Supporting Information

The Hydration of Carbon Dioxide in Copper-Alkoxide Functionalized Metal-Organic

Frameworks: A DFT Study
Chadchalerm Raksakoon1,2, Thana Maihom1,2,4, Michael Probst5 and Jumras Limtrakul1,2,3*
1

Department of Chemistry, and NANOTEC Center for Nanoscale Materials Design for Green
Nanotechnology, Kasetsart University, Bangkok 10900, Thailand.

Center for Advanced Studies in Nanotechnology and Its Applications in Chemical, Food and
Agricultural Industries, Kasetsart University, Bangkok 10900, Thailand.

PTT Group Frontier Research Center, PTT Public Company Limited, 555 Vibhavadi Rangsit Road,
Chatuchak, Bangkok 10900, Thailand.

Department of Chemistry, Faculty of Liberal Arts and Science, Kasetsart University, Kamphaeng Saen
Campus, Nakhon Pathom 73140, Thailand.
5

Institute of Ion Physics and Applied Physics, University of Innsbruck, 6020 Innsbruck, Austria.

Figure S1. Optimized structures of the adsorption of H2O on the Zn site in Cu-MOFs.

Figure S2. Geometry of the extended Cu-MOFs clusters.

Table S1. Relative energies from E, H and G values at 298.15 K for the first pathway of the
hydration of CO2 in the Cu-MOFs as calculated on the M06-L/6-311+G(2df,2p)//M06-L/631G(d,p) level of theory.
Reaction coordinates

Relative energies (kcal/mol)

E

Ads_a

-10.7

-11.3

-2.4

Coads_a

-28.0

-29.2

-7.0

TS1_a

-15.0 (Ea1=13.0)

-16.2 (Ea1=13.0)

9.0 (Ea1=16.0)

Int1_a

-20.4

-21.6

2.7

TS2_a

8.0 (Ea2=28.4)

6.8 (Ea2=28.4)

30.9 (Ea2=28.2)

Int2_a

-34.1

-35.3

-9.6

TS3_a

-30.9 (Ea3=3.2)

-32.1 (Ea3=3.2)

-6.2 (Ea3=3.4)

Prod_a

-31.6

-32.8

-6.9

Table S2. Relative energies from E, H and G values at 298.15 K for the second pathway of
the hydration of CO2 in the Cu-MOFs calculated on the M06-L/6-311+G(2df,2p)//M06-L/631G(d,p) level of theory.
Reaction coordinates

Relative energies (kcal/mol)

E

Ads_b

-21.6

-22.2

-14.1

TS1_b

-5.8 (Ea1=15.8)

-6.4 (Ea1=15.8)

5.0 (Ea1=19.1)

Int1_b

-20.3

-20.9

-10.8

Int1_b/CO2

-23.5

-24.7

-5.4

TS2_b

-16.7 (Ea2=6.8)

-17.9 (Ea2=6.8)

6.1 (Ea2=11.5)

Int2_b

-20.7

-21.8

2.3

TS3_b

-15.2 (Ea3=5.5)

-16.3 (Ea3=5.5)

8.6 (Ea3=6.3)

Prod_b

-14.4

-15.5

8.4

Table S3. Relative energies for the first pathway of the CO2 hydration on the Cu-MOFs and on
the extended Cu-MOFs clusters as calculated with the M06-L/6-31G(d,p) level of theory.

Reaction coordinates

Relative energies (kcal/mol)

Cu-MOFs

Extended Cu-MOFs clusters

Ads_a

-13.6

-13.5

Coads_a

-38.1

-34.0

TS1_a

-25.5 (Ea1=12.6)

-16.4 (Ea1=17.6)

Int1_a

-32.1

-34.9

TS2_a

-2.7 (Ea2=29.4)

-4.5 (Ea2=30.4)

Int2_a

-48.1

-45.7

TS3_a

-43.5 (Ea3=4.6)

-40.4 (Ea3=5.3)

Prod_a

-45.7

-30.7

Table S4. Relative energies for the second pathway of the hydration of CO2 on the Cu-MOFs
and on the extended Cu-MOFs clusters calculated at the M06-L/6-31G(d,p) level of theory.

Reaction coordinates

Relative energies (kcal/mol)

Cu-MOFs

Extended Cu-MOFs clusters

Ads_b

-29.2

-29.8

TS1_b

-9.7 (Ea1=19.4)

-9.2 (Ea1=20.6)

Int1_b

-26.7

-27.1

Int1_b/CO2

-32.1

-33.3

TS2_b

-25.7 (Ea2=6.4)

-27.5 (Ea2=5.8)

Int2_b

-32.6

-34.4

TS3_b

-25.6 (Ea3=7.0)

-28.3 (Ea3=6.1)

Prod_b

-27.4

-29.4