materials for hydrogen storage: from nanostructures to ... · from nanostructures to complex...
TRANSCRIPT
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Materials for Hydrogen Storage:Materials for Hydrogen Storage:From Nanostructures to Complex From Nanostructures to Complex
HydridesHydrides
Virginia Commonwealth University, Richmond, VA.Virginia Commonwealth University, Richmond, VA.
International Symposium on Materials Issues in Hydrogen productiInternational Symposium on Materials Issues in Hydrogen production on and Storage and Storage –– Santa Barbara August 20Santa Barbara August 20--25, 200625, 2006
Puru Jena
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Outline
Materials Requirement for Hydrogen Storage
Nanostructured materials:
Boron Nitride Nano Cage
Metal Coated Carbon Fullerenes
Organo-Metallic Frameworks
Complex light metal hydrides - Sodium Alanates
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Acknowledgement
Carbon and Boron Nitride Nano Structures:
Q. Sun, Q. Wang, VCU
Organo-metallic frameworks
K. Boggavarapu, A. Kandalam
Sodium Alanates:
Sa Li, VCU,
C. M. Araujo, and R. Ahuja, Univ. of Uppsala Work Supported by the Department of Energy
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Hydrogen Storage RequirementsHydrogen Storage Requirements
High gravimetric (9 wt %) and volumetric density High gravimetric (9 wt %) and volumetric density (70 g/L)(70 g/L)Fast kineticsFast kineticsFavorable thermodynamicsFavorable thermodynamicsEffective heat transferEffective heat transferLong cycle lifetime for hydrogen Long cycle lifetime for hydrogen absorption/desorptionabsorption/desorptionSafety, durability, and cost effectivenessSafety, durability, and cost effectiveness
75% of U.S. oil consumption is used to meet 75% of U.S. oil consumption is used to meet transportation energy needstransportation energy needs
Transportation ApplicationsTransportation Applications
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Hydrogen Storage MediaHydrogen Storage Media
Gaseous storage Gaseous storage –– High PressureHigh PressureEnergy content = 4.4 MJ/L (at 10,000 Energy content = 4.4 MJ/L (at 10,000 psipsi))compared to that of 31.6 MJ/L for fossil fuel. compared to that of 31.6 MJ/L for fossil fuel. Costs associated with compression, leakage and safety Costs associated with compression, leakage and safety
are issues of concern. are issues of concern.
Liquid Storage Liquid Storage -- Cryogenic TemperaturesCryogenic TemperaturesDensity of liquid of HDensity of liquid of H22 at 20 K= 70 g/Lat 20 K= 70 g/LEnergy content = 8.4 MJ/L Energy content = 8.4 MJ/L
Solid State StorageSolid State Storage
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Materials RequirementsMaterials Requirements
For high gravimetric density (9 wt %) host For high gravimetric density (9 wt %) host materials must consist of light elements: Li, Be, materials must consist of light elements: Li, Be, B, C, N, Na, Mg, AlB, C, N, Na, Mg, AlDifficulties: Bonding of hydrogen is strong Difficulties: Bonding of hydrogen is strong (covalent or ionic) and thermodynamics and (covalent or ionic) and thermodynamics and kinetics are not idealkinetics are not idealIdeal Bonding: not too weak or not too strongIdeal Bonding: not too weak or not too strongWays of altering the chemistry of hydrogen Ways of altering the chemistry of hydrogen bonding: bonding: nanostructuringnanostructuring or catalysisor catalysis
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Atomic and Electronic StructureAtomic and Electronic Structure
Linear combination of atomic orbitalsLinear combination of atomic orbitalsGradient Corrected Density Functional TheoryGradient Corrected Density Functional TheoryGaussian Basis sets, and Gaussian 98 codeGaussian Basis sets, and Gaussian 98 codeGeometries optimized without symmetry constraintGeometries optimized without symmetry constraint
CrystalsCrystals
SupercellSupercell Band Structure Methods within Gradient Corrected Band Structure Methods within Gradient Corrected Density Functional TheoryDensity Functional Theory
Atomic Clusters
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Boron Nitride Cage
Q. Sun, Q. Wang, and P. Jena, “Storage of molecular hydrogen in B-N cage: Energeticsand thermal stability”, Nano Letts. 5, 1273 (2005)
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Passage of H2 into the B36N36 cage
square hexagon
BNH
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How many H2 can be inserted inside the cage ?
36H2 24H2 18H220H2
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0 2 4 6 8 10 12 14 16 18 20
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
∆ = -0.017n3+0.162n2-0.463n+5.332
calculation fitting
HO
MO
-LU
MO
gap
∆ (e
V)
n (number of H2)
0 2 4 6 8 10 12 14 16 18 20
0
5
10
15
20
25
30
35
40
ε = 0.1133n2-0.0684n-0.0247
calculation fitting
Form
atio
n en
ergy
ε (e
V)
n (number of H2)
Energy and gap
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0 2 4 6 8 10 12 14 16 18 200.735
0.740
0.745
0.750
R2 = 0.736 + 0.0156exp(-0.157n)
calculation fitting
H-H
bon
d le
ngth
R2
n (number of H2)0 2 4 6 8 10 12 14 16 18 20
1.46
1.47
1.48
1.49
1.50
1.51
R1 = 1.4576 + 0.0067exp(0.1079n)
calculation fitting
B-N
bond
leng
th R
1
n (number of H2)
Changes in bond length
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SummarySummary
Boron Nitride Cage can store hydrogen in Boron Nitride Cage can store hydrogen in molecular form, but the energy costs are high molecular form, but the energy costs are high and thermodynamically unstableand thermodynamically unstable
Boron Nitride Cages are not suitable for Boron Nitride Cages are not suitable for hydrogen storagehydrogen storage
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Nature of Hydrogen BondNature of Hydrogen Bond
0.76 Å
> 3.0 Å
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Nature of Hydrogen BondNature of Hydrogen Bond
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Nature of Hydrogen BondNature of Hydrogen Bond
~0.90 Å
~2.5 Å~2.5 Å
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Lessons from early studies on Lessons from early studies on clustersclusters
J. J. NiuNiu, B. K. Rao, and P. Jena, , B. K. Rao, and P. Jena, ““Binding of Binding of hydrogen molecules by a transitionhydrogen molecules by a transition--metal ionmetal ion””, , Phys. Rev. Letters Phys. Rev. Letters 6868, 2277 (1992), 2277 (1992)B. K. Rao and P. Jena, B. K. Rao and P. Jena, ““Hydrogen uptake by an Hydrogen uptake by an alkali metal ionalkali metal ion””, , EurophysEurophys. Lett. . Lett. 2020, 307 (1992), 307 (1992)J. J. NiuNiu, B. K. Rao, P. Jena, and M. Manninen, , B. K. Rao, P. Jena, and M. Manninen, ““Interaction of HInteraction of H22 and He with metal atoms, and He with metal atoms, clusters, and ionsclusters, and ions””, Phys. Rev. B , Phys. Rev. B 5151, 4475 (1995), 4475 (1995)G.J. G.J. KubasKubas, Acc. Chem. , Acc. Chem. ResRes, 21, 120(1988), 21, 120(1988)
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Ti2: r =1.90 (exp. 1.91) EB = 3.68eV moment =2.0
H2: r =0.749 (exp. 0.741) EB= 4.536 eV (exp. 4.533)
2.992
1.751
117.4
EB = -1.115eV
TiH2
EB = -1.073eV
Ti+H2
0.774
2.01
+
TiH2 and Ti+H2 cluster
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Ti coated C60
Q. Sun, Q. Wang, P. Jena, and Y. Kawazoe, J. Am. Chem. Soc. (Communication) 127, 14582 (2005).
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E_ab = 0.55eV/H2
R(Ti-H) = 2.0
R(H-H) = 0.81
Moment = 2.0
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1.902eV/Ti M=6.0 2.384eV/Ti M=4.0
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2.915eV/Ti M=1.90 2.958eV/Ti M=2.0 3.03eV/Ti M=1.80
2.162
2.24
1
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1.960.811
EB = 0.55 eV /H2
Moment = 4.0
1.9781.936
1.985
2.31
32.278
0.8050.827
EB = 0.378 eV / H2
Moment = 2.24
(0.0)(+ 0.924eV )
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5 H2 molecules on each TiH2 seen to desorb
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4 H2 molecules on each Ti atom
E = 0.40 eV / H2
R(Ti-Ti) = 2.855
R(Ti-C) =2.333—2.347
R(Ti-H2) =1.94
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NM
E=0.0eV
M=0.0
C1
FM
E=+24.8eV
M=36.0
Ih
Ferri
E=+24.52eV
M=12.0
C2v
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SummaryHexagonal site is the most stable site for Ti atom.
Ti atoms tend to form clusters on C60 surface.
For isolated Ti atom on hexagonal site, hydrogen is absorbed in molecular form.
Clustering of Ti atoms make some hydrogen molecules dissociate, resulting in hydrogen bonded to Ti in atomic form more strongly. This would affect the hydrogen release and storage efficiency.
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Li Coated CLi Coated C6060 FullereneFullerene
Q. Sun, P. Jena, Q. Wang, and M. Marquez, Q. Sun, P. Jena, Q. Wang, and M. Marquez, ““First Principles Study of Hydrogen Storage of First Principles Study of Hydrogen Storage of LiLi1212CC6060,,”” J. Am. Chem. Soc, 128, 9741J. Am. Chem. Soc, 128, 9741--9745, 9745, (2006)(2006)
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E=0.0eV E= + 2.20eV
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0.755
0.755
2.072.07
2.236
C60-Li-H2
Li+-H2
C60-Li
2.04
0.75
2.04
2.229
1.461 1.461
C60
1.457
E=0.18 eV E=0.25 eV
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H H
Li
C60
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Interaction energy: 4.50eV
Weight percent: 13%
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Interaction between Li12C60 clusters-I
E=0.4 eV
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Interaction between Li12C60 clusters-II
E=1.18 eV
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Interaction of H2 with Li12C60 dimer
EH2= 0.18 eV
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E= 0.18 eV/H2
Interaction of H2 with Li12C60 dimer
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SummarySummary
Li atoms do not cluster on CLi atoms do not cluster on C6060 fullerene surfacefullerene surfaceLi atoms bind strongly to the fullereneLi atoms bind strongly to the fullereneHydrogen atoms bind molecularlyHydrogen atoms bind molecularlyBinding energy of HBinding energy of H22 is small, but significantis small, but significantHigh gravimetric and volumetric densityHigh gravimetric and volumetric densityLiLi1212CC6060 has already been synthesized in the lab.has already been synthesized in the lab.Interaction between LiInteraction between Li1212CC6060 dimersdimers do not do not destroy the cluster geometrydestroy the cluster geometry
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Interaction of HInteraction of H22 with Ti supported with Ti supported on organic moleculeson organic molecules
CC55HH55
CC44HH44
CC88HH88
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1.75Å
2.40Å1.76Å1.76Å
0.832Å
1.91Å
0.82Å
1.75Å
1.76Å
1.96Å
1.98Å
0.80Å
0.80Å
1.95Å1.75Å
1.95Å 1.76Å
0.83Å
0.80Å
1.91Å
1.93Å
2.00Å 1.90Å
1.90Å
1.90Å
0.84Å
0.84Å
0.84Å
0.84Å
(b)(a) (b′)
(c) (c′) (d)
1.75Å
2.40Å
1.75Å
2.40Å1.76Å1.76Å
0.832Å
1.91Å
1.76Å1.76Å
0.832Å
1.91Å
0.82Å
1.75Å
1.76Å
1.96Å
1.98Å
0.82Å
1.75Å
1.76Å
1.96Å
1.98Å
0.80Å
0.80Å
1.95Å1.75Å
1.95Å
0.80Å
0.80Å
1.95Å1.75Å
1.95Å 1.76Å
0.83Å
0.80Å
1.91Å
1.93Å
2.00Å1.76Å
0.83Å
0.80Å
1.91Å
1.93Å
2.00Å 1.90Å
1.90Å
1.90Å
0.84Å
0.84Å
0.84Å
0.84Å1.90Å
1.90Å
1.90Å
0.84Å
0.84Å
0.84Å
0.84Å
(b)(a) (b′)
(c) (c′) (d)
Optimized geometries of Ti C5H5 (H2)n, (n=1-4) along with important bond lengths (Å). The energy difference (∆E) between (b) and (b′) is 0.12 eV; (c) and (c′) is 0.02 eV
with (b) and (c) being lower in energy than (b′) and (c′), respectively.
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Hydrogen Storage and the 18 Hydrogen Storage and the 18 electron ruleelectron rule
Ti 3dTi 3d22 4s4s2 2 Total number of electrons = 4Total number of electrons = 4CC55HH55 Total number of electrons = 5Total number of electrons = 5TiCTiC55HH55(H(H22))4 4 Total number of electrons = 17Total number of electrons = 17TiCTiC55HH5 5 cannot accommodate more than 4 Hcannot accommodate more than 4 H22molecules molecules TiCTiC44HH44 can accommodate 5 Hcan accommodate 5 H22 moleculesmoleculesTiCTiC88HH88 can accommodate 3 Hcan accommodate 3 H22 moleculesmolecules
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1.73Å
2.20Å
1.75Å0.82Å
2.22Å
1.89Å0.83Å
0.83Å
0.88Å
1.93Å
1.83Å1.90Å
2.20Å
0.84Å0.84Å
0.84Å0.84Å
1.90Å
2.20Å 0.83Å
0.83Å 0.84Å
0.84Å
0.77Å
2.17Å
1.89Å1. 90Å
2.23Å
0.81Å0.81Å
1.79Å
1.72Å
1.93Å
1.96Å
2.31Å
(b′)
(c′) (d)
(d′) (e) (f)
2.06Å
(a′)
2.20Å 2.04Å
1.72Å
(b)
(c)
2.04Å 0.92Å
0.92Å
1.82Å1.81Å
(a)
1.73Å
2.20Å
1.73Å
2.20Å
1.75Å0.82Å
2.22Å
1.89Å 1.75Å0.82Å
2.22Å
1.89Å0.83Å
0.83Å
0.88Å
1.93Å
1.83Å1.90Å
2.20Å
0.83Å
0.83Å
0.88Å
1.93Å
1.83Å1.90Å
2.20Å
0.84Å0.84Å
0.84Å0.84Å
1.90Å
2.20Å
0.84Å0.84Å
0.84Å0.84Å
1.90Å
2.20Å 0.83Å
0.83Å 0.84Å
0.84Å
0.77Å
2.17Å
1.89Å1. 90Å
2.23Å0.83Å
0.83Å 0.84Å
0.84Å
0.77Å
2.17Å
1.89Å1. 90Å
2.23Å
0.81Å0.81Å
1.79Å
1.72Å
1.93Å
1.96Å
2.31Å
0.81Å0.81Å
1.79Å
1.72Å
1.93Å
1.96Å
2.31Å
(b′)
(c′) (d)
(d′) (e) (f)
2.06Å2.06Å
(a′)
2.20Å
(a′)
2.20Å 2.04Å
1.72Å
2.04Å
1.72Å
(b)
(c)
2.04Å 0.92Å
0.92Å
1.82Å1.81Å
(c)
2.04Å 0.92Å
0.92Å
1.82Å1.81Å
(a)
Optimized geometries of Ti C4H4 (H2)n (n=1-5) along with important bond lengths (Å). The energy difference (∆E) between (a) and (a′) is 0.35 eV, (b) and (b′) is 0.29 eV,
(c) and (c′) is 0.07 eV, and (d) and (d′) is 0.05 eV with (a), (b), (c), and (d) being lower in energy than (a′), (b′), (c′), and (d′), respectively.
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0.83Å0.83Å
1.96Å1.96Å
1.90Å 0.83Å
1.90Å
1.70Å
2.30Å
0.86Å0.86Å
1.90Å
1.85Å
0.81Å1.71Å
1.70Å 1.97Å
1.93Å
(a) (b)
(b′) (c)
0.83Å0.83Å
1.96Å1.96Å
1.90Å 0.83Å
1.90Å
0.83Å0.83Å
1.96Å1.96Å
1.90Å 0.83Å
1.90Å
1.70Å
2.30Å
1.70Å
2.30Å
0.86Å0.86Å
1.90Å
1.85Å 0.86Å0.86Å
1.90Å
1.85Å
0.81Å1.71Å
1.70Å 1.97Å
1.93Å 0.81Å1.71Å
1.70Å 1.97Å
1.93Å
(a) (b)
(b′) (c)
Optimized geometries of Ti C8H8 (H2)n (n=1-3) along with important bond lengths (Å). The energy difference (∆E) between (b) and (b′) is 0.02 eV with (b) being lower in
energy than (b′).
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Table I. Energy gain ∆En (in eV) due to the successive addition of H2 molecules to
Ti(CmHm) complexes
System n ∆En (eV) DMola Gaussianb
TiC5H5(H2)n 1 1.36 1.26 2 0.51 0.47 3 0.45 0.54 4 0.56 0.56
TiC4H4(H2)n 1 1.03 1.10 2 0.26 0.43 3 0.47 0.30 4 0.75 0.77 5 0.22 0.35
TiC8H8(H2)n 1 1.07 1.12 2 0.28 0.30 3 0.36 0.20
a: PW91/DNP b: PW91PW91/(SDD: Ti; 6-31G**: C, H)
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Hydrogen Storage in multiHydrogen Storage in multi--deckerdeckercomplexescomplexes
(C(C55HH55Ti)Ti)nn, (C, (C55HH55))n+1n+1TiTinn
(C(C66HH66Ti)Ti)nn, (C, (C66HH66))n+1n+1TiTinn
Choosing substrates to prevent clusteringChoosing substrates to prevent clustering
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[(C[(C55HH55Ti)Ti)22] (H] (H22))88 [(C[(C55HH55Ti)Ti)22] (H] (H22))99
BE/HBE/H22 = 0.35 eV= 0.35 eV BE/HBE/H22 = 0.30 eV= 0.30 eV
(C(C55HH55Ti)Ti)22
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(C(C55HH55Ti)Ti)22
∆∆E = 0.00 eVE = 0.00 eV ∆∆E = 0.50 eVE = 0.50 eV ∆∆E = 1.02 eVE = 1.02 eV
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(C(C55HH55))33TiTi22
?? ??
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Complex Light Metal Hydrides Complex Light Metal Hydrides
and and
Role of catalystsRole of catalysts
C.M. Araujo, R. Ahuja, J.M.O. Guillen, and P. Jena, Appl. Phys. Letts. 86, 251913 (2005); C. M. Araujo, S. Li, R. Ahuja, and P. Jena, Phys. Rev. B (in press)
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Sodium Alanates
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For more information, see website http://www.sc.doe.gov/bes/hydrogen.pdf
Structure of Alanates
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Sodium Sodium AlanateAlanate –– NaAlHNaAlH44
4 3 6 2
3 6 2
1 23 3
3 32
NaAlH Na AlH Al H
Na AlH NaH Al H
↔ + +
↔ + +
Discovered: (Finholt & Schlesinger 1955)Direct Synthesis: THF, 140ºC, 150 bar H2 (Ashby 1958, Clasen 1961)Principal Use: Chemical Reducing AgentSensitive to air and water exposure reacting strongly with O2 and OH
NaAlH4 melts at 182ºCPCT Desorption Measurements2-step Decomposition
Dymova, T. N., Eliseeva, N. G., Bakum, S. I.,And Dergachev, Y. M., Doklady Akademii
Nauk. SSSR, 215 (6) (1974) 1369
4 3 6 2
3 6 2
1 23 3
3 32
NaAlH Na AlH Al H
Na AlH NaH Al H
↔ + +
↔ + +
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Fundamental Questions
What is the nature of hydrogen bonding and how is it altered by the presence of TiCl3?
What happens to TiCl3?
Where does Ti go? (surface, substitutional, interstitial)
What does it do and how does it do it?
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Hypotheses
TiCl3 + 3Na 3NaCl + Ti
Ti can occupy the Na or Al site on the surface, interstitial, or bulk site.
Ti can combine with Al to form TiAlx.
Vacancies can be created at the Na and/or Al site.
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NaAlHNaAlH44 super cellsuper cell
2x2x1
96 atom
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Total electron density of states of NaAlH4 crystal
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Formation EnergyFormation Energy
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
(a) Intrinsic
(e) Alvac
(d) Navac
(c) Ti→Al
(b) Ti→Na
Form
atio
n en
ergy
(eV
)
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Ti SubstitutionTi Substitution
Intrinsic Ti→Na
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Na vacancyNa vacancy(AlH4)- perfect
Na vacancy –local minimum
Na vacancy –global minimum
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Al vacancyAl vacancyAl vacancy –
global minimumAl vacancy –
local minimum(AlH4)- perfect
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Hydrogen desorption energyHydrogen desorption energy
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
(b) Ti→Na
(d) Navac (e) Alvac
(a) Intrinsic
(c) Ti→Al
H2 d
esor
ptio
n en
ergy
(eV
)
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ConclusionsConclusions
Boron nitride and carbon nanoBoron nitride and carbon nano--cages are not suitablecages are not suitable
Coating these cages with metal atoms may increase the Coating these cages with metal atoms may increase the hydrogen uptakehydrogen uptake
The presence of Na and Al vacancies are more important The presence of Na and Al vacancies are more important than Ti substitution at metal sites: Hydrogen desorption is than Ti substitution at metal sites: Hydrogen desorption is molecular and exothermicmolecular and exothermic
The dominant role of Ti in reducing hydrogen desorption The dominant role of Ti in reducing hydrogen desorption temperature may be an indirect one temperature may be an indirect one -- it leads to vacancy it leads to vacancy formation which in turn reduces hydrogen desorption formation which in turn reduces hydrogen desorption energy. energy.
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November 12 - 15, 2007Richmond, Virginia
International Symposium on Scientific and Technological Issues in a Hydrogen
Economy
http://www.has.vcu.edu/phy/ishe/