红外和拉曼光谱在金属氢化物结构分析中的应用

红外光谱和拉曼光谱是分析金属氢化物结构的强有力工具,通过红外、拉曼光谱分析并结合理论计算,可以获得二元(MgH₂,CaH₂,AlH₃)和三元(Mg₂FeH₆)金属氢化物中金属原子与氢原子局域成键环境信息,从而鉴别金属氢化物不同的相结构,还可以获得三元金属氢化物M₂RuH₆(M=Ca,Sr,Eu)中由于金属原子的不同而导致的结构差异,以及三元金属氢化物与其氘化物的结构差异。利用原位拉曼光谱分析技术分析高压或高温下金属氢化物的形成与分解反应过程,可以获得金属氢化物在高压加载及卸压过程中的结构变化,更好的理解金属氢化物的衍射数据。PAIR(photoacoustic infrared spectroscopy)光谱技术增强了红外活性和拉曼活性组合谱带的强度,从而避免了空气及潮湿环境对傅里叶红外变换光谱实验结果的影响。红外光谱和拉曼光谱用于金属氚化物的结构分析,获得金属氢化物中金属原子与氢同位素原子局域成键环境的差异,更好的研究氢同位素效应。而且,拉曼光谱已被成功用于分析氢同位素混合气体的组成。因此,将金属氢化物结构的红外和拉曼光谱分析与氢同位素气体组分的拉曼光谱分析相结合,可用于研究金属与氢同位素气体反应的动力学过程及同位素效应。     

Electronic structure and bonding in metal hydrides,studied with photoelectron spectroscopy

We present photoemission spectra of various binary and ternary metal hydrides and of some intermetallic compounds. An analysis of these data with respect to the known heats of hydrogen solution in the metals demonstrates two important properties of the metal-hydrogen bond: First we find that core level, shifts in ternary systems are not simply related to those in binary ones. In contrast to a frequently used assumption, metal-hydrogen interaction in a ternary hydride cannot be a pair interaction between the atomic constituents. Secondly, we find from our studies of the valence band spectra of some intermetallic compounds an inverse correlation between the heat of hydrogen solution and the density of states at the Fermi level.We analyse the core level shift data from binary hydrides using the experimental heats of hydrogen solution. We find a very good agreement between calculated and measured core level shifts in transition metal hydrides. However, in rare earth hydrides our approach fails. The reason for this behaviour originates in the photoemission process itself. A thermochemical interpretation of core level shifts can only be successful in the adiabatic limit of core excitation. The systematic behaviour of our results can be explained, if core excitation is considered to be adiabatic in transition metal hydrides but sudden in the rare earth hydrides. We also discuss the impact of such an interpretation on the concepts of adiabatic and sudden core excitation in metals.     

Predicted formation of superconducting platinum-hydride crystals under pressure in the presence of molecular hydrogen

Noble metals adopt close-packed structures at ambient pressure and rarely undergo structural transformation at high pressures. Platinum (Pt) is normally considered to be unreactive and is therefore not expected to form hydrides under pressure. We predict that platinum hydride (PtH) has a lower enthalpy than its constituents solid Pt and molecular hydrogen at pressures above 21.5?GPa. PtH transforms to a hexagonal close-packed or face-centered cubic (fcc) structure between 70 and 80 GPa. Linear response calculations indicate that PtH is a superconductor at these pressures with a critical temperature of about 10-25?K. These findings help to shed light on recent observations of pressure-induced metallization and superconductivity in hydrogen-rich materials. We show that the formation of fcc noble metal hydrides under pressure is common and examine the possibility of superconductivity in these materials.     

Hydrides of intermetallic compounds

Aspects of the progress over the recent years on hydrides of intermetallic compounds are reviewed with emphasis on structure, stability, solid-state properties, catalysis, and kinetics. Some new routes to an understanding of hydride phenomenology are indicated. Generally speaking hydrides represent but one special aspect of intermetallic compounds. They are, however, unique as model systems for questions concerning the stability of intermetallics in general, as thermodynamic data become more readily available during synthesis than is the case with most other metallic systems. Stability criteria are exemplified on model systems chosen to represen instructive or extreme cases. Hydrides are, moreover, unique with respect to the unusual properties of hydrogen as a “metallic” component, especially concerning such characteristics as mass (light), size (ranging from average to exceedingly small as a proton) and electronegativity (relatively high and comparable to B). This promises a wealth of special solid-state properties concerning magnetism, electrical conductivity or superconductivity. Some selected examples in this direction are discussed with emphasis on questions pertaining to the electronic state and the stability of the hydrides. The kinetics of compound (hydride) formation are often extraordinarily fast around ambient conditions opening this facet of intermetallics to rigorous study. Also intriguing new catalytic activity has been identified with metal hydrides implicating in one way or another the special surface properties of metal hydrides. Finally, metal hydrides are gaining in importance with respect to technological applications within a projected hydrogen economy (H or heat storage, electrochemical cells, etc.). Many of the fundamental aspects of metal hybrides have therefore become of practical relevance. Financial support by the Department of Energy, Division of Basic Energy Sciences, is acknowledged.     

Structural and valence changes of europium hydride induced by application of high-pressure H₂

Europium hydride EuH(x), when exposed to high-pressure H?, has been found to exhibit the following structural and valence changes: Pnma(x = 2, divalent) → P6?/mmc(x = 2, 7.2-8.7 GPa) → I4/m(x > 2, 8.7-9.7 GPa) → I4/mmm(x > 2, 9.7 GPa-,trivalent). With a trivalent character and a distorted cubic fcc structure, the I4/mmm structure is the β phase commonly observed for other rare-earth metal hydrides. Our study clearly demonstrates that EuH(x) is no longer an irregular member of the rare-earth metal hydrides.     

Mechanically alloyed metal hydride systems

Mechanosynthesis of metal hydrides is a new field in which important progress has been reported. In this paper, we present recent developments in mechanosynthesis of magnesium-based hydrides for storage applications. The effect of intense milling on magnesium and magnesium hydrides is presented. The influence of various additives on hydrogen-sorption properties is discussed with special emphasis on nanocomposite MgH₂+5 at. % V, where hydrogen-storage characteristics, cycling properties and the mechanism of hydrogen desorption are presented. The production of novel nanocrystalline porous structures by mechanical alloying followed by a leaching technique is discussed. Hot ball-milling, as a new method for rapid synthesis of alloys, is also presented. Finally, two other methods of production of metal hydrides are discussed. One is reactive milling where metal hydrides are synthesized by mechanical alloying under hydrogen pressure, while the other is milling elemental hydrides to produce complex hydrides. Received: 15 August 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Compressibility of hydrogen in Ni and Re hosts at pressures to 123 GPa

Abstract

Ni-H and Re-H binary systems have been studied at room temperature by X-ray diffraction in a diamond-anvil cell. The formation of the hydrides NiH and ReHo.4 with no change in the types of the host metal lattices was observed through the expansion of the host lattices. No structure changes were observed in the metal sub-lattice of either hydride under increasing pressure and the equations of state have been obtained to 123GPa. The difference in the partial hydrogen volume as a function of pressure between the Ni-H and Re-H systems can be understood with reference to the behaviour of conduction electrons. The pressure dependence of the partial hydrogen volume in these hydrides supports the hypothesis of the apparent common-volume behaviour of hydrogen in a metallic environment.     

Structure, catalysis and atomic reactions on the nano-scale: a systematic approach to metal hydrides for hydrogen storage

We show how reducing structure, catalysis and atomic reactions to the nano-scale may be used in a systematic way to substantially enhance the hydrogenation properties of metal hydrides. We examine, with examples from a wide range of hydrides, the direct impact of nano-scale structure, subsequent improvements in kinetics through nano-scale solid state catalysis, the special properties of nano-composites, and the role played by nano-scale reactions. Received: 25 August 2000 / Accepted: 14 November 2000 / Published online: 9 February 2001     

Properties suggesting H3+-type clusters in some metallic hydrides

The p-c-T relationships for the hydrogen-rich phase of some metallic hydrides are calculated supposing the formation of H₃⁺ -type clusters in the metal lattice in equilibrium with the hydrogen gas. The experimental data for the hydride phase of LaNi₅, Pd, Nb (H?Nb? 0.75) and U are consistent with this model. Other properties reported in literature which seem to support this model are discussed.     

Ab initio study of H and He migrations in β-phase Sc, Y, and Er hydrides

Ab initio calculations based on the density functional theory have been performed to investigate the migrations of hydrogen(H) and helium(He) atoms in β-phase scandium(Sc),yttrium(Y),and erbium(Er) hydrides with three different ratios of H to metal.The results show that the migration mechanisms of H and He atoms mainly depend on the crystal structures of hydrides,but their energy barriers are affected by the host-lattice in metal hydrides.The formation energies of octahedral-occupancy H(H oct) and tetrahedral vacancy(V tet) pairs are almost the same(about 1.2 eV).It is of interest to note that the migration barriers of H increase with increasing host-lattice atomic number.In addition,the results show that the favorable migration mechanism of He depends slightly on the V tet in the Sc hydride,but strongly on that in the Y and Er hydrides,which may account for different behaviours of initial He release from ScT2 and ErT2.     

Magnetic properties of titanium vanadium hydrides

Measurements have been made of the magnetic susceptibility X in ternary titanium-vanadium hydrides Ti_1?yV_yH_x in the range 0<y< 0.5 and with a hydrogen to metal ratio from 1.6 to 1.92; they cover the temperature interval from 80 to 440 K. The x^?T curves of some of the ternary hydrides possess a maximum similar to that seen in binary hydrides. Its occurrence depends upon both hydrogen and vanadium concentration. Comparison with the lattice constants shows that this dependence is related to the transition from the cubic γ-phase to the tetragonal δ-phase. The x^?T curves of those samples showing the phase transition were extrapolated from the cubic phase down to lower temperatures. Conclusions were drawn from the measured and extrapolated susceptibility values, as to the influence of both hydrogen and vanadium concentrations on the electronic structure of these hydrides. The dependence of the magnetic susceptibility on the vanadium concentration shows that, in the cubic phase, the fermi energy lies on the increasing side of a maximum in the density of states curve. The degree of occupation of the conduction band does not depend on the hydrogen concentration. The rigid band model cannot be used in the hydrides studied here to account for the effects of varying their hydrogen concentration.     

Water formation on oxygen exposure of some hydrides of intermetallic compounds

It is found that a large number of metal hydrides such as hydrides of materials in Ca−Mg−Ni can form water when exposed to O₂ largely without signs for concomitant substrate oxidation. One can speak of a catalytic reaction in this connection as the H-depleted metal matrix can in most cases be rehydrided and water synthesis repeated on exposure to O₂. In some cases a considerable portion of the H combustion reaction takes place in a matter of seconds. Some of the metal hydrides such as hydrides of CaNi₄B, CeNi₃, and YbNi₂, are relatively stable concerning decomposition of the alloy by the product water, while others, for example hydrides of CaNi₃, and CaNi₂, are rapidly decomposed by the product water forming the hydroxide of the electropositive metal. They also produce fine ferromagnetic Ni-particles which could be interesting for other catalytic purposes. Guest professor, work also performed at University of California at San Diego where support by a grant from DOE, Basic Energy Sciences, is acknowledged.     

Energetics and electronic properties of Mg7TMH16 (TM=Sc, Ti, V, Y, Zr, Nb): An ab initio study

First-principles calculations have been performed on the face-centered cubic (FCC) magnesium-transition metal (TM) hydrides Mg₇TMH₁₆ (TM=Sc, Ti, V, Y, Zr, Nb). The cohesive energies are calculated to analyze the stability, and the obtained enthalpies of formation for hydrides Mg₇TMH₁₆ have been used to investigate the possible pathways of formation reaction. The calculated enthalpy changes show that the decomposition temperatures of Mg₇TMH₁₆ are lower than that of MgH₂. The electronic densities of states reveal that all the hydrides studied here exhibit metallic characteristics. The bonding nature of Mg₇TMH₁₆ is investigated, showing stronger covalent bonding between TM and H than between Mg and H.     

Why does hydrogen destroy superconductivity in niobium and lanthanum?

Starting from a theoretical study of the electronic properties of the corresponding stoichiometric metal hydrides by means of an augmented plane wave band structure calculation, we present an evaluation of the electron-phonon coupling parameter λ, using the McMillan formalism. The electronic term η is calculated from first principles using the rigid ion approximation while experimental data are used to estimate the phonon contribution. From a detailed analysis of both the electron-acoustic phonon coupling and of the electron-optic phonon coupling we discuss the reasons why hydrogen kills superconductivity in the high T_c metals Nb and La. These results in conjunction with our studies of a series of metal hydrides are used to draw general conclusions and make some predictions about the possible occurrence of superconductivity in transition metal hydrides.     

Heats of formation of 3d and 4d transition metal hydrides

One electron energy spectra are used to explain the heats of formation of stoichiometric transition metal hydrides across the 3d and 4d rows. The trends agree reasonably with existing experimental information. The magnitudes are predominantly (but not exclusively) determined by the formation of a metal-H bonding band. In contrast to the screened proton model, the result is not directly related to the Fermi level density of states.     

Formation of transition metal hydrides at high pressures

Silane (SiH₄) is found to (partially) decompose at pressures above 50 GPa at room temperature into pure Si and H₂. The released hydrogen reacts with surrounding metals in the diamond anvil cell to form metal hydrides. A formation of rhenium hydride is observed after the decomposition of silane and reaction of hydrogen with Re gasket. From the data of a previous experimental report [M.I. Eremets, I.A. Trojan, S.A. Medvedev, J.S. Tse, Y. Yao, Science 319 (2008) 1506], the claimed high-pressure metallic and superconducting phase of silane is identified as platinum hydride, that forms after the decomposition of silane. These observations show the importance of taking into account possible chemical reactions that are often neglected in high-pressure experiments.     

On the thermodynamics of phase transitions in metal hydrides

Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier’s principle of thermodynamics to a particular phase transition in TiH _x , which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H⁺ ions and of the distance between adjacent H⁺ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H⁺ ions (‘collective modes’) increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H⁺ ions with collective modes makes a tiny suprathermal fraction of the H⁺ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.     

Al掺杂对合金Mg1-xTix及其氢化物稳定性的影响

用密度泛函理论,研究了Al对合金Mg_1-xTi_x及其氢化物稳定性和电子结构的影响. 通过计算不同掺杂浓度的Mg-Ti-Al合金的形成焓,发现当Al和Ti的浓度之比为1:1时, 合金结构最稳定,有利于氢的可逆吸收;而掺杂体系的氢化物稳定性降低, 可提高放氢性能.通过对态密度,电子密度和键长的分析, 表明Al改善Mg-Ti系统的放氢性能的原因是掺杂后减少了低能级区成键态的电子以及减弱了Mg-H, Ti-H原子间的相互作用. 关键词： 1-xTi_xH₂储氢材料')" href="#">Mg_1-xTi_xH₂储氢材料 赝势平面波 电子结构 稳定性     

Violation of the minimum h-h separation "Rule" for metal hydrides

Using gradient-corrected, full-potential, density-functional calculations, including structural relaxations, it is found that the metal hydrides RTInH1.333 (R=La, Ce, Pr, or Nd; T= Ni, Pd, or Pt) possess unusually short H-H separations. The most extreme value (1.454 A) ever obtained for metal hydrides occurs for LaPtInH1.333. This finding violates the empirical rule for metal hydrides, which states that the minimum H-H separation is 2 A. The paired, localized, and bosonic nature of the electron distribution at the H site are polarized towards La and In which reduces the repulsive interaction between negatively charged H atoms. Also, R-R interactions contribute to shielding of the repulsive interactions between the H atoms.     

Structural phase stability,electronic structure and mechanical properties of alkali metal hydrides AMH4 (A=Li,Na; M=B,AL)

The structural stability of Alkali metal hydrides AMH₄ (A=Li, Na; M=B, Al) is analyzed among the various crystal structures, namely hexagonal (P6₃mc), tetragonal (P4₂/nmc), tetragonal (P-42₁c), tetragonal (I4₁/a), orthorhombic (Pnma) and monoclinic (P2₁/c). It is observed that, orthorhombic (Pnma) phase is the most stable structure for LiBH₄, monoclinic (P2₁/c) for LiAlH₄, tetragonal (P4₂/nmc) for NaBH₄ and tetragonal (I4₁/a) for NaAlH₄ at normal pressure. Pressure induced structural phase transitions are observed in LiBH₄, LiAlH₄, NaBH₄ and NaAlH₄ at the pressures of 4 GPa, 36.1 GPa, 26.5 GPa and 46 GPa respectively. The electronic structure reveals that these metal hydrides are wide band gap insulators. The calculated elastic constants indicate that these metal hydrides are mechanically stable at normal pressure.