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 284.6 (red) 285.8 (blue) and 286.5 (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
TCD signal (a.u.) TCD signal (a.u.) a H 2 -TPD1 H 2 -TPD2 H 2 -TPD3 0 200 400 600 800 Temperature b H 2 -TPD1 H 2 -TPD2 H 2 -TPD3 500 600 700 800 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
Supplementary Figure 3. Raman spectra. Spectra for fresh (a) and graphenes tested in hydrogenation of the acetylene/ethylene mixture (b)
A) B) C)
D) E)
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.
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
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.
Produced C 2 H 6 (%) Gas Flow (ml/min) % Acetylene/ethylene (10% /90%) 1.7 C2H2 1% First step Second step N2 + 10% NH3 15.2 87% Third step Fourth step N2 + 10% CO2 15.2 87% Fifth step 5 4 3 0 50 100 150 200 250 300 350 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
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 4 87.4 12.6 0 0 RT 7 12 87.8 12.1 0 1 50 9 18 88.2 11.5 2 1 110 11 39 88.9 8.5 1.1 1.5 120 15 75 92.4 4.1 1.2 2.3 150 41 77 62.9 3.7 1.8 31.5
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 8 16 50 10 39 110 14 81 120 21 99 Product distribution % C 2 H 4 C 2 H 2 C 2 H 6 C 4 87.4 12.6 0 0 88.1 11.8 0 1 91 9.2 6 1 92.2 3.2 1.1 3.5 91.6 9 1.2 6.3
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 4 0 - - 87.4 12.6 - - 15 2.2 14.2 88.7 18 4 1 30 11.4 21.9 88.8 19 4 0 45 12.2 26.0 88.7 13 5 4 60 8.4 22.1 88.5 14 5 5 75 1.4 19.2 88.8 11 6 6 90 1.9 19.6 88.6 11 6 7 105 1.1 19.4 88.7 10 6 7 120 1 20 88.8 9.8 7 7 135 1 18.6 88.6 10 6 8 150 8 23.1 89.0 9.5 7 8 165 1.8 21 88.5 10 6 9 180 7 23.0 89.0 9.5 7 7
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 C4+ 87.5 12.5 87.5 12.5 0 0 0 0 0 0 50 0 1.7 87.8 12.0 1 0 0 70 0 4.2 88.0 11.6 2 0 0 90 0 13.3 88.6 16 5 3 0 110 0 22.5 48.1 5.0 3 46.6 0 130 0 32.4 56.5 5.1 3 38.1 0 150 0 56 54.2 3.8 3 41.8 0
Supplementary Table 5. Time Evolution of the conversion for GO at 110 o C flow 1.9 ml/min Time C2H4 (%) C2H2 (%) 15 0 22.51 30 0 25.57 45 0 310 60 0 348 75 0 31.59 90 0 31.55 105 0 33.15 120 65 33.07 135 67 33.39 150 1.24 33.26 165 68 34.08 180 68 34.08 195 1.44 34.31 210 1.60 33.38 225 1.55 31.78 240 1.22 32.17 255 1.53 33.49 270 1.58 33.83 285 2.17 34.23 300 1.60 36.13
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 C4+ 87.5 12.5 0 0 0 RT 3 1.7 88.9 9.1 3 1 0 50 4 17.3 88.9 15 4 1 0 70 1.6 35 87.9 8.8 6 2 0 90 1.6 54.8 54.1 3.5 8 41.6 0 110 4.7 87.5 55.1 1.2 1.3 42.4 0 130 5.0 97.5 56.6 4 2.1 48 0 150 5.2 98.0 53.6 2 9 45.4 0
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 C4+ 87.4 12.6 0 0 0 RT 0 0 63.7 8.7 0 2.1 27.5 50 6.7 13 62.8 8.7 1 2.1 26.2 70 6.8 15.8 63.4 8.7 2 5.9 25.7 90 6.7 19.1 61.0 7.9 5 4.4 24.7 110 6.7 26.7 62.5 7.2 7 11.5 25.2 130 6.4 33.0 58.3 6.2 5 2.1 23.5
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 C4+ 0 0 0 87.4 12.6 RT 7.6 4.6 87.4 12.5 0 0 0 50 5.2 3.3 87.5 12.4 1 0 0 70 3.5 3.6 87.6 12.1 2 0 0 90 3.6 7.8 88.0 11.6 4 0 0 110 2.7 14.6 72.7 8.8 7 17.7 1 130 1.7 23.1 74 7.6 7 21.2 1 150 1.7 29.4 84 8.0 8 7.8 3.0
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 - - 87.4 12.6 0 0 0 RT 3.1 2 87.5 12.5 0 0 0 50 3.4 2.4 87.5 12.3 2 0 0 70 3.7 6.3 87.5 11.8 4 4 0 90 4.9 15.7 88.2 11.2 6 0 0 110 6.4 24.7 54.1 6.3 4 0 39.1 130 1.4 33.4 52.5 5.4 4 0 41.7 150 1.7 41.3 65.5 5.4 6 0 28.5
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 - - 89.7 13 0 0 0 70 0 63 88.5 3.4 8.0 0 0 100 10 88 71.5 1.1 11 9. 5 7.8 115 11 100 61.6 0 11.8 0 26.6 130 17 100 53.8 0 16.6 0 29.5 150 27 100 43.7 0 21.9 0 34.4
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 - - 87.5 12.5 0 0 0 45 13 81 80 15 93 100 16 100 115 17 100 130 24 100 150 25 100 46.1 1.4 11 34.9 4 18 32.5 0 11.3 29.7 0 10 26.2 0 12.5 23.3 0 15 0 42.4 0 53.9 0 56.2 0 63 0 61.2 0 66.2
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 - - 70 0 45 100 12 61 115 16 74 130 21 87 150 25 91 Products observed (%) C 2 H 4 C 2 H 2 C 2 H 6 C 4 Polymerizatio n products 89.7 13 0 89.2 4.6 6.2 78.3 4.1 9.2 74.3 2.6 19 69.8 1.3 14.3 65.2 8 17.2 0 0 0 0 0 0 0 0 8.4 12.2 14.6 16.8
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 - - 87.2 12.8 0 0 0 50 0 0 80 0 14 100 0 30 115 0 38 130 0 42 150 0 45 87.9 12.1 0 88.3 9.8 2.0 89.2 7.8 3.0 87.2 6.8 3.9 94 6.5 3.1 91.2 6.2 2.6 0 0 0 0 0 0 0 0 0 0 0 0
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 - - 87.3 12.7 0 0 0 Tc 0 0 87.3 12.7 0 0 0 50 0 0 87.3 12.6 1 0 0 100 0 3 88.0 11.2 8 0 0 130 0 27 87.8 8.2 1.9 0 0 150 0 66 91.6 3.9 2.1 0 0 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 - - 87.8 12.2 0 0 0 Tc 0 0 87.8 12.2 0 0 0 50 0 3 87.8 11.8 3 80 0 5 86.7 11.0 1.1 0 0 100 0 6 86.5 18 1.4 0 0
130 0 34 87.6 7.3 2.4 0 0 150 0 68 91.6 3.7 2.3 0 0 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%
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 - - 87.5 12.5 0 0 0 50 4.0 32 80 3.5 73 100 3.6 53 115 6 79 130 10 89 150 7.8 95 66.6 6.8 1.6 65.3 2.6 3.3 61.3 4.3 4.7 54.0 1.7 5.4 51.4 9 7.1 67.8 5 7.6 0 25.0 1. 5 27.3 0 29.7 0 38.9 0 47 0 24.1
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 - - 87.2 12.8 0 0 0 80 11 59 87.7 6.0 6.3 0 0 100 12 70 87.2 4.4 8.5 0 0 115 11 82 87.0 2.6 15 0 0 130 8 89 86.7 1.5 11.9 0 0 150 7 93 85.6 9 13.5 0 0
Supplementary Table 18. Hydrogenation of cyclooctene Catalyst % Selectivity % Gr 37.0 100 GO 5.6 100 rgo 36.4 100 (N)Gr 2.9 100 (P)Gr 7 100 (S)Gr 2.7 100 Reaction conditions: 26 mg cyclooctene 5 ml heptane 80 C 4h 7mg catalyst 1400 rpm 30 bar H 2
Supplementary Table 19. Hydrogenation of Oleic Acid Catalyst % Selectivity to stearic acid % Gr 22.5 100 GO 3.1 100 rgo 22.8 100 (N)Gr 1.9 100 (P)Gr 9 100