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FUNDAMENTAL UNDERSTANDINGOF SELECTIVE HYDROGENATIONS
Núria López
Hydrogenations: at the basis of catalysis
Activity is important but SELECTIVITY is mandatory
Tools
What can we do?
ATOMISTIC
ENGINEERING
THERMODYNAMICS
Predict structure solids
Thermodynamics of processesMost-likely configurations under rx
Reaction pathsKinetics processes
Most-likely configurations under rx
Store and search for dataIdentify structure-activity correlations
Assess stabilityIn-silico Design systems with specific properties
KINETICS
Gold chemistry and hydrogenation
353 K0.2 wt.% Pd/Al2O3
X
S
X(C3H4)
S(C3H6)
C3H4:H2:He = 5:15:80
J. Catal. 247, 383 (2007)
0.49
0.63
General descriptor thermodynamic selectivity
F. Studt, F. Abild-Pedersen, T. Bligaard, R. Z. Sørensen,C. H. Christensen, J. K. NørskovScience , 320 1320(2008)
Industrial problem: Alkyne hydrogenation
Cracking reactions
Fuelgas
SteamCracking
or otherOlefin
Sources
Hydrogen
Selective Hydrogenation
Selective Hydrogenation
C2
C3
Dimerization
Oligomerization
Metathesis
1-Butene
Alpha-olefins
Ethene
Propene
2-Butenes
over-hydrogenation oligomerisation
Pd (0.04%)/ δ-Al2O3
T 350 Kp 20 bar
CO feeding (50-500 ppm)Salkenes
Hydrogenations: the problem
Hydrogenation: Reaction mechanism
Horiuti, J. and Polanyi, M. , Trans. Faraday Soc. 30, 1164 (1934)
Alkyne hydrogenation: Pd catalyst
Pd (0.04%)/ Al2O3 Experimental evidence
Salkenes
Pretreatment
State of Pd
Self-consistently analyze composition activity
X, Salkenes
pH2
pCO
pC2H2
Hydride formation
pH2
Greeley, et al. ACIE, 43, 4296 (2004)
-Hydride phase formation: BET equivalence
•The adsorption takes place on a lattice •First adsorbate layer is adsorbed on the solid surface•Second adsorbate layer is adsorbed on the first •Adsorption enthalpy first layer and then for other layers
pH2
Upt
ake
1
Hydride formation
Pd hydride
E ads -0.5 eV/atom1 ML
E ads -0.1 eV/atom
Pretreatment and State of Pd
pH2
Carbide formation
Pretreatment State of Pd
carbide
p alkynes
Teschner et al. Science 320, 86 (2008) Teschner, Sautet, ACIE (2008)
Carbide formation
Pretreatment and State of Pd
carbide
p alkynes
2.12 vs. 1.69
Dehydrogenations are lower in energyC-C splitting lower at steps
Andersin, et al. JPCC 113, 8278 (2009); Surf. Sci. 604, 762 (2010)
<1.5 eV
Carbide formation
0.8-1.0 eVCCC
Pretreatment and State of Pd
carbide
p alkynes
•Lateral repulsion between C atoms is very large no dense phases PdC0.13•Preferential decoration of corners and steps, due to high formation energies at surfaces•Near surface carbides, mostly•Ability to be formed depends on the alkyne-alkene pair
García-Mota, et al. J. Catal. 273, 92 (2010)
Hydride formation in the presence of carbide
carbide
palkynes
Hydride formation
1ML
Carbide prevents
hydride formation
Pretreatment and State of Pd
Alkyne hydrogenation: Pd catalyst
Industrial conditionsPd (0.04%)/ δ-Al2O3
T 350 Kp 20 bar
continuous CO feeding (50 < CO < 500 ppm)
CO covered Pd surface
p CO
Pretreatment and State of Pd
Hydride formation
Very dense layers
E ads -1.43 eV/atom
( p(2x2)-3CO ) CO prevents
hydride formation
Role of CO: hydride formation
Reaction paths and kinetic contributions
Horiuti, J. and Polanyi, M. , Trans. Faraday Soc. 30, 1164 (1934)
Kinetics pure Pd(111)
ethyne
vinyl
ethyl
ethylidene
ethane
ethene
Edes0.82 eV
Pd clean surface
Eads-2.02 eV
0.66
0.81 0.79
0.74 0.79
0.45
ts ts
0.81 0.79
50% 50%
vinyl
ethene ethylidene
ethyne
vinyl
ethyl
ethylidene
ethane
ethene
Edes0.15eV
Experimental evidence
p H2 pretreatmentEads‐0.94eV p = 1 bar
T = 348K
Pd /γ-Al2O3
Pd hydride
Kinetics -PdH
ethyne
vinyl
ethyl
ethylidene
ethane
ethene
Edes0.15 eV
0.58
0.36 0.06
0.75
PdH inducesEads
-0.94 eVPd hydride
Kinetics b-PdH
Experimental evidence
p H2 pretreatment
ethyne
vinyl
ethyl
ethylidene
ethane
ethene
Edes0.67 eV
0.70
0.57 0.69
0.89 0.57
Carbide
Carbide inducesEads
-1.49 eV
Kinetics Carbide phase
Experimental evidencep H2 pC2H2pretreatment
ethyne
vinyl
ethyl
ethylidene
ethane
ethene
Edes0.00eV
0.45
0.14 0.23
0.44 0.57
0.20
Eads‐1.24eV
Kinetics CO phase
CO covered
ethyne
vinyl
ethyl
ethylidene
ethane
ethene
Edes0.00 eV
0.45
0.14 0.23
0.44 0.57
CO covered
0.20
p C2H2 p H2
CO inducesEads
-1.24 eVp CO
p CO
Experimental evidencepretreatment
Kinetics CO phase
Oligomerization
Ea =1.38 eVEa(+CO) =1.40 eV
Reduction of ensembles
Oligomerization
Ea =1.38 eVEa(+CO) =1.40 eV
Reduction of ensembles
X
1. Thermodynamic selectivity Blocks subsequent reactions2. No active subsurface species Blocks overhydrogenation3. Small ensembles Reduces oligomerization
Requirements for a good hydrogenation catalyst
Carbide:Fulfills (1-3)LabileDifficult homogeneously
García-Mota, et al. J. Catal. 273, 92 (2010)
Hydride:Fulfills (1) and (3)
CO phase:Fulfills (1-3)RobustEasily homogeneousOverwrites the state of the catalyst
Hydrogenations: Technical solution
Molecular Modifier
Secondary metal
Active metal
Role of co-catalyst
Lopez, Vargas-Fuentes Chem. Comm.48, 1379 (2012)
Complex substrates on Pd
Bridier et al. ChemCatChem 4, 1420 (2012)
1. Thermodynamic selectivity2. Inability to form active subsurface
species3. Definition of small ensembles
Organic synthesis: Pd Lindlar Catalyst (1952)
Selective for MultifunctionalizedAcetylenic molecules (Solvent)
Vitamin A (Retinol)
BaSO4 +Pd Pd/BaSO4 +Pb(AcO)295ºC
Pb-Pd/BaSO4+
Lindlar Catalyst
N
Comparison between Pd catalysts
Hydrorefining Catalyst Lindlar Catalyst
Substrate Ethyne, propyne Long chain alkynes
Medium Gas phase or liquid phase Liquid phase
Pd content 0.01 – 0.05 % 1 – 5 %Second metal Ag, Au, etc. Pb, Bi, Cu
Selectivity modifier CO Quinoline
Support Al2O3 CaCO3, BaSO4
Temperature RT – 350 K RT
Solvent None Benzene, Toluene, Methanol
Regioselectivity --- Cis
PH2 Up to 20 bar 1 – 10 bar
Operation Continuous Batch
Lindlar preparation: I
Lindlar preparation: II
Pb(AcO)2 95ºC
Eisl
Formation of Pb islands
Unfavourable
Lindlar preparation: III
N
Santarosa, Iannuzzi, Vargas, Baiker, ChemPhysChem 9, 401 (2008)
Lindlar Tiling
Jujol, Gaudi 1906
Lindlar Tiling
Thermodynamic selectivity Blocks subsequent reactions
Lindlar Tiling
Inability to form hydride Achieved by tiles (solvent)
Lindlar Tiling
Definition of small ensembles Reduces oligomerization
Garcia-Mota et al. TCA 128, 663 (2011)
New generation catalyst: supported colloids
Witte, Patent NL50039, 2009 Witte et al., ChemCatChem 5, 582 (2013)
▶ Conventional technique
Difficult to scale up Low-boiling point compounds Centrifugation required
Preparation of ligand-modified catalysts
Easy to scale up No centrifugation required Versatile
metalprecursor H2O solvent NaBH4PVP
metalprecursor H2O
carrier(C, TiSi2O6)
HHDMA
▶ NanoSelectTM technology
The structure: TEM
Comparison between Pd catalystsHydrorefining
Catalyst NanoSelectTM Lindlar Catalyst
Substrate Ethyne, propyne Terminal alkynes Long chain alkynes
Medium Gas phase or liquid phase Liquid phase Liquid phase
Pd content 0.01–0.05 % 0.1-0.5% 1 – 5 %Second metal Ag, Au, etc. Pb, Bi, Cu
Selectivity modifier CO HHDMA Quinoline
Support Al2O3 TiS CaCO3, BaSO4
Temperature RT – 350 K RT RT
Solvent NoneBenzene, Toluene Benzene, Toluene,
Methanol
PH2 Up to 20 bar 1 – 10 bar 1 – 10 bar
Operation Continuous Continuous Batch
State-of-the-art alkyne hydrogenation catalyst BASF
Lindlar, Helv. Chim. Acta 1952, 35, 446 Blaser et al., ChemCatChem 2009, 1, 210
Pb
ensemble
selective unselective
Pd, Pt
▶ Lindlar Drawbacks: Poor metal utilization Lead as a modifier
C20
tail
PO4
met
al
500 700 900
Wei
ght l
oss /
%
T / K
0
10
500 600 700
200 220 240
Inte
nsity
/ a.
u.
m/e / -
ToF-SIMS
31P MAS NMRCryo-TEM
TGA
metal-O-P
50 nm-100 0 100
Inte
nsity
/ a.
u.
/ ppm
-PO4
Structure of the ligand-modified catalyst
The interface structure
0 5 10 15 200
20
40
60
80
100Fr
eque
ncy
/ %
dPd / nm0 5 10 15 20
0
20
40
60
80
100
Freq
uenc
y / %
dPt / nm
0 5 10 15 200
20
40
60
80
100
Freq
uenc
y / %
dPt / nm0 5 10 15 20
0
20
40
60
80
100
Freq
uenc
y / %
dPd / nm
palladium platinum
D = 6%
D = 17%
D = 8%
D = 49%231 m2 g–1 234 m2 g–1
4 m2 g–110 m2 g–1
10 nm
Chem. Eur. J. 2014, 20, 5926 ACS Catal. 2015, 5, 3767
Textural and compositional characterization
5 wt.% Pd or Pt1-4 wt.% Pb/CaCO3
0.5 wt.% Pd or PtHHDMA/C
0 20 40 60 80 10080
90
100
S(C
6H12
)/ %
X(C6H10) / %
Wcat = 0.1 g, T = 30°C, P = 1 barF(H2) = 18-36 cm3 min-1
F(C6H10+solv.) = 0.3-3 cm3 min-1
alkyne
t = 0 ps t = 0.5 ps t = 1 ps
▶ 1-hexyne hydrogenation
Pd-HHDMA in alkyne hydrogenation
Chem. Eur. J. 20, 5926 (2014)
Pd-PbPd-HHDMA Pd Eads(C2H2) = -1.6 eVEads(C2H4) = -1.2 eV
Eads(C2H2) = -0.8 eVEads(C2H4) = -0.2 eV
Eads(C2H2) = -0.9 eVEads(C2H4) = -0.4 eV
Pd-Pb
Pd-HHDMA
▶ Classical MD simulations
▶ DFT calculations over Pd(111)
-4
-3
-2
-1
0
1
Reaction coordinate
E /
eV
Pt-HHDMA in nitroarene hydrogenation
Facile -NO2 adsorption and H2 activation enhance the activity of Pt-HHDMA
ACS Catal. 2015, 5, 3767
reactant product
Pt-Pb
Pt-HHDMA
Pt-HHDMA Pt-Pb
4
5
TOF(4-chloronitrobenzene hydrogenation) / 103 h-1
1
23
45
Wcat = 0.1 g, F(H2) = 18 cm3 min-1, F(C6H10+solv.) = 0.3 cm3 min-1
All strategies are based on
Large amount of Pd
Poisoned in some way
Is it possible to use the minimum ensemble without poisoning
mpg-C3N4 support
G. Vilé, D. Albani, M. Nachtegaal, Z. Chen, D. Dontsova, M. Antonietti, N. López, J. Pérez-RamírezAngew. Chem., Int. Ed. 2015, doi: 10.1002/anie.201505073R1
Single site hydrogenation catalyst
G. Vilé, D. Albani, M. Nachtegaal, Z. Chen, D. Dontsova, M. Antonietti, N. López, J. Pérez-RamírezAngew. Chem., Int. Ed. 2015, doi: 10.1002/anie.201505073R1
Active 1-hexyne
Selective
Stable
Single site hydrogenation catalyst
G. Vilé, D. Albani, M. Nachtegaal, Z. Chen, D. Dontsova, M. Antonietti, N. López, J. Pérez-RamírezAngew. Chem., Int. Ed. 2015, doi: 10.1002/anie.201505073R1
Active 1-hexyne•mechanism as homogeneous PdSelective•thermodynamic selectivityStable•low Pd concentration in pores
Conclusions
•Integration of DFT and experiments is crucial tounderstand the chemistry
•The strategies in Pd chemistry for hydrogenationare the same independently application
•Reduction of the catalyst to smallest ensemble ispossible
AcknowledgementsM. Garcia-MotaG. Novell-LeruthC. Vargas-FuentesL. BellarosaN. Almora-Barrios
Experimental Collaborations
Prof. J. Pérez-Ramírez (ETH)G. Vilé
CeO2: Oxygen Vacancy formation
CeO2 is able to reversible adsorb O2 in volume
Bulk vacancies more stable than surface ones
Huang et al. Sol. State. Sci. (2005)Lindemer and Brynestad, J. Am. Ceram. Soc. (1986)
CeO2: STM images localization and islanding
Annealing 900ºC 5 min
Esch et al. Science (2005)
CeO2 vs. RuO2
RuO2 CeO2
↑↑↑↑ ↑↑2D 2D-3D
Cl*+Cl*→Cl2+2* Cl# +Cl*→Cl2+#+*
O2 adsorption O2 adsorption
-Hydride phase formation: BET equivalence
> 1 Hydride Pd
-Hydride phase formation: BET equivalence
Role of the molecular modifier
Continuous CO feeding (50 < CO < 500 ppm)
pictures
Rose, et al. Surf. Sci. 512, 48 (2002)
Reaction paths: Thermodynamic factor
Segura, Lopez and Pérez-Ramírez, J. Catal. 247, 383 (2007); Lopez et al. JPCC 112, 9346 (2008); Studt et al., Science, 320, 1320 (2008)
X
BEP-relationships
Activation and reaction energiesare linked by a BEP-likerelationship
Activity of Colloidal Pd, Pt nanoparticles
66
Chemical applications
Pd Pd-CO Ni Au Cu0.0
0.2
0.4
0.6
0.8
1.0
X,Y
/ -
Catalytic systems
Y(C3H6)
Y(C3H8)Y(oligomers)
Alternative systems
-2,0
-1,5
-1,0
-0,5
0,0
0,5
1,0
1,5
2,0
M-C 3H 6TS 2TS 1
M-H-C 3H 5
M-2H-C 3H 4
M-2H+C 3H 4TS H2
M+H 2+C 3H 4
C3H4
E, e
V
Au Cu Pd Ni
C3H6
Cu can be attractive under some conditions but … requires higher T and generates more oligomers
Bridier, et al. J. Catal 269, 80 (2010); Dalton Transac. 39, 8412 (2010)
Carbide exclusion area
Pretreatment and State of Pd
carbide
p alkynes
García-Mota, et al. J. Catal. 273, 92 (2010)
•Large exclusion areasaround C species