Creating new catalytic properties for Co(salen)

complex by coordination with N-modified graphene

Yeunhee Lee
Advisor : Professor Yong-Hyun Kim

Quantum nano-bio Materials Simulation Group

Graduate School of Nanoscience and Technology

2019. 01. 01.

Jacobsen Catalyst

H2(salen) Co(salen)

 Jacobsen catalyst is the organometallic compounds composed of the metal cation and salen type lig-

and to facilitating the epoxide ring opening reaction.

Preparation of Jacobsen and ArGO hybrids (JArGO)

XRD patterns Deconvoluted N 1s XPS spectra

 According to the TEM image and XRD spectrum of JArGO, there is no

formation of nanoparticles such as metallic Co or cobalt oxides.
 Chemical analysis by NMR, FT-IR and XANES/EXAFS confirmed the
TEM image of JArGO-60 attachment of Co(salen) entities to ArGO.
 The peak of pyridinic N in XPS spectra of JArGO relatively decrease.
The electrocatalytic performances of the hybids

(a) LSV curves for the ORR at 1600 rpm in 0.1 M KOH
(b) Tafel slopes at 1600 rpm.

 The JArGO hybrid samples showed the comparable activity to commercial Pt/C catalyst.
 The onset and half-wave potentials of the JArGO-60 is 0.91 and 0.80 V, respectively.
 The slope for JArGO-60 is smaller than those of the Pt/C and ArGO, indicating the rapid kinetics.
Computational details
 VASP code
 PBE exchange correlation functional
 PAW ionic core potential
 Plane wave energy cutoff = 400 eV
 3 x 1 x 1 k-point set for 10 zigzag graphene nanoribbon (zGNR) super-
cells, 1 x 1 x 1 k-point set for molecule
 SCF energy criterion < 10-4 eV
 Force relaxation < 10-2 eV/Å
 Spin polarized calculation

 Atomic structure N

Co

10 zigzag graphene nanoribbon (zGNR) supercells Co(salen)

containing the pyridine like nitrogen
Formation energy of Co(salen) & Cohesive energy of Co
ethylene cyclohexane

H2(salen) Co(salen)

Cosingle+ H2(salen) → Co(salen) + H2

Eformation(eV)
Ecohesive(eV)
Eformation = E(Cosalen) + E(H2) – {E(Cosingle) + E(H2salen)} ethylene cyclohexane
-5.46 -4.47 5.33
Ecohesive = - {E(Cobulk)/N- E(Cosingle)}

 The formation of Cosalen molecule having ethylene bridge is thermodynamically more favorable than the
formation of cobalt bulk.
 If the cyclohexyl group is contained, it is less favorable the preservation of molecule entities than the forma-
tion of metal crystal.
Atomic structure and Formation energy of JArGO
Salen molecule
Co(salen) molecule

Salen type ligand + ArGO → JArGO

Ebinding = E(JArGO) – {E(salen ligand) + E(ArGO)}

cyclohexyl Co(salen) ethyl-Co(salen) Salen

Ebinding(meV) -11.9 -4.2 -704.5
Distance (Å) 3.97 3.84 3.78
 The distance is the length between cobalt atom and nitrogen in graphene and the z value differ-
ence between the nitrogen in salen and graphene in the case of no cobalt.
 Binding affinity of the salen ligand is more strong when the cobalt metal is coordinated to the salen ligand,
and the bulkier ligand results in the smaller binding energy.
 Electronic structure

 Pyridinic nitrogen  Adsorbate oxygen

Co d Co d

Op

Np

 The cobalt of salen molecule moiety hybridize with the nitrogen in the graphene, making the square pyrami-
dal coordination.

 The adsorbates attach to the cobalt atom forming the six coordinated octahedral structure.
Free energy diagram of Oxygen Reduction Reaction
6
O2(g)
*O2

Free energy (eV)

*OOH
4
*O

2
*OH
pH =14

H2O(g)
0
Reaction coordinate

 Potential determining step (PDS) : *O2 → *OOH (0.20V) at pH=14

 Each oxygen reduction reaction (ORR) steps on cobalt site is downhill following the four electron pathway.
 In experimental alkaline condition, ORR can occur with lower voltage.
Conclusion

 The formation of Cosalen molecule is more favorable than the cobalt metal structure.

 Binding affinity of salen ligand improves when the cobalt metal incorporated into the salen mole-
cule.

 Bulky functional group hampers the binding of salen ligand to the graphene basal plane.

 Considering the distance between the Jacobsen catalyst and N-doped graphene, salen molecule
binds to the graphene in the form of van der waals interaction.

 The ORR steps are downhill, while the small overpotential is needed to overcome the energy
barrier when the alkaline condition is considered.