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by: Kobe Dare


Kobe Dare
GPA 3.6


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Class Notes
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This 18 page Class Notes was uploaded by Kobe Dare on Thursday October 22, 2015. The Class Notes belongs to THTR 262 at University of California Santa Barbara taught by Staff in Fall. Since its upload, it has received 39 views. For similar materials see /class/226862/thtr-262-university-of-california-santa-barbara in Theatre at University of California Santa Barbara.

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Date Created: 10/22/15
Hydrides of the Transition Metals Katharine Page MATRL 262 Fall 2005 Overview I Motivation I De nitions I Binary Transition Metal Hydrides Structure Properties I Complex Ternary Metal Hydrides El Structure in Hydrogen Storage Properties LJ Motivation Metals can absorb large quantities of hydrogen at relatively low pressures and temperatures making them attractive for onboard hydrogen storage Vehicles will need compact light safe and affordable containment Reversible hydrogen exchange properties of intermetallic hydrides are utilized in rechargeable batteries Structures are also of interest with respect to hydrogen embrittlement and the failure of metals under stress A Jzno m Schlapbach and A Zuttel Nature 414 2001 353358 Definitions What is a metal hydride Disassociated hydrogen atoms absorb or dissolve into the metal phase The interrnetalic phase Where H dissociates at random is known as the aphase I The elements V Nb and Ta have lSOlid solutions to V005 NbM and Tao2 in their bcc metal structures Within the metallic phase the hydrogen atoms can start to arrange themselves in a speci c con guration With the metal atoms forming the metal hydride phase called the Bphase LaNi5 I phase Fl l Im 39 imnhm 1 1 1mquot 5 5 3 PW 1l r 1 x f If u3phese I i I f 25cth I w l I E i Err 39 131 do d2 054 a on m EHIH MI L Schlapbach and A Zuttel Nature 414 2001 353 39 JBinary Hyd rides fcc BiF3 The known binary hydrides With de nite structures bcc Most form in MHZ fluorite 0r MH3 tysonite structures NiAS MnH N4f MH2 a d MH3 5f MH2 andor MH3 Fr h lH I J A F Wells Structural Inorganic Chemistry 5th ed Oxford Univ Press 1984 U Muller Inorganic Structural Chemistry John Wiley amp Sons 1993 39 I J MHZ Fluorite type TiH2 I Fm3m I a 44316 A I Ti 0 0 0 I H 025 025 025 Structure of the dihydrides of Cr the hop elements Ti Zr and Hf and 4far1d 5f metals except Eu and Yb Cubic above transition points Tetragonal symmetry at lower temperatures MH3 LaF3 or Tysonite type HoD3 I P3cl tetragonal a 630 A u c 656 A Both 3 and 4coordinate H Metal is llcoordinate Structure OfIhe trihydrides 0f 4f and 5f metals exceptfor La Ce Pr Nd and U I The surplus hydrogen in the MH19 uorite to MH3 tysonite transition occupies the octahedral interstices of the uorite structure I Trihalides of La Ce Pr and Nd remain fcc to MH3 Properties of Binary Hydrides I Larger interatomic distances than parent metal I Metallic or graphitic in appearance I Metallic conductivity or semiconductivity u n Resistivity increases with hydrogen absorption metal to semiconductor I LaH29LaH3 I YH29YH3 NdH NdH3 I 4f hydrides are usually pyrophoric PdH06 for example holds 056 of its mass in hydrogen Pressure and temperature range for reversible exchange are not attractive for mobile storage Complex Ternary Hydrides I AXMHZ Where A is an alkali or alkalineearth metal I Structures characterized by the presence of complex anions of the form MHZ2X39 I Geometries W Linear W Square Planar W Tetrahedral W Square Pyramidal W Octahedral W Bronger Angew Chem Int Engl 30 1991 759 R Bau M H Drabnis Inorganica Chimica Acta 259 1997 2750 Linear Geometry Contain MH2 39 ions LiZPdHZ Tetragonal LithH2 I4mrnm caIPdHI a 3599 A KKPdHK KHKZPdHZ c 11327 A 14 electron d1 coordination Eml Prn3m It s Perovsklte L1ke a3690A 39 canH2 Sci 8 5 8 5 8 5 I Statistical distribution of PdH2 239 39 units no preferred orientation 0 05 0 0 I H occupies the octahedral vertices to 23 on average 39 i Mquot Square Planar Geometry V k Tetragonal I4mmm Contain MH4 39 ions 3 a 5338 A Li3RhH4 j t c 6614 A NadeH4 ZrZCoH5 slightly distorted KthH4 16 electron d8 coordination Lt Higher Coordination or 39 3 33 PB 0x43 SquarePyramidal Octahedral Tetrahedral I I contain MH4nr iOHS Contaln MH5439 10115 Contaln MH6439 10115 Mg2NiH4 Mg2C0H5 MgZFeHS K3MnH5 KHKzMnHA SrthDsquot Sr2RuH6 Sr2IrH5quot CaQOsD6 MggRuHsquot Na3er6 18 electron dw 18 electron d8 18 electron d6 coordin tion coordination coordination Ni Mn Co Rh Ir Ru Fe Re RuPs R11 1r Disorder over octahedral sites The structures of these ternary hydrides can be related in a very simple way KZPtCl6 Parent Structure Octahedral Complexes MgZFeD6 I Fe and Mg form in the uorite structure I D or H decorate Fe in an octahedral coordination This is also the structure of many high temperature forms of the tetrahedral and square pyramidal coordination compounds I Ni equivalent 23 46 occupation of the octahedra l Co equivalent 56 occupation 39 Phase Transitions Tetragonal low temperature phase goes to cubic high temperature phase NaZPtD4 In this case the cubic phase has 23 occupancy of the hydrogen octahedral positions Uh Dynamic Hydrogen Ligand KZPtD4 The four hydrogens ligands attached to the Pt atom with d8 con guration give planar coordination Phase transition at 195K nix MI 8 T293K T210K T182K T83K I l inquot If k 5 IV 3 Tetra onal 3 J 5 H g Fm3m P42mnm a 8025 A was 373 a 5582 A c 8089 A W Bronger AngeW Chem Int Ed Eng 30 1991 759 Storage Properties new 5 9 ms 2 g s 1 g m u 7 9 ma Sn 7 N BH L E ZaK I Need 45 mass to be r 1 395 an 9 A 9quot 13me fea51b1e DOE targets 9 r 5351mm um 65 Equot A nu ma x muggy Equot sue I LaN15H5V for example 15 too if expensive 50 Hzphyslsarbed warmquot I MgNaH4 reqmres too hlgh w of a temperature my I Many are too heavy u m 3 am w massw The search continua Summary I Transition metal oxides are an important class of materials for reversible hydrogen storage I Binary transition metal hydrides form predominantly in the ourite or tysonite structures with stoichiometry MH2 and MH3 respectively I Ternary Metal Hydrides contain an alkali or alkaline earth metal and a transition metal or an alloyed phase of metals Structures can be depicted with coordination ions in familiar crystal structures I Many metal hydrides are not well characterized or understood


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