Reusable Nickel -Based Materials for Small Scale Ammonia Storage · 2012-05-22 · Reusable Nickel...
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Reusable NickelReusable Nickel--Based Based
Materials for Small Materials for Small
Scale Ammonia StorageScale Ammonia StoragePatrick J. DesrochersPatrick J. Desrochers
Dept. of Chemistry, University of Central Arkansas, Conway, AR [email protected]
AFV, Minneapolis, MN Sep 2008
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• Global energy gases—ammonia in context
• Tp*NiX(s) binding of ammonia
• Advantages of the organic anchorage
• Tp*NiBH4: ammine-borane hybrid
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yearreproduced from S. Dunn International Journal of Hydrogen Energy 2002, v. 27, p 235.
Gases
LiquidsIncreasinglySustainableEconomic GrowthDecentralized less capital-intensivetechnologies
Non-SustainableEconomic GrowthCentralized capital-intensivetechnologies
Solids
Global transition to energy gases Global transition to energy gases
Ammonia
1850 1900 1950 2000 2050 2100 2150
0
20
40
60
80
100
Oil and naturalgas liquids
Methane
Hydrogen
Wood and hay
Methane
Coaland Nuclear
PetroleumOil
OilandHydro
“City Gas”Hydrogen
Whale oil
perc
enta
ge o
f to
tal m
ark
et
1997
Actual Consumption
H:C 0.5:1coal 2:1oil 4:1NG �:1NH3,H
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The Chronicle of Higher Education Oct 10, 2003.
Thepromise of a hydrogeneconomy
Gasoline 48
Methane 56
Lithium 42
Hydrogen 143
Fuel ∆Hocomb,kJ/g
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Thechallenge of a hydrogeneconomy
• amides M(NH2)n
• boranes BH3NH3
• ammines M(NH3)nXm
storage
The Chronicle of Higher Education Oct 10, 2003.
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Orimo, S.; Nakamori, Y.; Eliseo, J. R.; Z�ttel, A.;Jensen, C. M. Chem. Rev. 2007, 107, 4111.
Amides Amides
• Mixed amide/hydrideimproved desorption T
• Variable compositions provide tunable control
• T(H2) formation < T(NH3)
Mg(NH2)2 + nLiH Mg3N2 + LixNHy + nH2
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N O F NeB C
He
P S Cl ArAl Si
AmmineAmmine--boraneborane
ethane(g)
C C
H
HH
H
H
HC C
H
HH
H
H
H
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N O F NeB C
He
P S Cl ArAl Si
AmmineAmmine--boraneborane
ammine-borane(s)
B N
H
HH
H
H
HB N
H
HH
H
H
H+
-
+
-
THFNaBH4 + NH4Cl H2 + BH3NH3 + NaCl
Ramachandran, P. V.; Gagare, P. D. Inorg. Chem. 2007, 46, 7810-7817.
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Mg(BH4)2(NH3)2(s)
Soloveichik, G.; Her, J. –H.; Stephens, P. W.; Gao, Y.; Rijssenbeek, J.; Andrus, M.; Zhao, J. -C.Inorg. Chem. 2008, 47, 4290-4298.
original report: Konoplev, V. N.; Silina, T. A. Zh. Neorg. Khim. 1985, 30 (5), 1125.
m.p. 94 oC
Mg
NH3
NH3
H
BH H
H
H
BH H
H
AmmineAmmine--boraneborane hybrids hybrids
• N-H…H and B-H…H parameters comparable to BH3NH3(s)• endothermic H2/NH3 release vs BH3NH3(s)
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“Metal Derivatives of Ammonia-borane: Potential hydrogen storage materials”
Diyabalanage, H. V. K.; Shrestha, R. L.; Semelsberger, T. A.; Scott, B. L.; Burrell, A. K. 236th ACS Natl. Mtg, Philadelphia, August 2008: FUEL 56.
AmmineAmmine--boraneborane hybrids hybrids
M(NH2BH3)n (M = Ca, Mg, Ti, Sc; n = 1-6)
• variable thermal properties• H2 without foaming• thermal stability improvement • controlled H2 release
Fuel DivisionInorganic Division
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Carl Bosch
(shared with Friedrich Bergius)
1931Fritz Haber
1918
HaberHaber--Bosch: Nobel worthy chemistry Bosch: Nobel worthy chemistry
motivated by national security interests
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motivated by national security interests
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Ammines Ammines
Sørensen, R. Z.; Hummelshøj, J. S.; Klerke, A.; Reves, J. B.; Vegge, T.; Nørskov, J. K.Christensen, C. H. J. Am. Chem. Soc. 2008, 130, 8660–8668.Christensen, C. H.; Sørensen, R. Z.; Johannessen, T. ; Quaade, U. J.; Honkala, K.; Elmøe, T. D.; Køhler, R.; Nørskov, J. K. J. Mater. Chem., 2005, 15, 4106 – 4108.
Ca(NH3)8Cl2 9.8 0.116Mn(NH3)6Cl2 8.0 0.112Mg(NH3)6Cl2 9.2 0.115Ni(NH3)6Cl2 7.8 0.119
mass% H kg H/L
M
H3N
H3N NH3
NH3
H3N
NH3
X
X
incre
asin
g T
des
• ρpellet 95 – 99% of crystalline• nanopores facilitate NH3 transport• heat transport controls NH3 loss
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• Global energy gases—ammonia in context
• Tp*NiX(s) binding of ammonia
• Advantages of the organic anchorage
• Tp*NiBH4: ammine-borane hybrid
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X
Cl - 490Br - 500I - 520
Tp*Tp*NiXNiX and ammonia and ammonia
λmax (nm)
NN
NNB
NN
H
Ni
X
Desrochers, P. J.; Telser, J.; Zvyagin, S. A.;Ozarowski, A.; Krzystek, J.; Vicic, D. A.Inorg. Chem. 2006, 45, 8930-8941.
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Form of bound ammonia independent of X Form of bound ammonia independent of X
light absorptionmaxima
380 nm570
similar to Ni(NH3)6X2NN
NNB
NN
H
Ni
X
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Form of bound ammonia independent of X Form of bound ammonia independent of X
NN
NNB
NN
H
Ni
X
NN
NNB
N
N
H
Ni NH3
NH3
NH3
+ -X
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NN
NNB
N
N
H
Ni NH3
NH3
NH3
Form of bound ammonia independent of X Form of bound ammonia independent of X
+ -X
300 400 500 600 700 800 900
wavelength (nm)
Cl
Br
I
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0
0.1
0.2
0.3
0.4
300 400 500 600 700 800 900
wavelength (nm)
Largest optical absorption change with iodideLargest optical absorption change with iodide
Tp*NiI
NH3 form
absorb
ance
Tp*Ni(NH3)3I(s) Tp*NiI(s) + 3NH3(g)
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9.6 %
11.5 %
theory
Tp*Ni(NH3)3X(s) Tp*NiX(s) + 3NH3(g)
Cl
I
Quantitative ammonia uptake/release by Tp*Quantitative ammonia uptake/release by Tp*NiXNiX
0
2
4
6
8
10
12
280 300 320 340 360 380
temperature (K)
perc
en
t m
ass l
oss
1 K/min
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0
10
20
30
40
50
300 350 400 450 500 550 600 650
temperature (K)
perc
en
t m
ass l
oss
Compare to [Ni(NHCompare to [Ni(NH33))66]Cl]Cl22
44.0 %
[Ni(NH3)3Cl2]
NiCl2
5 K/min
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NH3
NH3
Halide typically along 3-fold axis of metal-ammines.Hwang, I. –C.; Drews, T.; Seppelt, K. J. Am. Chem. Soc. 2000, 122, 8486.Scheibel, P.; Prandl, W.; Papoular, R.; Paulus, W. Acta Cryst 1996 A52, 189.
3 fold symmetry
Halogen control may follow three fold axisHalogen control may follow three fold axis
NH3
NN
NN
B
NN
H
Ni
X
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NH3
3 fold symmetry
Halogen control may follow three fold axisHalogen control may follow three fold axis
NH3
NH3
NN
NN
B
NN
H
Ni
X
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NH3
NH3
NH3 NH3
NH3
NH3
NH3
NH3
NH3
crystalline Tp*NiX[Tp*Ni(NH3)3+][X-] ?
Directional expansion with ammonia uptake Directional expansion with ammonia uptake
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Tp*NiCl
Tp*NiBr
2θ
λ = 1.541 �
IsostructuralIsostructural solids solids
powder patterns simulated using Mercury v1.4.1 CCDC
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Tp*Ni(NH3)3X(s) Tp*NiX(s) + 3NH3(g)
∆H – T∆S = -RTlnK
Energetics of ammonia loss Energetics of ammonia loss
enthalpy (∆H): Ni-NH3 bond strengthNi-X bond strengthLattice alterations
entropy (∆S): mostly 3NH3(g)3(192 J/K) = 576 J/K
for Cl form ∆H = 190 kJ/mol
PNH3 ~ 0.1 bar @ 300 K
∆S ~ 576 J/K
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Affinity for nitrogen substrates Affinity for nitrogen substrates
TpRCoI + 3NCMeTpRCo(NCMe)3+I�
Reinaud, O. M.; Rheingold, A. L.; Theopold, K. H. Inorg. Chem. 1994, 33, 2306-2308.TpR = TpiPrMe (in chloroform solution)
K = 45 (-22 oC)4x104 ( 27)
enthalpy (∆H = 87 kJ): Co-NCMe bond strengthCo-I bond strength
entropy (∆S = 377 J/K): mostly 3NCMe3(151 J/K) = 453 J/K
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NN
NNB
NN
H
Ni NCCH3
iPr
iPr
iPr
iPr
iPr
iPr
NCCH3
NCCH3
OTf
Uehara, K.; Hikichi, S.; Akita, M. J. Chem. Soc., Dalton Trans. 2002, 3529.
Metals with high affinity for nitrogen substrates Metals with high affinity for nitrogen substrates
Stabilize anchored-nickel in a pliable environment.
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Co Ni Cu
PdRh Ag
Zn
Cd
Fe
Ru
PtIr Au HgOs
Metals with high affinity for nitrogen substrates Metals with high affinity for nitrogen substrates
cobalt nickel copper zinc
• numerous transition elements with NH3 affinity• could combine storage, decomp. catalyst• variable magnetic and optical properties
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• Global energy gases—ammonia in context
• Tp*NiX(s) binding of ammonia
• Advantages of the organic anchorage
• Tp*NiBH4: ammine-borane hybrid
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• bulk solid: distinct ammonia uptake
• phys-isorbed:1) silica thin-layer
bulk powder2) cellulose fiber
• chemically attached: tunable ancillary ligandreduce nickel leaching
Solid supports for Tp*Solid supports for Tp*NiXNiX
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Si
Si
O
Si
Si
O
Si
O
O
H
OO
O O
Si O
N N
N N
B N NH Ni
NH3
NH3
NH3
-
- -+-+
+
Silica supports for Tp*Silica supports for Tp*NiXNiX
silica
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O
H
N N
N N
B N NH Ni
NH3
NH3
NH3
HC
cellulose
CH2 O
H
Cellulose supports for Tp*Cellulose supports for Tp*NiXNiX
--- -
+
++
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N
N
NNB
NN
H
Ni
X
Cl Br I
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Tp*NiBr on silica
Optical Monitoring of Ammonia Uptake Optical Monitoring of Ammonia Uptake
NH3 flow
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0
10
20
30
40
50
60
70
80
90
100
0 20 40 60 80 100 120 140 160 180
time (sec)
% i
nti
al
Ab
s
64% NH3
36147
NH3 at 12 mL/min, 25 oCsensor reset: 80 oC, 3 min, pure N2
Ammonia uptake by Tp*Ammonia uptake by Tp*NiNiII
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0
0.1
0.2
0.3
0.4
300 400 500 600 700 800 900
wavelength (nm)
Largest optical absorption change with iodideLargest optical absorption change with iodide
Tp*NiI
NH3 form
absorb
ance
Tp*Ni(NH3)3I(s) Tp*NiI(s) + 3NH3(g)
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N N
N N
C N NCH2Ni
NH3
NH3
NH3
po
lysty
ren
e
Potential covalent supports for Tp*Potential covalent supports for Tp*NiXNiX
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• Global energy gases—ammonia in context
• Tp*NiX(s) binding of ammonia
• Advantages of the organic anchorage
• Tp*NiBH4: ammine-borane hybrid
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AmmineAmmine--boraneborane and and NiNiPtPt
Cheng, F.; Ma, H.; Li, Y.; Chen, J. Inorg. Chem. 2007, 46, 788-794.
small % Pt in Ni catalyzes rapidhydrolysis
NH3BH3 + H2O NH4+ + BO2
- + 3H2
NiPt
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A stable borohydride A stable borohydride
Tp* anchorage tempers reducing power of H-rich substrates
• inert to hot water
• stable in air
0
20
40
60
80
100
0 50 100 150 200 250time (sec)
% B
H4-
rem
ain
ing
1098
7.46
pH
Davis, R. E.; Bromels, E.; Kibby, C. L. J. Am. Chem. Soc. 1962, 84, 885.
Contrasts hydrolysis of MBH4
Desrochers, P. J.; LeLievre, S.; Johnson, R. J.; Lamb, B. T.; Phelps, A. L.; Cordes, A. W.;Gu, W.; Cramer, S. P. Inorg. Chem. 2003, 42, 7945.
N
N
N
N
B
N
N
H
Ni
HH H
B
H
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FE
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
covalent anchorage
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FE
Ni Ni Ni Ni
covalent anchorage
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FE
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
covalent anchorage
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FE
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
covalent anchorage
NH3H3NNH3 NH3H3N
NH3 NH3H3NNH3 NH3H3N
NH3
Mg(NH3)6Cl2Mg(NH3)6(BH4)2
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● Tp*NiX(s) binds ammoniareversible, quantitative 3NH3:1NiX-dependent uptake, release; 3-fold axis controlcolorimetric, magnetic signals, sensor potential
● Organic anchorage advantageslowers ammonia release Tsynthetically modifiable for specialized applications
● Tp*NiBH4 stable H-rich substrateimplications for ammonia-only reactionspotential NH3BH3 interactions
Acknowledgements:Kristin Thorvilson, Chris Sutton, Josh Brown
Prof. R. Tarkka (UCA)
Prof. A. Biris (UA, Little Rock)Ms. E. Dervishi (UA, Little Rock)
$$ Petroleum Research Fund (Am. Chem. Soc.),Natl. Sci. Foundation, UCA Research Council