Supplementary Materials for

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1 advances.sciencemag.org/cgi/content/full/3/1/e17129/dc1 Supplementary Materials for A highly selective and stable ZnO-ZrO2 solid solution catalyst for CO2 hydrogenation to methanol Jijie Wang, Guanna Li, Zelong Li, Chizhou Tang, Zhaochi Feng, Hongyu An, Hailong Liu, Taifeng Liu, Can Li This PDF file includes: Published 6 October 217, Sci. Adv. 3, e17129 (217) DOI: /sciadv table S1. The BET results of catalysts and intrinsic property. table S2. The catalytic performance of mechanically mixed and supported catalysts. table S3. DRIFT peak assignments of the surface species for the CO2 + H2(D2) reaction on 13% ZnO-ZrO2. fig. S1. The dependence of methanol selectivity on the Zn/(Zn + Zr) molar ratio at a 1% CO2 conversion. fig. S2. The effect of pressure, H2/CO2 ratio, and GHSV on CO2 hydrogenation. fig. S3. XRD patterns of ZnO-ZrO2 catalysts. fig. S4. HRTEM of the 13% ZnO-ZrO2 catalyst. fig. S5. The UV-vis absorbance and Raman spectra of ZnO-ZrO2. fig. S6. XPS of ZnO, ZrO2, and 13% ZnO-ZrO2. fig. S7. H2-TPR of ZnO, ZrO2, and 13% ZnO-ZrO2. fig. S8. XRD of mechanically mixed and supported catalysts. fig. S9. DRIFT results of CO2 + H2 substituted by CO2 + D2. fig. S1. Structure of ZrO2 and ZnO-ZrO2. fig. S11. Local geometries of the reaction intermediates of CO2 hydrogenation to methanol via formate on the ZnO-ZrO2 (11) surface. fig. S12. Local geometries of the reaction intermediates of CO2 hydrogenation to methanol via CO on the ZnO-ZrO2 (11) surface. fig. S13. Structure of ZnO. fig. S14. Hartree potential of the Zn-terminated ZnO (1) surface calculated by different dipole correction methods.

2 fig. S15. Local geometries of the reaction intermediates on the ZnO (1) surface. fig. S16. Reaction diagram of CO2 hydrogenation to CH3OH via formate on the Zn-terminated ZnO (1) surface. fig. S17. The catalytic performance contrast of the ZnO-ZrO2 catalyst for CO2 + H2 and CO + H2. fig. S18. The catalytic performance contrast of Cu/ZnO/Al2O3 and ZnO-ZrO2 catalysts for CO2 hydrogenation. fig. S19. The stability test of the Cu/ZnO/Al2O3 catalyst.

3 table S1. The BET results of catalysts and intrinsic property. ZnO ZrO2 13%ZnO-ZrO2 SBET (m 2 /g) STY(CH3OH) (mg/(g h)) STY(CH3OH) (mg/(m 2 h)) Normalized intensity of CO2-TPD (mmol/g) Normalized intensity of CO2-TPD (mmol/m 2 ) Normalized intensity of HD (A/g) Normalized intensity of HD (A/m 2 ) S(CH 3 OH)(%) X(CO 2 )=2.2 1 X(CO 2 )= Zn(Zn+Zr) (%) fig. S1. The dependence of methanol selectivity on the Zn/(Zn + Zr) molar ratio at a 1% CO2 conversion. The results were obtained by varing GHSV at 5. MPa, 32 o C.

4 STY(CH 3 OH) (mg/(m 2 h)) S(CH 3 OH) STY(CH 3 OH) X(CO 2 ) /1 3/1 4/ X(CO 2 ), S(CH 3 OH) (%) p (MPa) H 2 /CO 2 GHSV(h -1 /1) fig. S2. The effect of pressure, H2/CO2 ratio, and GHSV on CO2 hydrogenation. Standard reaction conditions: 2. MPa, H2/CO2 = 3/1, 33 o C, GHSV = 24 ml/(g h). (1) (11) (2) ZnO 8%Zn 67%Zn 5%Zn Intensity(a.u.) 33%Zn 25%Zn 2%Zn 17%Zn 13%Zn 1%Zn t-zro 2 (11) 5%Zn m-zro 2 (111) ZrO Theta( o ) fig. S3. XRD patterns of ZnO-ZrO2 catalysts.

5 fig. S4. HRTEM of the 13% ZnO-ZrO2 catalyst.

6 Absorbance(a.u.) A %ZnO-ZrO 2 C Intensity(a.u.) nm ZrO /12 5%Zn 64 1/12 1% 1/ %Zn 1/8 2%Zn 1/4 D Intensity(a.u.) 325 nm ZrO 2 5%ZnO-ZrO %ZnO-ZrO %ZnO-ZrO 2 2%ZnO-ZrO Wavelength(nm) 25%Zn Raman shift (cm -1 ) 25%ZnO-ZrO Raman shift(cm -1 ) fig. S5. The UV-vis absorbance and Raman spectra of ZnO-ZrO2. (A) The UV-Vis absorbance of 13%ZnO-ZrO2. (B) The schematic description of characterizing the structure information of ZnO-ZrO2 catalysts obtained from Raman spectroscopy with different laser. (C) The Raman spectra of ZnO-ZrO2 with 266 nm laser. (D) The Raman spectra of ZnO-ZrO2 with 325 nm laser. Raman spectroscopy with different laser sources could detect phases in different depths due to light absorption and scattering {I (1/λ) 4 }. ZnO-ZrO2 exhibits a strong UV-Vis absorption band at 215 nm, so the Raman scattering information excited by shorter wavelength laser (close to 215 nm) gives the phase information in relatively skin layer of sample, since most of excited laser was absorbed by sample and only the laser scattered in the skin layer can escape and be detected by Raman. Therefore the Raman spectroscopy with laser sources at 244, 266 and 325 nm could detect the phases gradually from the skin layer to the bulk of the catalyst (fig. S5B). The Raman spectroscopy with a 244 nm excitation laser can detect the phase near the utmost skin layer, the depth approximately 2 nm. The probing depths of 266 nm and 325 nm Raman spectroscopy are approximately 5 nm and 1 nm, respectively.

7 A XPS-ZnLM B Zr-3d Intensity(a.u.) ZnO Intensity(a.u.) ZrO 2 13%ZnO-ZrO 2 13%ZnO-ZrO B.E.(eV) B.E.(eV) fig. S6. XPS of ZnO, ZrO2, and 13% ZnO-ZrO2. H 2 -TPR H 2 uptaken(a.u.) 13%ZnO-ZrO 2 ZrO 2 ZnO T ( o C) fig. S7. H2-TPR of ZnO, ZrO2, and 13% ZnO-ZrO2.

8 table S2. The catalytic performance of mechanically mixed and supported catalysts. catalyst X(CO2) S(product) (%) STY(CH3OH) (%) CH3OH CO (mg/(g h)) 13%ZnO-ZrO %ZnO/ZrO ZnO+ZrO2(13:87) ZnO+ZrO2-5-3h ZnO+ZrO2-5-24h MPa, 3 o C, 24 ml/(g h). 13%ZnO/ZrO 2 ZnO+ZrO 2-5-3h Intensity(a.u.) ZnO+ZrO 2 13%ZnO-ZrO 2 ZrO 2 ZnO Theta( o ) fig. S8. XRD of mechanically mixed and supported catalysts.

9 table S3. DRIFT peak assignments of the surface species for the CO2 + H2(D2) reaction on 13% ZnO-ZrO2. Peaks (cm 1 ) Assignment Species νas(oco) νs(oco) ν(ch) δ(ch) δ(ch)+νas(oco) δ(ch)+νs(oco) ν(ch3) ν(ch3) ν(och3) 152, 1341, 1321 CO , HCO νas(cd) ν(cd3)

10 .5 DCOO* 9 min CO 2 +D 2 Absorbance(a.u.) CH 3 O* CD 3 O* 4 min HCOO* Wavenumbers(cm -1 ) fig. S9. DRIFT results of CO2 + H2 substituted by CO2 + D2. The spectra were obtained by subtracting the spectrum of CO2 + H2 reaching stable-state level..1 MPa, 28 o C, 1 ml/min CO2 + 3 ml/min H2 (D2). fig. S1. Structure of ZrO2 and ZnO-ZrO2. Side and top views of the (11) surface of tetragonal ZrO2 (a, b) and Zn-doped ZnO-ZrO2 (c, d).

11 fig. S11. Local geometries of the reaction intermediates of CO2 hydrogenation to methanol via formate on the ZnO-ZrO2 (11) surface.

12 fig. S12. Local geometries of the reaction intermediates of CO2 hydrogenation to methanol via CO on the ZnO-ZrO2 (11) surface.

13 fig. S13. Structure of ZnO. Side and top views of the slab model of Zn-terminated ZnO (1) surface. fig. S14. Hartree potential of the Zn-terminated ZnO (1) surface calculated by different dipole correction methods.

14 fig. S15. Local geometries of the reaction intermediates on the ZnO (1) surface.

15 fig. S16. Reaction diagram of CO2 hydrogenation to CH3OH via formate on the Znterminated ZnO (1) surface.

16 A 1 35 S(product) (%) S(CH 3 3 OH) 25 2 X(CO 2 ) 15 1 S(CO) 5 S(HC) T( o C) X(CO 2 ) (%) B 8 S(CH 3 OH) 3 S(Product) (%) X(CO) S(DME) S(CO 2 ) S(HC) T ( o C) 2 1 X(CO) (%) fig. S17. The catalytic performance contrast of the ZnO-ZrO2 catalyst for CO2 + H2 and CO + H2. (A) CO2 + H2. (B) CO + H2. 13%ZnO-ZrO2 catalyst, H2/CO2(CO) = 3/1, 2. MPa, 24 ml/(g h).

17 1 8 ZnO-ZrO 2 4 S(CH 3 OH)(%) Cu-ZnO-Al 2 O 3 Cu-ZnO-Al 2 O 3 ZnO-ZrO X(CO 2 )(%) T( o C) fig. S18. The catalytic performance contrast of Cu/ZnO/Al2O3 and ZnO-ZrO2 catalysts for CO2 hydrogenation. Reaction conditions: 2 MPa, 24 h 1.

18 A STY(CH 3 OH)(mg/(g h)) B II STY(CH 3 OH)(mg/(g h)) Time on stream(h) I Time on stream(h) STY(CH 3 OH) (mg/(g h)) Befor 25% Reaction at 32 o C for 24 h After Befor After fig. S19. The stability test of the Cu/ZnO/Al2O3 catalyst. (A) I was operated on the conditions of 2 MPa, 24 h 1, 24 o C for 55 h; II was operated on the conditions of 2 MPa, 24 h 1, 24 o C with the feed gas of 4 ml/min (CO2 + H2) + 4 ml/min 5 ppm SO2/Ar. (B) The heat resistance test for Cu/ZnO/Al2O3 catalyst. The reaction was operated at 24 o C and increased to 32 o C keeping for 24 h than decreased to 24 o C.