High pressure X-ray diffraction study of copper hydride at room temperature

Abstract

High pressure X-ray studies on CuH up to 23 GPa have been performed at room temperature using a gasketed diamond anvil cell. The experimental data on the molar volume of CuH as a function of pressure have been fitted to Murnaghan's equation of state giving a bulk modulus: B₀ = 72.5±2 GPa and B₀ = 2.7 ± 0.3. By comparison with the equation of state for pure copper the effective additive volume of hydrogen has been evaluated as a function of pressure. It decreases from 3.2 cm³/mol H, at ambient pressure reaching a flattening value of 1.7cm³hol H at about 60 GPa. This suggests a continuous transition of CuH from ionic or covalent character at normal pressure to metallic hydride behavior at high pressure     

Effect of Sn and Nb on generalized stacking fault energy surfaces in zirconium and gamma hydride habit planes

We have investigated the effects of Sn and Nb on dislocation properties in a Zr lattice to elucidate the role of these alloying elements in hydride nucleation processes. According to experimental observations, γ-hydride habit planes are close to the prismatic plane in pure Zr and close to the basal plane in Zircaloy. Dislocation loops are observed around hydride precipitates, implying they play a part in hydride formation. Our ab initio generalized stacking-fault energy calculations showed remarkable effects of Sn on unstable-stacking energy and stacking-fault energy: these parameters for basal slip were considerably reduced while those for prismatic slip were increased in the presence of Sn. These results suggest selective stabilization and enhancement of dislocation spreading in the basal plane, promoting possible elementary processes of hydride precipitation with basal habit plane, i.e. screw-dislocation spreading and edge-dislocation emission in the basal plane.     

Hydrides as materials for semiconductor electronics

Systematic studies using density functional theory have shown that some hydrides possess the features of semiconductors. These features include larger fundamental band gap, well dispersed bottom-most conduction band and/or top-most valence band, small electron/hole effective masses and small intrinsic carrier concentration. It is demonstrated that depending upon the composition, hydrides possess a wide range of band gap values and hence they can be regarded as materials for narrow to wide band gap semiconducting applications. The possibility of designing hydride-based p–n junctions, and also their advantages as well as deficiencies compared to existing oxide semiconductors, are discussed. Replacing oxide-based semiconductors by hydrides can help to avoid problems such as formation of an oxide layer, band offsets, large concentration of defect states at the interface between the oxide and semiconductor, etc. Moreover, hydrides can be regarded as an alternative to conventional semiconductors and hence can be used in future-generation electronic devices called “hydride electronics”.     

Development of neutron detectors and neutron radiography at Bhabha Atomic Research Centre

Design and development of neutron detectors and R&D work in neutron radiography (NR) for non-destructive evaluation are important parts of the neutron beam and allied research programme of Solid State Physics Division (SSPD) of Bhabha Atomic Research Centre (BARC). The detectors fabricated in the division not only meet the in-house requirement of neutron spectrometers but also the need of other divisions in BARC, Department of Atomic Energy units and some universities and research institutes in India and abroad for a variety of applications. The NR facility set up by SSPD at Apsara reactor has been used for a variety of applications in nuclear, aerospace, defense and metallurgical industries. The work done in the development of neutron detectors and neutron radiography is reported in this article.      

Catalytic Generation and Chemoselective Transfer of Nucleophilic Hydrides from Dihydrogen

Copper(I)–N-heterocyclic-carbene (NHC) complexes enabled the catalytic generation of nucleophilic hydrides from dihydrogen (H₂) and their subsequent transfer to allylic chlorides. The highly chemoselective catalyst displayed no concomitant hydrogenation reactivity; in fact, the terminal double bond formed in the hydride transfer remained intact. Switching to deuterium gas (D₂) allowed for regioselective monodeuteration with excellent isotope incorporation.     

Diborylated Magnesium Anthracene as Precursor for B2H5−‐Bridged 9,10‐Dihydroanthracene

9,10‐(Bpin)₂‐anthracene ( 3 , HBpin=pinacolborane) was synthesized from 9,10‐dibromoanthracene in a stepwise lithiation/borylation sequence. The reaction of 3 with highly activated magnesium furnished the diborylated magnesium anthracene 4 , which was quenched in situ with ethereal HCl to yield cis‐9,10‐(Bpin)₂‐DHA (cis‐ 5 , DHA=9,10‐dihydroanthracene). Compound cis‐ 5 , in turn, can be reduced with Li[AlH₄] in THF to give its diborate Li₂[cis‐9,10‐(BH₃)₂‐DHA] (Li₂[cis‐ 6 ]). In the crystal lattice, the THF solvate Li₂[cis‐ 6 ] ? 3 THF establishes a dimeric structure with Li‐(μ‐H)‐B coordination modes. Hydride abstraction from Li₂[cis‐ 6 ] with Me₃SiCl yields the B?H?B‐bridged DHA Li[ 7 ]. This product can also be viewed as a unique cyclic B₂H₇^? derivative with a hydrocarbon backbone. Treatment of Li₂[cis‐ 6 ] with the stronger hydride abstracting agent Me₃SiOTf (HOTf=trifluoromethanesulfonic acid) in THF affords the THF diadduct of cis‐9,10‐(BH(OTf))₂‐DHA.     

Determination of lead in complex sample matrices by atomic fluorescence spectrometry: optimisation of online hydride generation

Lead hydride or plumbane (PbH₄) generation was optimised by exploiting a simple flow-injection method coupled to atomic fluorescence spectrometry (HG-AFS), and allowing ultra-trace lead determination. Plumbane was generated through two methods: (1) 5% (v/v) H₂O₂ was employed as oxidant with 1.5% (m/v) KBH₄ as a reducing agent and 1.5% (v/v) HCl solution; (2) with 1.5% (m/v) K₃[Fe(CN)₆] as an oxidant/sensitiser, 1% (m/v) KBH₄ as a reducing agent and 1.5% (v/v) HCl. Variables such as reagent concentrations, flow rates and sample and reagent volumes were tested and critically compared. The best results were obtained with potassium ferricyanide K₃[Fe(CN)₆], achieving a detection limit of 0.03 μg Pb L^?1 and a relative standard deviation (RSD) of 1.1%. The selected method was validated by analysis of certified reference materials such as SRM-2976 (mussel tissue) and BCR-610 (groundwater), with good agreement with the certified values. The developed methodology was successfully applied to different environmental sample matrices, such as rain water, tap water, ground water, spring water and drinking water, and biological samples, i.e., human blood, plasma and serum.     

Single‐Site Zeolite‐Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry

A family of HY zeolite‐supported cationic organoiridium carbonyl complexes was formed by reaction of Ir(CO)₂(acac) (acac=acetylacetonate) to form supported Ir(CO)₂ complexes, which were treated at 298 K and 1 atm with flowing gas‐phase reactants, including C₂H₄, H₂, ¹²CO, ¹³CO, and D₂O. Mass spectrometry was used to identify effluent gases, and infrared and X‐ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. Because the support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, these were characterized by a high degree of uniformity, which allowed a precise determination of the species involved in the replacement, for example, of one CO ligand of each Ir(CO)₂ complex with ethylene. The supported species include the following: Ir(CO)₂, Ir(CO)(C₂H₄)₂, Ir(CO)(C₂H₄), Ir(CO)(C₂H₅), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species.