Diffusion of [Cu(NH3)2]+ Complexes in Cu-CHA Catalysts

under NH3-SCR-NOx Reaction Conditions: Insights from

AIMD Simulations

Institute of Chemical Technology

Universitat Politècnica de València

Reisel Millán
Mercedes Boronat
Selective catalytic reduction (NH3-SCR-NOx) Introduction
Problematic of NOx
hν
NOx (NO and NO2), HC PHOTOCHEMICAL SMOG

NOx emissions from stationary power plants and mobile sources (75%
diesel vehicles)

Standard: 4NH3 + 4NO + O2 → 4N2 + 6H2O

Fast: 4NH3 + 2NO + 2NO2 → 4N2 + 6H2O

2
Selective catalytic reduction (NH3-SCR-NOx) Introduction
Cu location in CHA Isolated copper: SII > SIV > SI > SIII
Aluminosilicate Cu-SSZ-13
D6R silicoaluminophosphate Cu-SAPO-34
• SI
• SII
Cu2+
•
SIV
cha • SIII
(7.4 Å) 8R
(3.8 Å) [Cu2+(OH-)]+

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Selective catalytic reduction (NH3-SCR-NOx) Introduction
Standard: 4NH3 + 4NO + O2 → 4N2 + 6H2O
Fast: 4NH3 + 2NO + 2NO2 → 4N2 + 6H2O

Reduction half-cycle

Oxidation half-cycle Ea = 6 kcal mol-1

Mao et al. ACS Catal. 2016, 6, 7882

At high T (> 250ºC) Eap= 34 kcal mol-1

At low T (< 250ºC) Eap= 10-20 kcal mol-1
Gao et al. J. Catal. 2014, 319, 1; Paolucci et al. Science 2017, 357, 898 4
Selective catalytic reduction (NH3-SCR-NOx) Introduction

At low T NH3 adsorbs strongly on Cu+ sites

Mobilized Cu+(NH3)2 ions that travel through zeolite

windows

Transient ion pairs (NH3)2 Cu+-O-O-Cu+(NH3)2

Catalyze the oxidation step with Ea = 14 kcal mol-1

At low T (< 250ºC) apparent Ea= 10-20 kcal mol-1

At high T (> 250ºC) isolated copper ions are attached to

framework

Paolucci et al. Science 2017, 357, 898

Gao et al. J. Am. Chem. Soc. 2017, 139, 4935
Chen et al. J. Catal. 2018, 358, 179
Marberger et al. Nature Catal. 2018, 1, 221 5
Ab initio molecular dynamics Results
Diffusion of diamine-copper(I)

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Ab initio molecular dynamics Results
Diffusion of diamine-copper(I)

28

17

7
Ab initio molecular dynamics Results
Diffusion of diamine-copper(I)

50

26
24

8
Ab initio molecular dynamics Results
Diffusion of diamine-copper(I)

48
28

22

9
Ab initio molecular dynamics Results
Diffusion of diamine-copper(I)

76 kJ/mol

22 kJ/mol

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Ab initio molecular dynamics Results
Stability of [Cu(NH3)2]+(NO)x

Snapshots Trajectory of Cu+ at 523 K

298 K 523 K 673 K

The complex [Cu(NH3)2]+(NO)x is relatively stable at the three temperatures considered.

No diffusion through the 8-ring was observed

Ab initio molecular dynamics Results
Stability of [Cu(NH3)2]+(NO)x. Interaction with O2

Snapshots
298 K 523 K 673 K Trajectory of Cu+ at 523 K

2NO+O2 = 2NO2 Spontaneous diffusion

The O2 molecule weakens the interaction of NO with Cu.

Spontaneous diffusion of [Cu(NH3)2]+ through the 8-ring was observed at 573 K
The reaction 2NO+O2 = 2NO2 occurs spontaneously at 673 K
Ab initio molecular dynamics Results
Oxidation of NO with O2 at 423 K
CNox = CN2 - CN1
 Conclusions

AIMD simulations show that the diffusion of an isolated [Cu(NH 3)2]+ complex through the 8-ring
windows of the CHA structure is relatively fast in the presence of another [Cu(NH 3)2]+ monomer or
additional molecules in the final cavity B.

This diffusion is significantly hindered when NH 3 and NO, are present in the initial cavity A.
Therefore, the concentration of these reactants is identified as a key factor strongly influencing the
mobility of [Cu(NH3)2]+ species at low temperature.

The presence of O2 in the reaction media modifies strongly the interaction of NO with Cu +. At low
temperature O2 facilitates the migration of the [Cu(NH3)2]+ species through the 8-ring windows.

At high temperature O2 reacts spontaneously with the two NO molecules present in the cavity to
form two NO2 molecules, which may oxidize Cu+ to Cu2+ according to the fast SCR reaction, thus
enhancing the global SCR reaction rate.

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Diffusion of diamine-copper(I)
Al distributions

2Al different 8R

2Al same 8R

2Al spiro-24
Thanks