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 72035patrickd@uca.edu
AFV, Minneapolis, MN Sep 2008
• Global energy gases—ammonia in context
• Tp*NiX(s) binding of ammonia
• Advantages of the organic anchorage
• Tp*NiBH4: ammine-borane hybrid
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
The Chronicle of Higher Education Oct 10, 2003.
Thepromise of a hydrogeneconomy
Gasoline 48
Methane 56
Lithium 42
Hydrogen 143
Fuel ∆Hocomb,kJ/g
Thechallenge of a hydrogeneconomy
• amides M(NH2)n
• boranes BH3NH3
• ammines M(NH3)nXm
storage
The Chronicle of Higher Education Oct 10, 2003.
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
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
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.
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)
“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
Carl Bosch
(shared with Friedrich Bergius)
1931Fritz Haber
1918
HaberHaber--Bosch: Nobel worthy chemistry Bosch: Nobel worthy chemistry
motivated by national security interests
motivated by national security interests
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
• Global energy gases—ammonia in context
• Tp*NiX(s) binding of ammonia
• Advantages of the organic anchorage
• Tp*NiBH4: ammine-borane hybrid
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.
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
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
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
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)
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
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
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
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
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
Tp*NiCl
Tp*NiBr
2θ
λ = 1.541 �
IsostructuralIsostructural solids solids
powder patterns simulated using Mercury v1.4.1 CCDC
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
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
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.
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
• Global energy gases—ammonia in context
• Tp*NiX(s) binding of ammonia
• Advantages of the organic anchorage
• Tp*NiBH4: ammine-borane hybrid
• 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
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
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
--- -
+
++
N
N
NNB
NN
H
Ni
X
Cl Br I
Tp*NiBr on silica
Optical Monitoring of Ammonia Uptake Optical Monitoring of Ammonia Uptake
NH3 flow
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
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)
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
• Global energy gases—ammonia in context
• Tp*NiX(s) binding of ammonia
• Advantages of the organic anchorage
• Tp*NiBH4: ammine-borane hybrid
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
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
FE
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
covalent anchorage
FE
Ni Ni Ni Ni
covalent anchorage
FE
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
Ni
HHH
H
B
covalent anchorage
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
● 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
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