A First-Principles Approach to Catalytic H Production and Chemistry
Transcript of A First-Principles Approach to Catalytic H Production and Chemistry
A First-Principles Approach to Catalytic H2 Production and Chemistry:
Reaction Mechanismsand
Identification of Promising Catalysts
Manos Mavrikakis
Department of Chemical and Biological EngineeringUniversity of Wisconsin – Madison
Madison, Wisconsin 53706
Acknowledgements
A. Gokhale, S. Kandoi, L. Grabow, M. Han, D. Ford, A. Unrean
J. Greeley, Y. Xu, A. Nilekar, R. Nabar, P. Ferrin
J. A. Dumesic (UW Madison)
Jens Nørskov and colleagues @ CAMP - Denmark
DoE Catalysis Science Grant (BES-Chemical Sciences)
NSF - CTS
NPACI, DOE-NERSC, PNNL (supercomputing resources)
Outline
• H2 production:– An alternative mechanism for the Low Temperature
Water Gas Shift Reaction
• H2 catalytic chemistry:– Identifying Promising Catalysts from 1st Principles:
H2 and H on Bimetallic Near Surface Alloys (NSAs)
Water Gas Shift Reaction (WGSR)Ovesen, Stoltze, Nørskov, Campbell – J. Cat. 134, 445 (1992)
Ovesen, et.al. – J. Cat. 158, 170 (1996)C.T. Campbell – Studies in SS and Catalysis 38, 783 (1988)
NH3Synthesis
H2 Production
MeOH
Synthesis
CO + H2O CO2+H2 H = - 41 kJ/mol∆
Reaction Mechanisms
Red-ox Mechanism
OH* + * O* + H*OH* + OH* H2O* + O*CO* + O* CO2* + *
Formate Reactions CO2* + H* HCOO**
CO2* + H2O* + * HCOO** +OH*
CO2* + OH* + * HCOO** +O*
Carboxyl MechanismCO* + OH* COOH* + *COOH* + * CO2* + H*COOH* + OH* CO2* + H2O*COOH* + O* CO2* + OH*
CO(g) + * CO*H2O(g) + * H2O*
H* + H* H2(g) + 2*CO2* CO2(g) + *
H2O* + * OH* + H*
MethodsDensity Functional Theory – DACAPO total energy code 1,2
Periodic self-consistent PW91-GGA 3
Ultra-soft Vanderbilt pseudo-potentials 4
Plane wave basis sets with 25-Ry kinetic energy cut-off
Spin polarization as needed
Four-metal-layer slabs; (2x2) unit cell; top two layers relaxed
First Brillouin zone sampled at 18 k-points
Nudged Elastic Band method for reaction paths 5
1. B. Hammer, L. B. Hansen, J. K. Nørskov, Phys. Rev. B 59, 1999, 7413.2. J. Greeley, J. K. Nørskov, M. Mavrikakis, Annu. Rev. Phys. Chem. 53, 2002, 319.3. J. P. Perdew et al., Phys. Rev. B 46, 1992, 6671.4. D. H. Vanderbilt, Phys. Rev. B 41, 1990, 7892.5. G. Henkelman, H. Jónsson, J. Chem. Phys. 113, 2000, 9978.
-5.00
-4.00
-3.00
-2.00
-1.00
0.00
1.00
2.00
3.00
Ene
rgy
(eV
)
CO(a)+2H2O(a)
CO(a)+2H(a)+2OH(a)
CO(a)+ 2H(a) +O(a) +H2O(a)
CO2(a)+2H(a)+ H2O(g)
Thermochemistry of WGS on TM(111)Redox Mechanism
Complete Dissociation : OH* +* O* + H*
CO(g)+2H2O(g)
CO(a)+2H2O(g)
Ru
Ni
RhIr
PdPtCu
Ag
AuDisproportionation : OH* + OH* H2O* + O*
Co
CO2(g)+H2(g)+H2O(a)CO2(a)+H2(g)
+H2O(a)
-2.00
-1.50
-1.00
-0.50
0.00
0.50
1.00
-1.00
CO2(a)+2H(a) +H2O(a)
CO(g)+2H2O(g)
CO(a)+2H2O(g)
CO(a)+2H2O(a)
H--OH(TS)1.36
CO(a) + H(a)+ OH(a)+H2O(a)
CO2(g)+ H2(g)+H2O(g)
CO(a)+ O(a) +2H(a)+ H2O(a)
CO2(a)+ H2(g)+H2O(a)
H--O (TS)1.76
H--H(TS)1.07
CO--O(TS)
0.82
Ener
gy (e
V)
PES for Water Gas Shift Reaction on Cu(111)
OH DissociationOH+OH MechanismCOOH MechanismCOOH+OH Mechanism
CO2(a)+2H(a) +H2O(a)
CO(g)+2H2O(g)
CO(a)+2H2O(g)
CO(a)+2H2O(a)
H--OH(TS)1.36
CO(a) + 2H(a)+ 2OH(a)
CO2(g)+ H2(g)+H2O(g)
CO(a)+ O(a) +2H(a)+ H2O(a)
CO2(a)+ H2(g)+H2O(a)
OH--OH (TS)0.23
H--H(TS)1.07
CO--O(TS)
0.82
COOH(a) +H2O(a)+H(a)
CO2(g)+2H(a) +H2O(a)
CO(g)+2H2O(g)
CO(a)+2H2O(g)
CO(a)+2H2O(a)
H--OH(TS)1.36
CO(a) + OH(a) + H(a) + H2O(a)
CO2(g)+ H2(g)+H2O(g)
CO2(g)+ H2(g)+H2O(a)
CO--OH (TS)0.61
H--H(TS)1.07
COO--H (TS) 1.41
COOH(a)+ OH(a) +2H(a)
CO2(a)+2H(a) +H2O(a)
CO(g)+2H2O(g)
CO(a)+2H2O(g)
CO(a)+2H2O(a)
H--OH(TS)1.36
CO(a) + 2H(a)+ 2OH(a)
CO2(g)+ H2(g)+H2O(g)
CO2(a)+ H2(g)+H2O(a)
CO--OH (TS)0.61
H--H(TS)1.07
COOH--OH(TS)
0.42
//
H2O Dissociation on Cu(111)
//
Carboxyl Formation on Cu(111)
COOH + OH reaction on Cu(111)
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WGSR/Cu Mechanism:Key points
• WGSR mainly proceeds via COOH intermediate, which decomposes via the COOH+OH reaction.
• H2O Activation is the RCS.
• Formate, a stable spectator species, is formed from CO2* and H*. Formate formation is equilibrated with CO2and H*.
• The combination of DFT and Microkinetics shows that we can fairly accurately predict experimental WGSR rates directly from First Principles.
Ideal Bimetallic Near Surface Alloys • Segregation properties of two metals are
critical• Consider two special classes:
– Overlayers– Subsurface Alloys
Overlayers* Subsurface Alloys
1. J. Kitchen, N. Khan, M. Barteau, J. Chen, B.
Yashhinskiy, and T. Madey, Surf. Sci. 544 (2003) 295
1Ni/Pt(111)
H2/Rh(111)
2. R. Schennach, G. Krenn, B. Klötzer, K. Rendulic, Surf. Sci. 540 (2003) 237
Hydrogen on NSA’s
2V/Rh(111 )
-
-
Eseg
Pt subsurface alloys
Pd subsurface alloys
Ir subsurface alloys
Ru subsurface alloys
Rh subsurface alloys
Re based overlayers
Ru based overlayers
H-induced segregation
-1.25 -1.00 -0.75 -0.50 -0.25 0.00 0.25 0.50 0.75 1.00 1.25
-1.25
-1.00
-0.75
-0.50
-0.25
0.00
0.25
0.50
0.75
1.00
1.25
|B.E
. Hhost
|Hso
l-|
B.E
.
|
Stability of NSA’s with respect to Hydrogen-induced Segregation
-
-
CoFe Ru Pd CuW IrNi
PtMoReTa Rh AuV
B.E.H (eV)-3.2 -3.1 -3.0 -2.9 -2.8 -2.7 -2.6 -2.5 -2.4 -2.3 -2.2-3.3
H Binding Energy Spectrum
Rh subsurfacealloys
Ru based overlayers
Re based overlayers
ThermoneutralH2 Dissociation
Pt subsurface alloys*
*Cu,Ir,Rh,Ni,Ru,Re,Co,Fe,W,Mo,V,Ta
Pd subsurfacealloys†
†Ir,Ru,Re,Fe,Mo,W,V,Ta
Overlayers Subsurface Alloys
Correlation of B.E.H with Clean Surface Properties
d ε (eV)
-3.4 -3.2 -3.0 -2.8 -2.6 -2.4 -2.2 -2.0
B.E
. H(e
V)
-3.2
-3.0
-2.8
-2.6
-2.4
-2.2
-2.0
-1.8
Pt subsurface alloysPd subsurface alloys
Rh subsurface alloys
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
-6.0 -5.0 -4.0 -3.0 -2.0 -1.0 0.0
EbFS (eV, PW91)
Eb
TS (e
V, P
W91
)
O2 dissociation: Does EbTS follow Eb
FS?
Pt
Cu
Ir
Ag
Au +10%
Pt3Co
Pt3Co skin
Pt -2%
Pt3Fe
Pt3Fe skin
Y. Xu, A. V. Ruban, M. Mavrikakis, JACS 126, 4717 (2004).
Hydrogen B.E. (eV)
- 0.3 - 0.2 - 0.1 0.0 0.1 0.2
ETS
(eV
)
- 0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Au
Cu
Noble metals
V/Pd
Pd*/Re
Re/Pd
Ta/PdPd-terminated alloys
Ta/Pt
Mo/Pt
Re/Pt
Ru/PtPt-terminated alloys
BEP Plot for H2 Dissociation on NSA’sJ. Greeley, M. Mavrikakis, Nature Materials 3, 810 (2004)
---------------
Metal or Alloy
Sur
face
-Sub
surfa
ce
Ther
moc
hem
ical
Bar
rier (
eV)
0.0
0.2
0.4
0.6
0.8
1.0
Pt
Ir/P
t
Ru/
Pt
Rh/
Pt
Fe/P
t
Mo/
Pt
Co/
Pt
Cu/
Pt
Ni/P
t
Pd
Ta/P
d
V/P
d
-----
-----
Surface to Subsurface Diffusion of HThermochemical Barrier
J. Greeley, M. Mavrikakis, J. Phys. Chem. B 109, 3460 (2005)
Pt2+
Pd Pd
CuUPD/Pd + Pt 2+ Pt/Pd + Cu2+
Cu2+
Cu Pt
Pt
Ru
Pt
Ru
Metal monolayer deposition by galvanic displacement of a less noble
metal monolayer deposited at underpotentials
Electroless (spontaneous) deposition of one metal on
another metal
Brankovic, S. R.; Wang, J. X.; Adzic, R. R. Surf. Sci. 2001, 474, L173
Brankovic, S. R.; McBreen, J.; Adzic, R. R. J. Electroanal. Chem. 2001, 503, 99
Sasaki, K.; Wang, J. X.; Balasubramanian, M.; McBreen, J.; Uribe, F.; Adzic, R. R. Electrochim. Acta 2004, 49, 3873
Zhang, J.; Vukmirovic, M.; Xu, Y.; Mavrikakis, M.; Adzic, R. R. Angew. Chem. Int. Ed. (in press).
NSA’s - Summary• First-Principles Methods can help with identifying promising
bimetallic NSAs with interesting catalytic properties
• Example: 1. H and H2 on NSA’s: Fine-tuning BEH is possible2. Some NSA’s:
2.1. Activate H2 easily AND bind atomic H weakly useful for highly selective low TH-transfer reactions2.2. Allow easy H diffusion into the bulk (catalysis of H-storage)
• Developing Catalyst Preparation Techniques with Layer-by-Layer control of metal deposition (ALD-like) is critical for making the desired NSAs
Lars GrabowShampa Kandoi
University of Wisconsin-Madison
Department of Chemical and Biological Engineering
Amit Gokhale
Dr. Ye XuDr. Jeff Greeley
Acknowledgements
A. Gokhale, S. Kandoi, L. Grabow, M. Han, D. Ford, A. Unrean
J. Greeley, Y. Xu, A. Nilekar, R. Nabar, P. Ferrin
J. A. Dumesic (UW Madison)
Jens Nørskov and colleagues @ CAMP - Denmark
DoE Catalysis Science Grant (BES-Chemical Sciences)
NSF - CTS
NPACI, DOE-NERSC, PNNL (supercomputing resources)