Supporting Information:

Catalytic Hydrogenation of Carbon Dioxide to

Methanol: Synergistic Effect of Bifunctional
Cu/perovskite Catalysts

Matej Huš,∗,†,‡ Drejc Kopač,† and Blaž Likozar†

†Department of Catalysis and Chemical Reaction Engineering, National Institute of

Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia
‡Department of Physics, Chalmers University of Technology, Fysikgränd 3, SE-41296
Gothenburg, Sweden

E-mail: matej.hus@ki.si

1 Catalyst synthesis and characterisation

Cu0.5 M0.3 Ti0.2 Oy (M = Ca, Ba) catalysts were synthesized with the solution combustion
method using citric acid as a complexation agent and fuel. Adequate amounts of Cu(NO3 )2 ,
M(NO3 )2 and citric acid (fuel ratio 1.5) were dissolved in distilled water. Titanium iso-
propoxide was separately poured in distilled water to form TiO(OH)2 , which was dissolved
in 5 M HNO3 and added to the rest of the liquid. The solution was mixed and heated at
353 K until a viscous gel formed. It was then placed in a furnace in the presence of air
at 923 K for 12 h. Powder XRD analyses (Figure S1 and S2) showed that all the samples
contained CuO, perovskite phases (CaTiO3 and BaTiO3 ) and some amounts of other phases
because non-equimolar amounts of M and Ti were used for synthesis. On account of the

S-1
predominating phases, the catalysts are veraciously described by the theoretical model. The
BET surface areas were 17.6 and 4.5 m2 g−1 for the catalysts with Ca and Ba as M, respec-
tively. Catalytic performance of the catalysts was evaluated in a parallel packed-bed reactor
system. The catalysts were pelletized and pre-reduced (to convert CuO into Cu) in H2 flow
at 300 ◦ C for 12 h.

Figure S1: Powder X-ray diffraction of the Ca-type perovskite catalyst before reduction.

Figure S2: Powder X-ray diffraction of the Ba-type perovskite catalyst before reduction.

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Table S1: Reference COD IDs of standards for XRD analysis of the catalysts before reduc-
tion.

Phase COD ID
CuO 7212243
BaCO3 9006839
BaTiO3 1525438
CaTiO3 9013384
CaCO3 2310544

2 Catalyst testing

The catalysts were tested in a packed bed reactor. Catalytic testing was performed at 20 bar
at the temperatures between 473.15 and 553.15 K in a flow of H2 /CO2 with the molar ratio
3:1 and GHSV 12,000 h−1 . Gaseous products was analysed online using an Agilent 490 Micro
GC system.
In Figures S3 and S4, productivity of the catalysts is shown. At lower temperatures, more
CH3 OH is produced, while at higher temperatures the production of CO starts to form.
0
Ba
[mmol / m2 h-1]

Ca
-1

-2
3OH

-3
ln rCH

-4
18 19 20 21 22
4 -1
10 / T (K )

Figure S3: Productivity of the catalysts for production of methanol per surface area.

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 4
Ba
Ca
ln rCO [mmol / m2 h-1]

-2

-4

-6
18 19 20 21 22
104 / T (K-1)

Figure S4: Productivity of the catalysts for production of CO per surface area.

S-4