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Supporting Information

Highly Selective Conversion of Carbon Dioxide to


Lower Olefins
Zelong Li, Jijie Wang, Yuanzhi Qu, Hailong Liu, Chizhou Tang, Shu Miao, Zhaochi
Feng, Hongyu An, Can Li*

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese


Academy of Sciences, Dalian 116023, China

Corresponding Author
*E-mail: canli@dicp.ac.cn

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Table of Content

Catalyst preparation.....................................................................................................3
Catalyst characterization………………………………………………........……......….......…..........3
Catalytic evaluation …………………………………………………....………………………………………5
Figures S1-10…………………………………………………………………………………………………………6

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Catalyst Preparation.
The co-precipitation method was used to prepare the ZnO-ZrO2 binary oxides.
The mixture of aqueous solution of zirconium and zinc nitrates (total
concentration of Zn and Zr is 0.6 mmol/mL) and the aqueous of ammonium
carbonate were added dropwise into water in flask under vigorous stirring at 70
o
C. The pH value of the solution was kept at about 7.0 by adjusting the adding
rate of aqueous solution of ammonium carbonate. The obtained precipitate was
stirred for about 4 hours, and the precipitate was aged for 12 hours at 70 oC, and
then was filtered with deionized water and dried at 110 oC for 12 hours. Finally,
the precipitate was calcined at 500 oC for 5 hours. Similar procedures were used
to prepare ZrO2, ZnO, ZnO-Cr2O3 catalysts. CuZnAlOx was prepared by
following the above procedure but using sodium carbonate to replace
ammonium carbonate, and the catalyst was calcined at 250 oC for 5 hours. The
tandem catalysts were prepared through physical mixing the metal oxide solid
solution and SAPO-34 zeolite. The mass ratio of these two components was 1:1,
unless otherwise indicated. Zn-SAPO-34 was synthesized according to the
literature1. The composition of the Zn-SAPO is as follows: 3TEA: 0.2SiO2: A12O3:
P2O5: 50H2O, and 0.05Zn(OAc)2:Al2O3 molar ratio.
Catalyst Characterization.
X-ray powder diffraction (XRD) patterns was recorded on a Philips PW1050/81
diffractometer operating in Bragg-Brentano focusing geometry and using CuKα
radiation (λ = 1.5418 Å) from a generator operating at 40 kV and 30 mA.
Transmission Electron Microscopy (TEM) and High-Resolution Transmission
Electron Microscopy (HRTEM) were performed on a Philips Analytical FEI
Tecnai 30 electron microscopy operated at an acceleration voltage of 300 Kv.
The high angle annular dark field imaging (HAADF) and Zn and Zr element
mapping were performed with an aberration-corrected JEM-ARM200F
microscope.
UV–vis diffuse reflectance spectra were recorded on a JASCO V-650 equipped
with an integrating sphere.
Raman spectrosco py: UV Raman spectra were recorded on a home-as-
UV Raman spectrograph using a Jobin-Yvon T64000 triple-stage spectrograph
with spectral resolution of 2 cm-1. The laser line at 325 nm of an He–Cd laser
was used as exciting source with an output of 50 mW. The power of the laser at
samples was about 1.0 mW. The 244 nm line from a Coherent Innova 300 Fred
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laser was used as another excitation source. The power of the 244 nm line at
samples was below 1.0 mW. The UV laser source (266 nm) was a Coherent
Innova 300 Fred300 cw UV laser equipped with an intracavity
frequency-doubling system using a BBO crystal to produce SHG (second
harmonic generation) outputs at different wavelengths.
CO2-Temperature-programmed-desorption (CO2‒TPD) were performed on a
Micromeritics AutoChem 2910 equipped with a thermal conductivity detector
(TCD). The procedures for CO2-TPD: the catalysts were first reduced in a
flowing Ar at 380 oC for 1 hour, after cooling down to 50 oC, the catalyst was
treated by Ar for 30 min. Then the sample was exposed to CO2/He for 30 min at
50 oC. Subsequently, the sample was swept by He at 50 ºC till a stable baseline
was obtained. Signal was recorded while the temperature was increased from 50
to 800 ºC at a heating rate of 10 ºC/min.
In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)
experiment were performed using an FTIR spectrometer (Thermo, Nicolet
6700) with a MCT detector. First, the catalyst was treated under H2 flow at 300
o
C for 2 h, and then the N2 was purged at 450 oC for 2 h and then the catalyst
was cooled down to 280 oC. The background spectrum was obtained at 280 oC
in N2 flow. Then, the catalyst sample was exposed to a CO2/H2 mixture (4
mL/min CO2 and 12 mL/min H2, 40 mg catalyst), and the catalyst was treated at
this temperature for 10 min, and then the temperature increased to 290 oC , the
temperature can be ramped every 10 oC from 280 oC to 380 oC, and the
temperature was kept for about 10 min for recording the FT-IR spectra of the
surface species generated on catalyst. In-situ DRIFT spectra were recorded by
collecting 64 scans at 4 cm−1 resolution, and the In-situ DRIFT data that shown
in Figure 4a for ZnZrO/SAPO catalyst has been enlarged 2 times.
H2-D2 exchange reaction was performed on manual operated CO2-TPD
combined with mass spectroscopy. The catalyst was first pretreated with Ar at
380 oC for one hour, and then cooled to 50 oC. The H2 and D2 with 20 mL/min
flow rate passed the catalyst, and the reaction temperature was ramped from 50
o
C to 400 oC.
Chemical trapping experiment was performed on manual operated TPD
combined with mass spectroscopy. The catalyst was first pretreated with Ar at
380 oC for one hour, and then cooled to 50 oC. The mixture of H2/CO2 (molar
ratio is 3, 30 mL/min) passed through catalyst bed for hydrogenation of CO2,
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and the chemical trapping reagent, CD3OD was introduced into the reactor by
using Ar as carrier (30 mL/min). The reaction temperature was ramped from 50
o
C to 340 oC, and kept at this temperature for about 30 minutes and then
increased to 400 oC. The Mass signals of all species were followed as the
temperature was ramped from 50 oC.

Catalytic Evaluation.
The catalytic reaction of CO2 hydrogenation was evaluated on a high-pressure
tubular fixed-bed reactor, and the products were detected by a gas
chromatography. Typically, the catalyst (0.2 g, 40-80 mesh) was first pretreated
in an Ar flow (30 mL/min) at 380 oC for 1 hours. The reaction was conducted at
the pressure of 2 MPa and at 380 oC, and the gas flow composition was, 72H2:
24CO2: 4Ar (volume ratio), unless otherwise indicated. The selectivity of
hydrocarbon products was calculated on a molar carbon basis. The selectivity of
CO was calculated separately. All the data discussed in article was collected
after 8 hours of reaction for CO2 hydrogenation reaction.
The Ar, CO, and CO2 contents of the outlet gases were determined by using a
carbon molecular sieves column (TDX-1) with a thermal conductivity detector
(TCD), using H2 as the carrier gas. Hydrocarbons were analyzed using a
KCl-modified alumina capillary column with an argon carrier and a hydrogen
flame ionization detector (FID). The conversion of CO2 was calculated
according to an internal standard method (Ar as an internal standard),
assuming that the amount of Ar remained constant in the reaction process.
Methanol was analyzed using a TG-BOND-Q column with Ar carrier by FID.
CO2 conversion (denoted as X(CO2)) and the carbon-based selectivity (denoted
as S(product)) for the carbon-containing products, including CH4, lower olefins
(C2=-C4=), lower paraffins (C20-C40), C5+, methanol, and CO, were calculated with
an internal normalization method.
X(CO2), S(CO), S(CnHm) were calculated from following equations:

(CO 2)inlet  (CO 2)outlet S (CO) 


(CO)outlet
X (CO2 ) 
(CO 2)inlet (CO 2)inlet  (CO 2) outlet

CnHm
S (CnHm) 
C1  C 2  C 3  C 4  C5

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Figure S1∣ZnZrO structure characterization. a) Raman spectra of ZnZrO; b) UV-Vis
absorption spectrum of ZnZrO.

The appearance of the peaks at 307, 342, 377, 477, 635 cm-1 in Raman spectra
(λ=244 nm) reveals that monoclinic phase exists on the surface, however, the
peaks corresponding to tetragonal phase were hardly observed, probably
because of the small amount of this phase and the stronger Raman scatter of
the monoclinic phase in the mixture of monoclinic and tetragonal phase. A
peak at 564 and 265 cm-1 as characteristic peak of tetragonal phase is appeared
in Raman spectra (λ=266 nm), confirmed that the ZnZrO possesses the mixed
phase both of monoclinic and tetragonal phase, the increasing of relative
intensity of 564 cm-1 (λ=325 nm) of ZnZrO reveals the tetragonal phase has been
dominated in bulk phase2-3.

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Figure S2∣XRD patterns of SAPO, ZnZrO, and ZnZrO/SAPO.

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Figure S3∣SAPO characterization. a) and b): STEM images of SAPO and P, Al, Si, Zn
elements distribution.

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Figure S4∣Catalytic function Characterization of ZnO, ZrO2, 13% ZnZrO, 25% ZnZrO. a)
H2-D2 exchange reaction for ZnO, ZrO2, 13% ZnZrO, 25% ZnZrO; b) CO2-TPD for ZnO, ZrO2,
13% ZnZrO, 25% ZnZrO.

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Figure S5∣Catalytic performance of ZnZrO for hydrogenation of CO2. (Reaction condition:

2 MPa, 3600 mL/gcat/h).

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Figure S6∣Stability of ZnZrO/SAPO. a) The catalyst stability toward the sulfur containing

molecules (H2S or SO2) and annealing. (Reaction condition: 380 oC, 2 MPa, 3600 mL/(g h)); b)
The stability of ZnZrO/SAPO. (2 MPa, 380 oC, 3600 mL/gcat/h).

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Figure S7∣Catalytic performance of x%ZnO-ZrO2/SAPO. a) Catalytic performance of x%
ZnO-ZrO2/SAPO for hydrogenation of CO2 to lower olefins (x stands for the molar ratio of
Zn:(Zn+Zr), 2 MPa, 380 oC, 3600 mL/gcat/h); b) The catalytic performance of ZnZrO/SAPO at
different H2/CO2 molar ratio(reaction condition: 2 MPa, 380 oC, 3600 mL/gcat/h); c) The catalytic
performance of ZnZrO/SAPO at different reaction pressure (reaction condition: 380 oC, 3600
mL/gcat/h); d) The influence of mass ratio of ZnZrO/SAPO on CO2 hydrogenation to lower
olefins (2 MPa, 380 oC, 3600 mL/gcat/h); e) CO selectivity with different space velocity over
ZnZrO/SAPO (2 MPa, 380 oC); f) CO2 conversion for hydrogenation of CO2 over ZnZrO and
ZnZrO/SAPO at reaction temperatures 360-400 oC (2 MPa, 3600 mL/gcat/h).

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Figure S8∣Catalytic performance of SAPO for conversion of methanol. Conversion of
methanol over SAPO zeolite for synthesis lower olefins (380 oC, 3 mL/gcat/h for methanol).

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Figure S9∣a) CuZnAlOx/SAPO, ZnCrAlOx/SAPO, and ZnZrO/SAPO catalytic performance for
hydrogenation of CO2 (2 MPa, 380 oC, 3600 mL/gcat/h); b) The ethylene, propylene, and
butylenes distribution over SAPO and ZnZrO/SAPO for conversion of methanol and
hydrogenation of CO2 respectively (methanol: 380 oC, 3 mL/gcat/h).

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Figure S10∣Gibbs free energy changes at different temperatures for methanol synthesis,
methanol to lower olefins (ethylene and propylene as examples), and CO2 hydrogenation to
lower olefins (ethylene and propylene as examples).

References
(1) Xu, L.; Liu, Z.; Du, A.; Wei, Y.; Sun, Z., In Studies in Surface Science and Catalysis, Elsevier:
2004; Vol. 147, pp 445-450.
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(2) Li, M. J.; Feng, Z. C.; Ying, P. L.; Xin, Q.; Li, C., Phy. Chem. Chem. Phy. 2003, 5, 5326-5332.
(3) Kim, H.; Kosuda, K. M.; Van Duyne, R. P.; Stair, P. C., Chem. Soc. Rev. 2010, 39,
4820-4844.

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