Technische Universitt Mnchen

Towards a
First-Principles Chemical Engineering

Karsten Reuter
Chemistry Department and Catalysis Research Center
Technische Universitt Mnchen
 Challenges across the scales

Self-consistent coupling to reactive

flow field and appropriate
heat balance

Surface chemistry:
adsorption, diffusion,
reaction, desorption

Accurate (first-principles) energetics Quantitative transient and

of individual elementary processes steady-state surface kinetics
 Multiscale modeling

Ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions
K. Reuter, C. Stampfl, and M. Scheffler, in: Handbook of Materials Modeling Vol. 1,
(Ed.) S. Yip, Springer (Berlin, 2005). http://www.fhi-berlin.mpg.de/th/paper.html
 I. Bottom up best practice:
Multiscale modeling approach to
in-situ CO oxidation at RuO2(110)
Electronic regime: Energetics of elementary processes

0.9 eV

COcus + Ocus CO2

Density-Functional Theory
Vxc = GGA (PBE)

K. Reuter and M. Scheffler, Phys. Rev. B 68, 045407 (2003)

 Mesoscopic regime: Tackling rare-event time scales

kBA

kAB
EAB EBA
Transition State kinetic
Theory Monte Carlo
TS N
k BT Z TS (i j )
ki j = B
h Zi B
A
Ei j
= o exp Molecular
k BT A Dynamics t

dPi (t )
= k i j Pi (t ) + k j i Pj (t )
dt j j

First-principles kinetic Monte Carlo simulations for heterogeneous catalysis: Concepts, status and frontiers
K. Reuter, in Modeling Heterogeneous Catalytic Reactions: From the Molecular Process to the Technical System,
(Ed.) O. Deutschmann, Wiley-VCH, Weinheim (2011). http://www.fhi-berlin.mpg.de/th/paper.html
Kinetic Monte Carlo: essentially coarse-grained MD

Molecular Dynamics: Kinetic Monte Carlo:

the whole trajectory coarse-grained hops

ab initio MD: ab initio kMC:

up to 50 ps up to minutes
Building a first-principles kinetic Monte Carlo model

CO oxidation @ RuO2(110)

CO

O
O
Ru

26 elementary processes (site-specific):

- O2 adsorption/desorption (dissociative/associative)
- CO adsorption/desorption (unimolecular)
- O and CO diffusion
- CO + O reaction
K. Reuter, Oil&Gas Sci. Technol. 61, 471 (2006)
K. Reuter and M. Scheffler, Phys. Rev. B 73, 045433 (2006)
Surface structure and composition in the reactive environment

CO oxidation at RuO2(110)

600 K pO2 (atm)

10-15 10-10 10-5 1 10+5
105
CO br/CO
br/CO cus cus
CO

pCO (atm)
T = 600 K, pO 2 = 1 atm, pCO = 7 atm 1

CObr/-
10-5
Obr/ - Obr
O/O cus
br/O cus

K. Reuter, D. Frenkel and M. Scheffler,

Phys. Rev. Lett. 93, 116105 (2004)
 Steady-state and transient parameter-free turnover frequencies

350 K TPR
pCO (10-9 atm)
0.0 1.0 2.0 3.0
TOFCO2 (1012 mol/cm2 s)

6 pO2 = 10-10 atm

xx Exp.
4 x
xx

x
x
2 x
x
x Theory
x
x x
xx xx
x x
0

K. Reuter and M. Scheffler, M. Rieger, J. Rogal, and K. Reuter,

Phys. Rev. B 73, 045433 (2006) Phys. Rev. Lett. 100, 016105 (2008)
 Macroscopic regime: Heat and mass transfer

Computational
Fluid Dynamics:
Stationary stagnation
T, pCO, pO2
point flow

pCO
pO2
pCO2

T p

Chemical source terms

from 1p-kMC
S. Matera and K. Reuter, Phys. Rev. B 82, 085446 (2010)
 Isothermal limit: Mass transfer limitations

T = 600 K
pO2 = 0.3 atm
uinl = 1 cm/sec
T = const

S. Matera and K. Reuter, Catal. Lett. 133, 156 (2009)

 II. Towards error-controlled
first-principles microkinetic models
 Key ingredients to predictive-quality microkinetic modeling

Accurate rate constants: Ei j

ki j = o exp
k BT
Transition state theory and beyond
DFT functionals: self-interaction
van der Waals interactions

Reaction mechanism:
CO + * CO*
Process identification O2 + 2* O* + O*
Lattice mapping / spatial distributions CO* + O* CO2

Hot chemistry beyond Markov
Mean-field approximation: Phenomenological rate equations

dPi (t )
= k i j Pi (t ) + k j i Pj (t )
dt j j

(Ocus) P (O br , CO cus , t )
(Obr)

(COcus)
(CObr) (O br , t ) (CO cus , t )

d (O cus , t )
dt
{
= f 1 k i j , (O cus , t ), (O br , t ), (CO cus , t ), (CO br , t ) }
d (O br , t )
dt
{
= f 2 k i j , (O cus , t ), (O br , t ), (CO cus , t ), (CO br , t ) }
K
 The power of fitting

CO oxidation
at RuO2(110)

104
TOF (site-1s-1)

102 MFA(kDFT) MFA(kFit)

kMC

pO2 = 1 atm, T = 600 K

100
0.5 5 100
pCO (atm)
Fitted rate constants deviate from real rate constants
by up to two orders in magnitude for dominant processes
Effective parameters without microscopic meaning B. Temel et al.,
J. Chem. Phys. 126, 204711 (2007)
Diffusion at metal surfaces: surprises

Hopping mechanism

Ag(100) E = 0.45 eV
Au(100) E = 0.83 eV

Exchange mechanism

Ag(100) E = 0.73 eV
Au(100) E = 0.65 eV

B.D. Yu and M. Scheffler, Phys. Rev. B 56, R15569 (1997)

 Automatized process identification

Accelerated molecular dynamics:

Hyperdynamics TAD

Other approaches: - metadynamics

- dimer method

Extending the Time Scale in Atomistic Simulation of Materials,
A.F. Voter, F. Montalenti and T.C. Germann,
Annu. Rev. Mater. Res. 32, 321 (2002)
 Error propagation through rate-determining steps

CO oxidation
at RuO2(110)

O-poisoned CO-poisoned
Sensitivity analysis:
pO2 = 1 atm
k TOF COcus + Ocus
X rc,i = i T = 600 K
TOF ki k j , K i Ocus/Ocus ad

C.T. Campbell,
rc,i

J. Catal. 204, 520 (2001); CObr ad

Nature 432, 282 (2004) COcus +Obr

Obr/Ocus ad

H. Meskine et al.,
Ertl Special Issue
pCO (atm) Surf. Sci. 603, 1724 (2009)
 Source for rough rate constants: Hybrid UBI-QEP ?!

Pt(111),
Rh(111)

Unity Bond-Index Quadratic Exponential Potential

[ [ ] ]
2
EE = =E ( P Emin
b, A +
UBI-QEP ( P D )
UBI-QEP
A +
ABAB B A+B
TS
AB A+ B
E ( E ) ) (
MEP
b , BAB D
=
AB
E b ,
AB
AB )
+
x AB
( P D )
AB

E. Shustorovich and H. Sellers, Surf. Sci. Rep. 31, 5 (1998)

M. Maestri and K. Reuter, Angew. Chemie 123, 1226 (2011)

 Tackling complexity: Bottom-up meets top-down

Start with working engineering microkinetic model

(semi-empirical rate constants, rate equations)

Perform sensitivity analysis

All rate-determining steps

already described ab initio?

No Yes

Refine rate constants

for rate-determining steps Done
with first-principles calculations
(switch to kMC if indicated)
 C1 microkinetic model for
methane conversion to syngas on Rh/Al2O3

H2
oxidation

CO
oxidation

coupling
H2 & CO

M. Maestri et al., AIChE J. 55, 993 (2009)

 C1 microkinetic model for
methane conversion to syngas on Rh/Al2O3

coupling H2 & CO

CH4
pyro-
lisis

M. Maestri et al., AIChE J. 55, 993 (2009)

 C1 microkinetic model for
methane conversion to syngas on Rh/Al2O3

CH4 pyrolisis
CH4 oxidation

M. Maestri et al., AIChE J. 55, 993 (2009)

 Identified key issues: Water-gas shift and r-WGS

RDS RDS

CO2/CO ratio not well captured by the model,

pointing at an incorrect description of WGS pathways
Same RDS for WGS/r-WGS inconsistent with experimental data

M. Maestri et al., Topics Catal. 52, 1983 (2009)

 First-principles refinement:
When an elementary step is not elementary

CO + OH CO2 + H

RDS

RDS

WGS proceeds through carboxyl mechanism

New RDS consistent with all experimental data

M. Maestri and K. Reuter (submitted)

 Multiscale catalysis modeling: From hype to reality

State-of-the-art in catalysis modeling:

- Prevalence of highly coarse-grained models
based on effective parameters without true
microscopic meaning
rate equation theory
based on empirical rate constants
- Emergence of ad-hoc dual-scale modeling
first-principles kinetic Monte Carlo
simulations for heterogeneous catalysis

Steps towards a predictive character multiscale catalysis modeling:

- Replace effective parameters by first-principles data
fitted vs. DFT-based rate constants
- Refined modeling at each individual level
necessity to resolve spatial arrangement at surface
integrate first-principles surface chemistry into reactor models
- Robust links between theories that enable reverse-mapping
sensitivity analysis to control flow of error across scales
 Technische Universitt Mnchen

www.th4.ch.tum.de