Ge2 were synthesized through the reactions run in liquid indium. Eu3Ag2In9 crystallizes in the La3Al11 structure type [orthorhombic space group (SG) Immm] with the lattice parameters: a = 4.8370(1) Å, b = 10.6078(3) Å, and c = 13.9195(4) Å. EuCu2Ge2 crystallizes in the tetragonal ThCr2Si2 structure type (SG I4/mmm) with the lattice parameters: a = b = 4.2218(1) Å, and c = 10.3394(5) Å. The crystal structure of Eu3Ag2In9 is comprised of edge-shared hexagonal rings consisting of indium. The one-dimensional chains of In6 rings are shared through the edges, which are further interconnected with other six-membered rings forming a three-dimensional (3D) stable crystal structure along the bc plane. The crystal structure of EuCu2Ge2 can be explained as the complex [CuGe](2+δ)- polyanionic network embedded with Eu ions. These polyanionic networks present in the crystal structure of EuCu2Ge2 are shared through the edges of the 011 plane containing Cu and Ge atoms, resulting in a 3D network. The structural relationship between Eu3T2In9 and EuCu2Ge2 has been discussed in detail, and we conclude that Eu3T2In9 is the metal deficient variant of EuCu2Ge2. The magnetic susceptibilities of Eu3T2In9 (T = Cu and Ag) and EuCu2Ge2 were measured between 2 and 300 K. In all cases, magnetic susceptibility data followed Curie-Weiss law above 150 K. Magnetic moment values obtained from the measurements indicate the probable mixed/intermediate valent behavior of the europium atoms, which was further confirmed by X-ray absorption studies and bond distances around the Eu atoms. Electrical resistivity measurements suggest that Eu3T2In9 and EuCu2Ge2 are metallic in nature.

17.
Inorg Chem ; 54(22): 10855-64, 2015 Nov 16.
Artículo en Inglés | MEDLINE | ID: mdl-26505762

RESUMEN

A new compound, Eu3Ir2In15, has been synthesized using indium as an active metal flux. The compound crystallizes in the tetragonal P4/mbm space group with lattice parameters a = 14.8580(4) Å, b = 14.8580(4) Å, and c = 4.3901(2) Å. It was further characterized by SEM-EDX studies. The effective magnetic moment (µeff) of this compound is 7.35 µB/Eu ion with a paramagnetic Curie temperature (θp) of -28 K, suggesting antiferromagnetic interaction. The mixed-valent nature of Eu observed in magnetic measurements was confirmed by XANES measurements. The compound undergoes demagnetization at a low magnetic field (10 Oe), which is quite unusual for Eu-based intermetallic compounds. Temperature-dependent resistivity studies reveal that the compound is metallic in nature. A comparative study was made between Eu3Ir2In15 and hypothetical vacancy-variant Eu5Ir4In10, which also crystallizes in the same crystal structure. However, our computational studies along with control experiments suggest that the latter is thermodynamically less feasible compared to the former, and hence we propose that it is highly unlikely that an RE5T4X10 would exist with X as a group 13 element.

18.
Inorg Chem ; 53(1): 653-60, 2014 Jan 06.
Artículo en Inglés | MEDLINE | ID: mdl-24358992

RESUMEN

A new organic-inorganic hybrid material [SiMo14O44](H4,4'-bpy)2·xH2O (4,4'-bpy = 4,4'-bipyridine) was synthesized using a hydrothermal method. The compound was characterized using single crystal X-ray diffraction (XRD), infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV-vis), and X-ray photoelectron spectroscopy (XPS). XRD studies on selected single crystals suggested that the compound consists of supramolecular 2D layer structures composed of capped α-Keggin polyoxomolybdate anions and 4,4'-bpy organic ligands. Absorption measurements show a band gap of 2.99 eV in the hybrid which suggests a semiconducting nature compared to the insulating free α-Keggin and 4,4'-bpy. The magnetic susceptibility of the hybrid material was investigated in the temperature range 1.8-300 K obeying the Curie-Weiss law above 70 K. Experimentally measured magnetic moment of 2.71 µB/formula indicates possible mixed valent molybdenum in the compound. The XPS measurements confirm the presence of both Mo(V) and Mo(VI) in the ratio 15:85 resulting in the structural formula of the hybrid as [SiMo(V)2Mo(VI)12O44](H4,4'-bpy)2·xH2O.

19.
Inorg Chem ; 53(13): 6615-23, 2014 Jul 07.
Artículo en Inglés | MEDLINE | ID: mdl-24921221

RESUMEN

The compound Yb6.6Ir6Sn16 was obtained as single crystals in high yield from the reaction of Yb with Ir and Sn run in excess indium. Single-crystal X-ray diffraction analysis shows that Yb6.6Ir6Sn16 crystallizes in the tetragonal space group P42/nmc with a = b = 9.7105(7) Å and c = 13.7183(11) Å. The crystal structure is composed of a [Ir6Sn16] polyanionic network with cages in which the Yb atoms are embedded. The Yb sublattice features extensive vacancies on one crystallographic site. Magnetic susceptibility measurements on single crystals indicate Curie-Weiss law behavior <100 K with no magnetic ordering down to 2 K. The magnetic moment within the linear region (<100 K) is 3.21 µB/Yb, which is ∼70% of the expected value for a free Yb(3+) ion suggesting the presence of mixed-valent ytterbium atoms. X-ray absorption near edge spectroscopy confirms that Yb6.6Ir6Sn16 exhibits mixed valence. Resistivity and heat capacity measurements for Yb6.6Ir6Sn16 indicate non-Fermi liquid metallic behavior.

20.
Inorg Chem ; 52(17): 9741-8, 2013 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-23964959

RESUMEN

A new intermetallic compound Eu2AgGe3 has been synthesized using high-frequency induction heating method. Single-crystal X-ray diffraction data showed that Eu2AgGe3 crystallizes in the orthorhombic Ba2LiSi3 structure type, with Fddd space group and lattice parameters a = 8.7069(17) Å, b = 15.011(3) Å, c = 17.761(4) Å. Eu2AgGe3 is composed of infinite arrays of hexagonal [Ag3Ge3] units stacked along the [001] direction, and the Eu sites are sandwiched between these parallel hexagonal networks. Temperature-dependent powder XRD data and DTA hint toward a structural phase transition from orthorhombic to hexagonal above 477 K and an unusual reversible transition to the original phase, i.e., orthorhombic phase at around 718 K. Magnetic measurements on Eu2AgGe3 sample show paramagnetic behavior above 100 K and weak ferromagnetic interactions below 80 K. Mössbauer spectroscopy and X-ray absorption near-edge spectroscopic (XANES) studies reveal that Eu atoms in Eu2AgGe3 exist in the divalent oxidation state.

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