Supplementary Figure 1. XP Spectra. XPS of fresh (a) and tested (b) graphenes in region of C1s level and spectra of graphenes in the region of N1s,

Transcription

1

2 Supplementary Figure 1. XP Spectra. XPS of fresh (a) and tested (b) graphenes in region of C1s level and spectra of graphenes in the region of N1s P2p S2p and O1s levels. The three components centered at (red) (blue) and (light blue) ev correspond to sp 2 bonded carbon sp 3 bonded carbon and to sp 2 carbon satellite peak due to π-π* transitions

3 TCD signal (a.u.) TCD signal (a.u.) a H 2 -TPD1 H 2 -TPD2 H 2 -TPD Temperature b H 2 -TPD1 H 2 -TPD2 H 2 -TPD Temperature Supplementary Figure 2. TPDs. a. H 2 -TPD desorption profiles after H 2 adsorption at room temperature on Gr; b. H 2 -TPD desorption profiles after H 2 adsorption at 120 C on Gr

4 Supplementary Figure 3. Raman spectra. Spectra for fresh (a) and graphenes tested in hydrogenation of the acetylene/ethylene mixture (b)

5 A) B) C)

6 D) E)

7 Supplementary Figure 4. TEM images. Photographs of Gr (A and B) and rgo (C D and E) after being used as catalysts for the selective acetylene hydrogenation under the conditions indicated in Tables SI-1 and SI-6.

8 a b Supplementary Figure 5. TPDs. a) CO 2 -TPD desorption profiles on Gr and (N)Gr; b) TPD-NH 3 desorption profiles for Gr and (N)Gr samples

9 Cleaning Ar 10 ml/min (H 2 in Ar) 10 ml/min Supplementary Figure 6. Isotopic scrambling. H 2 /D 2 scrambling after exposing Gr to D 2 subsequent evacuation and exposure of the sample to H 2.

10 Produced C 2 H 6 (%) Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% First step Second step N2 + 10% NH % Third step Fourth step N2 + 10% CO % Fifth step Time (min) Supplementary Figure 7. Poisoning experiments. Influence of the presence of CO 2 or NH 3 on the selectivity of ethane formation. Conditions: Catalyst graphene: 7 mg 100 o C

11 Supplementary Table 1. Acetylene-ethylene hydrogenation using Gr as catalyst at a flow of 1.7 ml/min. Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% Catalyst Gr: 7 mg Results Temperature Gas composition C2H4 (%) C2H2 (%) - - Product distribution % C 2 H 4 C 2 H 2 C 2 H 6 C RT

12 Supplementary Table 2. Acetylene-ethylene hydrogenation using Gr as catalyst at a flow of 9 ml/min Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 9 C2H2 1% Catalyst Gr: 7 mg Results Temperature Gas composition C2H4 (%) C2H2 (%) - - RT Product distribution % C 2 H 4 C 2 H 2 C 2 H 6 C

13 Supplementary Table 3. Time Evolution of the conversion for Gr at 110 o C at a flow 2.2 ml/min Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 2.2 C2H2 1% Catalyst Gr: 7 mg Time C2H4 (%) C2H2 (%) Product distribution % C 2 H 4 C 2 H 2 C 2 H 6 C

14 Supplementary Table 4. Acetylene-ethylene hydrogenation over GO Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% Catalyst 14Graphene: 7 mg Catalytic activity as a function of temperature: Temperature Gas composition C2H4 (%) C2H2 (%) - - RT - - Product distribution % C 2 H 4 C 2 H 2 C 2 H 6 C 4 C

15 Supplementary Table 5. Time Evolution of the conversion for GO at 110 o C flow 1.9 ml/min Time C2H4 (%) C2H2 (%)

16 Supplementary Table 6. Acetylene-ethylene hydrogenation over rgo Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% Catalyst rgo: 7 mg Catalytic activity as a function of temperature: Temperature Gas composition C2H4 (%) C2H2 (%) - - Product distribution % C 2 H 4 C 2 H 2 C 2 H 6 C 4 C RT

17 Supplementary Table 7. Acetylene-ethylene hydrogenation over (N)Gr Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% Catalyst graphene with nitrogen: 7 mg Results: Temperature Gas composition C2H4 (%) C2H2 (%) - - Product distribution % C 2 H 4 C 2 H 2 C 2 H 6 C 4 C RT

18 Supplementary Table 8. Acetylene-ethylene hydrogenation over (P)Gr Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% Catalyst graphene with phosphor: 7 mg Results: Temperature Gas composition C 2 H 4 (%) C 2 H 2 (%) - - Product distribution % C 2 H 4 C 2 H 2 C 2 H 6 C 4 C RT

19 Supplementary Table 9. Acetylene-ethylene hydrogenation over (S)Gr Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% Catalyst graphene with sulphur: 7 mg Results: Temperature C2H4 (%) C2H2 (%) Product distribution % C 2 H 4 C 2 H 2 C 2 H 6 C 4 C4+ Initial RT

20 Supplementary Table 1 Acetylene-ethylene hydrogenation over Pt/C. Conditions: Gas Flow (ml/min) % Acetylene/ethylene 1.7 C2H2 1% Catalyst 1% Pt/C - commercial: 7 mg Results: Temperatur e n C2H4 (%) n C2H2 (%) Products observed (%) C 2 H 4 C 2 H 2 C 2 H 6 C 4 Polymerizatio n product Initial

21 Supplementary Table 11. Acetylene/ethylene hydrogenation over Pd/C catalyst Conditions: Gas Flow (ml/min) % Acetylene/ethylene 1.7 C2H2 1% Catalyst 1% Pd/C - commercial: 7 mg Results: Temperatur e n C2H4 (%) n C2H2 (%) Products observed (%) C 2 H 4 C 2 H 2 C 2 H 6 C 4 Polymerizatio n product Initial

22 Supplementary Table 12 Acetylene-ethylene hydrogenation over 1% Ni/C Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% Catalyst 1% Ni/C : 7 mg Results: Temperatur e n C2H4 (%) n C2H2 (%) Initial Products observed (%) C 2 H 4 C 2 H 2 C 2 H 6 C 4 Polymerizatio n products

23 Supplementary Table 13. Acetylene-ethylene hydrogenation using dialysed GO as catalyst. Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% Catalyst GO after dialysis: 7 mg Results: Temperatur e n C2H4 (%) n C2H2 (%) Products observed (%) C 2 H 4 C 2 H 2 C 2 H 6 C 4 Polymerizatio n product Initial

24 Supplementary Tables 14 and 15. Acetylene-ethylene hydrogenation using Mn-impurified GO as catalysts. Conditions: Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% Supplementary Table 14 Catalyst 5 ppm MnCl2/graphene: 7 mg reduced under H2 300 C 2h Results: Temperatur e n C2H4 (%) n C2H2 (%) Products observed (%) C 2 H 4 C 2 H 2 C 2 H 6 C 4 Polymerizatio n product Initial Tc Supplementary Table 15. Catalyst 10 ppm MnCl2/graphene: 7 mg reduced under H2 300 C 2h Results: Temperatur e n C2H4 (%) n C2H2 (%) Products observed (%) C 2 H 4 C 2 H 2 C 2 H 6 C 4 Polymerizatio n product Initial Tc

25 Conditions for Supplementary Tables 16 and 17: Acetylene-ethylene hydrogenation using PdCl2 impurified GO as catalyst. Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1%

26 Supplementary Table 16. Catalyst 5 ppm PdCl2/graphene: 7 mg reduced under H2 300 C 2h Results: Temperatur e n C2H4 (%) n C2H2 (%) Products observed (%) C 2 H 4 C 2 H 2 C 2 H 6 C 4 Polymerizatio n product Initial

27 Supplementary Table 17. Catalyst 10 ppm PdCl2/graphene: 7 mg reduced under H2 300 C 2h Results: Temperatur e n C2H4 (%) n C2H2 (%) Products observed (%) C 2 H 4 C 2 H 2 C 2 H 6 C 4 Polymerizatio n product Initial

28 Supplementary Table 18. Hydrogenation of cyclooctene Catalyst % Selectivity % Gr GO rgo (N)Gr (P)Gr (S)Gr Reaction conditions: 26 mg cyclooctene 5 ml heptane 80 C 4h 7mg catalyst 1400 rpm 30 bar H 2

29 Supplementary Table 19. Hydrogenation of Oleic Acid Catalyst % Selectivity to stearic acid % Gr GO rgo (N)Gr (P)Gr 9 100