Graphene-Hemin Hybrid Material as Effective Catalyst for

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Supplementary Information
Graphene-hemin hybrid material as effective catalyst for selective oxidation of
primary C-H bond in toluene
Yongjia Li1, Xiaoqing Huang1, Yujing Li1, Yuxi Xu2, Yang Wang1, Enbo Zhu1, Xiangfeng
Duan2,3, Yu Huang1,3*
1
Department of Materials Science and Engineering, 2Department of Chemistry and
Biochemistry, and 3California NanoSystems Institute, University of California, Los
Angeles, California 90095, United States
* To whom the correspondence should be addressed. E-mail: [email protected]
Content
S1: Experimental Methods
Figure S1: Stability of H-GN and GN Samples in Ethanol
Figure S2: XPS Results
Figure S3: AFM Results
Figure S4 and Table S1: Toluene Conversion Process and Selectivity Using TBHP as
Oxidant with Different Catalysts
Figure S5: Comparison of Toluene Conversion with Different H-GN Catalyst
Dosage
Table S2: Comparison of Toluene Conversion and Selectivity by Repeated Addition
of Catalyst
Table S3: Absolute Production of Benzyl Alcohol, Benzaldehyde and Benzoic Acid
Table S4: Comparison of the catalytic activity for oxidation of different substrates
catalyzed by H-GN
Table S5: Comparison of Toluene Oxidation Catalyst Activity of H-GN with Other
Reported Catalysts
Reference
1
S1. Experimental Methods
S1.1. Construction of H-GN
Graphene Oxide (GO) is synthesized by modified Hummer’s method.S1
As-prepared GO aqueous suspension is transferred into ethanol by centrifuge, and
diluted to 0.5 mg/ml. 20 ml GO suspension is then mixed in 50 ml round bottom flask
with 20 ml 0.5 mg/ml hemin solution in ethanol under vigorous stirring. After 30 min,
0.2 ml ammonia (28%) and 50 μl hydrazine hydrate (35%) are added into solution.
After another 30 min vigorous stirring, flask is then placed in oil bath and heated up at
65 oC for 3.5 hours.
Hemin-Graphene (H-GN) dispersion in ethanol is washed by centrifuge for 5
circles to eliminate excessive hemin or hydrazine hydrate. The clean H-GN is stored
at room temperature in sealed vial.
Synthesis of Graphene (GN) is similar to H-GN, except for introduction of hemin
as stabilizer.
S1.2. Catalytic reactions
S1.2.1. Using O2 as oxidant
9 ml toluene is introduced into round bottom flask while vigorously stirring,
0.169 ml t-butyl hydroperoxide (TBHP) in decane (5 mol/l) is then added as initiator.
Slow O2 stream is bubbled continuously into solution. After one hour, desired amount
of H-GN is diluted to 9 ml in ethanol, and added into flask. After another 30 min
stirring, flask is heated up to 60 oC in oil bath. Subsequent catalyst additions (if
required) are done after 7 hours ± 1 min, and very 4 hours ± 1 min afterwards. The
reaction length varies from 12 hours to 48 hours.
S1.2.2. Using TBHP as oxidant
3 ml toluene is added into round bottom flask while vigorous stirring, 5.625 ml
TBHP in decane (5 mol/l) is then added as oxidant. After one hour, desired amount of
H-GN is diluted to 9 ml in ethanol, and added into flask. After another 30 min stirring,
flask is heated up to 80 oC in oil bath. The reaction lasts 12 hours.
2
S1.2.3. Sampling and analysis
Sampling is done per 15 ± 1 min for the first hour and 30 ± 1 min afterwards. All
samples are analyzed using Gas Chromatography-Mass Spectroscopy (GC-MS) with
chlorobenzene as internal standard. All precursors are pre-screened by GC-MS to
filter auto-oxidation products or contaminants.
Stability of H-GN and GN Samples in Ethanol
Figure S1. Representative images of GO, H-GN freshly prepared and after weeks.
a. Freshly made GO (left) and freshly made H-GN (right). b. H-GN in ethanol stored
at room temperature over a month (left). GN in ethanol stored at room temperature for
less than 3 weeks (right).
Stability of H-GN hybrid is tested. After storing H-GN solution for over 3 months,
the solution maintains homogenous and no color change is observed. Comparatively,
GN from GO solution without any stabilizer forms precipitate within less than 3
weeks. Moreover, the thermal stability is examined by annealing H-GN solution at 80
o
C for 48 hours in sealed vial protected by N2 gas. No aggregation or color change is
observed. The Soret band absorbance intensity reduces by less than 10%. Hence, it
clearly indicates H-GN is stable at room and elevated temperatures.
3
XPS Results
Figure S2. XPS survey of GO and H-GN. a. Survey of GO sample. b. Survey of
H-GN sample. c. Deconvolution of C1s in GO sample (1. C-C: 284.6 eV. 2. C-O:
286.7 eV. 3. C=O: 287.6 eV. 4. O=C-O: 288.7 eV). d. Deconvolution of C1s in H-GN
sample (1. C-C: 284.6 eV. 2. C-N: 285.7 eV. 3. C-O: 286.4 eV. 4. C=O: 287.6 eV. 5.
O=C-O: 288.7 eV.). e. Deconvolution of Fe2p in H-GN synthesized in water (1. Fe
2p2/3: 707.1 eV. 2. Fe pre-peak: 705.7 eV. 3. Fe-O: 710.5 eV. 4. Fe 2p1/2: 719.5 eV).S2,
S3
4
AFM Results
Figure S3. AFM results of GN and H-GN. a. Tapping-mode AFM image of GN.
Scale bar = 1 μm. b. Tapping-mode AFM image of H-GN. Scale bar = 1 μm. c. Height
profile of GN with selective line scan (taken along the white line in a.) d. Height
profile of H-GN with selective line scan (taken along the white line in b.)
Different Catalysts
1 µm
Figure S4. Toluene conversion using TBHP as oxidant. Reaction temperature is 80
o
C. Reaction time is 12 hours. Substrate/oxidant molar ratio is 1. Substrate/catalyst
molar ratio is 100,000.
5
Table S1. Comparison of selectivity of toluene oxidation using TBHP as oxidant.
Substrate/oxidant ratio is 1. Substrate/catalyst molar ratio is 100,000. Reaction
temperature is 80 oC and reaction time is 12 hours.
Time
Catalyst
Benzaldehyde %
Benzyl
Benzoic
Alcohol %
Acid %
97.4%
2.6%
0.0%
93.8%
3.2%
3.0
12
92.7%
2.7%
4.6%
4
90.8%
5.4%
3.8%
87.1%
5.0%
7.9%
12
85.6%
4.8%
9.6%
4
97.5%
2.5%
0.0%
92.5%
6.2%
1.3%
12
90.6%
6.2%
3.2%
4
76.7%
13.5%
9.8%
72.0%
13.2%
14.8%
54.7%
17.4%
27.9%
(hours)
4
8
8
8
8
12
N/A
Hemin *
GN †
H-GN
* Substrate/catalyst molar ratio is 100,000. † Dosage of GN is calculated based on GN
mass in H-GN for normal catalytic reaction, with substrate/catalyst molar ratio of
100,000.
6
Comparison of Toluene Conversion with Different H-GN Catalyst Dosage
Figure S5. Comparison of toluene oxidation conversion with different H-GN
catalyst concentrations. O2 is oxidant. O2 pressure is 1 atm. Reaction temperature is
60 oC. Reaction time is 20 hours.
Comparison of Toluene Conversion and Selectivity by Repeated Addition of
Catalyst
Table S2. Comparison of toluene conversion and selectivity with repeated addition of
catalyst. Toluene dosage is 9 ml. O2 is used as oxidant. O2 pressure is 1 atm. Reaction
temperature is 60 oC. Reaction time is 20 hours for single addition and 2 times
addition trials, 30 hours for 5 times and 7 times addition trials. TBHP is used as
initiator. Substrate/initiator molar ratio is 100. Substrate/catalyst molar ratio is
100,000. Catalyst dosage is identical for every addition in all trials.
Part a: Single addition results
Reaction
Conversion
Benzyl
Benzaldehyde
Benzoic
time
(%)
Alcohol
(%)
Acid (%)
(hours)
TON
(%)
0
0.00%
0.00%
0.00%
0.00%
0
1
0.79%
11.6%
88.4%
0.0%
790
2
0.96%
14.3%
82.5%
3.2%
960
3
1.19%
11.5%
79.6%
8.9%
1190
7
4
3.42%
12.5%
78.4%
9.1%
3420
5
4.91%
11.3%
79.7%
9.0%
4910
6
5.57%
12.8%
78.1%
9.1%
5570
7
7.62%
11.4%
78.3%
10.3%
7620
8
8.93%
11.0%
77.6%
11.4%
8930
9
9.12%
10.6%
75.4%
14.0%
9120
10
9.35%
10.4%
76.1%
13.5%
9350
11
9.40%
10.7%
74.9%
14.4%
9400
12
9.42%
10.8%
73.2%
16.0%
9420
13
9.67%
10.1%
69.3%
20.6%
9670
14
9.74%
9.8%
68.5%
21.7%
9740
15
9.82%
9.3%
68.7%
22.0%
9820
16
10.03%
9.7%
64.1%
26.2%
10030
17
10.10%
9.6%
66.2%
24.2%
10100
18
10.14%
8.8%
64.3%
26.9%
10140
19
10.23%
8.6%
60.1%
31.3%
10230
20
10.27%
8.4%
58.7%
32.9%
10270
Part b: 2 times addition results
Addition
Reaction
Conversion
Benzyl
Benzaldehyde
Benzoic
time
(%)
Alcohol
(%)
Acid
(hours)
1st
(%)
TON
(%)
0
0.00%
0.00%
0.00%
0.00%
0
1
0.75%
8.4%
91.2%
0.00%
750
2
0.94%
10.3%
86.4%
3.30%
940
3
1.97%
12.6%
82.4%
5.00%
1970
4
3.65%
12.4%
79.6%
8.00%
3650
5
5.12%
11.4%
79.7%
8.90%
5120
6
6.23%
12.0%
76.5%
11.50%
6230
8
2nd
7
7.28%
12.2%
76.3%
11.50%
7280
8
9.66%
17.4%
65.4%
17.18%
4830
9
11.26%
17.6%
62.3%
20.09%
5630
10
13.42%
16.9%
57.6%
25.50%
6710
11
16.37%
15.8%
52.5%
31.68%
8185
12
16.58%
15.4%
49.4%
35.24%
8290
13
17.38%
14.3%
47.4%
38.28%
8690
14
17.42%
12.7%
45.9%
41.45%
8710
15
17.69%
10.0%
45.3%
44.72%
8845
16
18.23%
9.6%
44.7%
45.69%
9115
17
18.64%
9.4%
44.4%
46.23%
9320
18
18.72%
9.5%
43.9%
46.60%
9360
19
18.79%
8.3%
43.3%
48.42%
9395
20
19.20%
8.7%
41.7%
49.59%
9510
TON
Part c: 5 times addition results
Addition
Reaction
Conversion
Benzyl
Benzaldehyde
Benzoic
time
(%)
Alcohol
(%)
Acid
(hours)
1st
2nd
(%)
(%)
0
0.00%
0.00%
0.00%
0.00%
0
1
0.68%
6.60%
90.60%
2.80%
680
2
1.04%
9.00%
83.40%
7.60%
1040
3
2.41%
11.30%
79.30%
9.40%
2410
4
3.51%
12.80%
78.20%
9.00%
3510
5
4.67%
11.70%
78.50%
9.80%
4670
6
6.04%
12.30%
77.10%
10.60%
6040
7
7.43%
12.20%
75.40%
12.40%
7430
8
8.92%
17.00%
68.10%
14.90%
4460
9
10.13%
16.35%
64.40%
19.25%
5065
9
3rd
4th
5th
10
13.18%
18.86%
59.70%
21.44%
6590
11
15.32%
17.53%
57.30%
25.17%
7660
12
17.91%
20.14%
52.80%
27.06%
5970
13
19.45%
17.70%
49.60%
32.70%
6483
14
21.42%
18.63%
45.70%
35.67%
7140
15
23.42%
16.89%
44.20%
38.91%
7807
16
24.78%
13.73%
43.60%
42.67%
6195
17
26.48%
11.73%
37.60%
50.67%
6620
18
27.39%
13.44%
37.50%
49.06%
6848
19
28.67%
13.77%
34.10%
52.13%
7168
20
30.14%
13.76%
30.00%
56.24%
6028
21
31.22%
11.49%
29.80%
58.71%
6244
22
32.65%
10.57%
27.40%
62.03%
6530
23
32.74%
9.23%
25.30%
65.47%
6548
24
33.06%
11.42%
25.40%
63.18%
6612
25
34.26%
10.91%
21.50%
67.59%
6852
26
34.31%
9.47%
21.30%
69.23%
6862
27
34.43%
9.18%
20.60%
70.22%
6886
28
34.57%
7.96%
20.80%
71.24%
6914
29
34.70%
5.28%
20.40%
74.32%
6940
30
34.75%
6.20%
19.60%
74.20%
6946
TON
Part d: 7 times addition results
Addition
Reaction
Conversion
Benzyl
Benzaldehyde
Benzoic
time
(%)
Alcohol
(%)
Acid
(hours)
1st
(%)
(%)
0
0.00%
0.00
0.00
0.00%
0
1
0.69%
6.2%
89.4%
4.4%
690
2
1.25%
10.5%
84.2%
5.3%
1250
10
2nd
3rd
4th
5th
6th
7th
3
1.87%
11.2%
80.6%
8.2%
1870
4
3.25%
13.3%
76.3%
10.4%
3250
5
4.33%
10.2%
78.2%
11.6%
4330
6
5.38%
10.8%
77.5%
11.7%
5380
7
7.02%
12.1%
74.7%
13.2%
7020
8
9.23%
16.0%
68.4%
15.6%
4615
9
10.48%
13.1%
64.6%
22.3%
5240
10
12.23%
15.4%
62.7%
21.9%
6115
11
16.01%
14.3%
57.9%
27.8%
8005
12
18.29%
16.7%
53.6%
29.7%
6097
13
19.80%
16.9%
52.7%
30.4%
6600
14
22.28%
12.8%
48.6%
38.6%
7427
15
24.52%
15.2%
42.1%
42.7%
8173
16
26.01%
12.9%
40.6%
46.5%
6503
17
27.44%
8.2%
42.7%
49.1%
6860
18
28.69%
9.0%
38.6%
52.4%
7173
19
30.34%
8.4%
35.2%
56.4%
7585
20
32.18%
8.1%
33.6%
58.3%
6436
21
34.70%
5.9%
31.7%
62.4%
6940
22
35.68%
5.1%
30.6%
64.3%
7136
23
35.92%
6.5%
26.8%
66.7%
7184
24
36.82%
4.9%
24.7%
70.4%
6137
25
37.34%
7.6%
23.9%
68.5%
6223
26
38.14%
7.3%
20.4%
72.3%
6357
27
38.54%
3.0%
18.6%
78.4%
6423
28
39.23%
2.4%
16.3%
81.3%
5604
29
39.72%
1.1%
15.7%
83.2%
5674
30
40.56%
2.2%
12.1%
85.7%
5794
11
Absolute Production of Benzyl Alcohol, Benzaldehyde and Benzoic Acid
Table S3. Absolute production of benzyl alcohol, benzaldehyde and benzoic acid.
Reaction temperature is 60 oC. Reaction time varies from 12 hours to 30 hours.
Catalysts used include hemin, H-GN and reference without catalyst. O2 is used as
oxidant. O2 pressure is 1 atm. TBHP is used as initiator. Substrate/catalyst molar ratio
is 100,000. Substrate/initiator molar ratio is 100. In repeated addition trials, dosage of
H-GN from each addition in all trials is identical. Absolute production is calculated by
multiplying selectivity of respective product with overall conversion of toluene.
Part a: Without catalyst result
Reaction
Conversion
time (hours)
(%)
Absolute Production
Benzyl
Benzaldehyde Benzoic Acid
Alcohol (%)
(%)
(%)
0
0.00%
0.00%
0.00%
0.00%
1
0.00%
0.00%
0.01%
0.00%
2
0.01%
0.00%
0.02%
0.00%
3
0.02%
0.00%
0.05%
0.00%
4
0.05%
0.00%
0.08%
0.00%
5
0.08%
0.00%
0.09%
0.00%
6
0.10%
0.00%
0.11%
0.00%
7
0.12%
0.00%
0.12%
0.00%
8
0.13%
0.00%
0.14%
0.00%
9
0.15%
0.00%
0.16%
0.01%
10
0.17%
0.01%
0.18%
0.01%
11
0.19%
0.01%
0.19%
0.01%
12
0.21%
0.01%
0.20%
0.01%
12
Part b: Hemin result
Reaction
Conversion
time (hours)
(%)
Absolute Production
Benzyl
Benzaldehyde Benzoic Acid
Alcohol (%)
(%)
(%)
0
0.00%
0.00%
0.00%
0.00%
1
0.15%
0.01%
0.14%
0.01%
2
0.23%
0.01%
0.21%
0.01%
3
0.34%
0.02%
0.31%
0.01%
4
0.36%
0.02%
0.33%
0.01%
5
0.39%
0.03%
0.35%
0.02%
6
0.41%
0.01%
0.36%
0.04%
7
0.43%
0.02%
0.38%
0.02%
8
0.61%
0.03%
0.53%
0.05%
9
0.73%
0.05%
0.62%
0.06%
10
0.82%
0.05%
0.70%
0.07%
11
0.94%
0.06%
0.79%
0.08%
12
1.02%
0.05%
0.87%
0.10%
Part c: H-GN single addition results
Reaction
Conversion
time (hours)
(%)
Absolute Production
Benzyl
Benzaldehyde Benzoic Acid
Alcohol (%)
(%)
(%)
0
0.00%
0.00%
0.00%
0.00%
1
0.79%
0.09%
0.70%
0.00%
2
0.96%
0.14%
0.79%
0.03%
3
1.19%
0.14%
0.95%
0.11%
4
3.42%
0.43%
2.68%
0.31%
5
4.91%
0.55%
3.91%
0.44%
6
5.57%
0.71%
4.35%
0.51%
13
7
7.62%
0.87%
5.97%
0.78%
8
8.93%
0.98%
6.93%
1.02%
9
9.12%
0.97%
6.88%
1.28%
10
9.35%
0.97%
7.12%
1.26%
11
9.40%
1.01%
7.04%
1.35%
12
9.42%
1.02%
6.90%
1.51%
13
9.67%
0.98%
6.70%
1.99%
14
9.74%
0.95%
6.67%
2.11%
15
9.82%
0.91%
6.75%
2.16%
16
10.03%
0.97%
6.43%
2.63%
17
10.10%
0.97%
6.69%
2.44%
18
10.14%
0.89%
6.52%
2.73%
19
10.23%
0.88%
6.15%
3.20%
20
10.27%
0.86%
6.03%
3.38%
Part d: H-GN 2 times addition results
Addition
Reaction
Conversion
time
(%)
(hours)
1st
2nd
Absolute Production
Benzyl
Benzaldehyde
Benzoic
Alcohol(%)
(%)
Acid (%)
0
0.00%
0.00%
0.00%
0.00%
1
0.75%
0.06%
0.68%
0.00%
2
0.94%
0.10%
0.81%
0.03%
3
1.97%
0.25%
1.62%
0.10%
4
3.65%
0.45%
2.91%
0.29%
5
5.12%
0.58%
4.08%
0.46%
6
6.23%
0.75%
4.77%
0.72%
7
7.28%
0.89%
5.55%
0.84%
8
9.66%
1.68%
6.32%
1.66%
9
11.26%
1.98%
7.02%
2.26%
14
10
13.42%
2.27%
7.73%
3.42%
11
16.37%
2.59%
8.60%
5.19%
12
16.58%
2.55%
8.18%
5.84%
13
17.38%
2.49%
8.24%
6.65%
14
17.42%
2.21%
7.99%
7.22%
15
17.69%
1.77%
8.01%
7.91%
16
18.23%
1.75%
8.15%
8.33%
17
18.64%
1.75%
8.27%
8.62%
18
18.72%
1.78%
8.22%
8.72%
19
18.79%
1.56%
8.13%
9.10%
20
19.20%
1.65%
7.93%
9.43%
Part e: H-GN 5 times addition results
Addition
Reaction
Conversion
time
(%)
(hours)
1st
2nd
3rd
Absolute Production
Benzyl
Benzaldehyde
Benzoic
Alcohol(%)
(%)
Acid (%)
0
0.00%
0.00%
0.00%
0.00%
1
0.68%
0.04%
0.62%
0.02%
2
1.04%
0.09%
0.87%
0.08%
3
2.41%
0.27%
1.91%
0.23%
4
3.51%
0.45%
2.74%
0.32%
5
4.67%
0.55%
3.67%
0.46%
6
6.04%
0.74%
4.66%
0.64%
7
7.43%
0.91%
5.60%
0.92%
8
8.92%
1.52%
6.07%
1.33%
9
10.13%
1.66%
6.52%
1.95%
10
13.18%
2.49%
7.87%
2.83%
11
15.32%
2.69%
8.78%
3.86%
12
17.91%
3.61%
9.46%
4.85%
13
19.45%
3.44%
9.65%
6.36%
15
4th
5th
14
21.42%
3.99%
9.79%
7.64%
15
23.42%
3.96%
10.35%
9.11%
16
24.78%
3.40%
10.80%
10.57%
17
26.48%
3.11%
9.96%
13.42%
18
27.39%
3.68%
10.27%
13.44%
19
28.67%
3.95%
9.78%
14.95%
20
30.14%
4.15%
9.04%
16.95%
21
31.22%
3.59%
9.30%
18.33%
22
32.65%
3.45%
8.95%
20.25%
23
32.74%
3.02%
8.28%
21.43%
24
33.06%
3.78%
8.40%
20.89%
25
34.26%
3.74%
7.37%
23.16%
26
34.31%
3.25%
7.31%
23.75%
27
34.43%
3.16%
7.09%
24.18%
28
34.57%
2.75%
7.19%
24.63%
29
34.70%
1.83%
7.08%
25.79%
30
34.75%
2.15%
6.81%
25.77%
Part f: H-GN 7 times addition results
Addition
Reaction
Conversion
time
(%)
(hours)
1st
Absolute Production
Benzyl
Benzaldehyde
Benzoic
Alcohol(%)
(%)
Acid (%)
0
0.00%
0.00%
0.00%
0.00%
1
0.69%
0.04%
0.62%
0.03%
2
1.25%
0.13%
1.05%
0.07%
3
1.87%
0.21%
1.51%
0.15%
4
3.25%
0.43%
2.48%
0.34%
5
4.33%
0.44%
3.39%
0.50%
6
5.38%
0.58%
4.17%
0.63%
16
2nd
3rd
4th
5th
6th
7th
7
7.02%
0.85%
5.24%
0.93%
8
9.23%
1.48%
6.31%
1.44%
9
10.48%
1.37%
6.77%
2.34%
10
12.23%
1.88%
7.67%
2.68%
11
16.01%
2.29%
9.27%
4.45%
12
18.29%
3.05%
9.80%
5.43%
13
19.80%
3.35%
10.43%
6.02%
14
22.28%
2.85%
10.83%
8.60%
15
24.52%
3.73%
10.32%
10.47%
16
26.01%
3.36%
10.56%
12.09%
17
27.44%
2.25%
11.72%
13.47%
18
28.69%
2.58%
11.07%
15.03%
19
30.34%
2.55%
10.68%
17.11%
20
32.18%
2.61%
10.81%
18.76%
21
34.70%
2.05%
11.00%
21.65%
22
35.68%
1.82%
10.92%
22.94%
23
35.92%
2.33%
9.63%
23.96%
24
36.82%
1.80%
9.09%
25.92%
25
37.34%
2.84%
8.92%
25.58%
26
38.14%
2.78%
7.78%
27.58%
27
38.54%
1.16%
7.17%
30.22%
28
39.23%
0.94%
6.39%
31.89%
29
39.72%
0.44%
6.24%
33.05%
30
40.56%
0.89%
4.91%
34.76%
17
Comparison of the catalytic activity for oxidation of different substrates
catalyzed by H-GN
Table S4. Comparison of the catalytic activity for oxidation of different substrates
catalyzed by H-GN. Reaction temperature is 60 oC. Reaction time is 12 hours. O2 is
oxidant and O2 pressure is 1 atm. TBHP is initiator. Substrate/catalyst molar ratio is
100,000. Substrate/initiator molar ratio is 100.
Substrate
Time
Conv.
hours
%
Main Product Selectivity (%)
Acetophenone
Phenylethanol
TON
Ethyl6
8.43%
52.17%
43.71%
8430
12
12.62%
54.26%
41.23%
12620
Cyclohexanone
Cyclohexanol
benzene
Cyclo6
6.41%
64.12%
12.08%
6410
12
8.24%
57.28%
14.93%
8240
Benzaldehyde
Styrene Oxide
hexane
Styrene
6
12.38%
76.4%
15.5%
12380
12
23.12%
73.6%
16.1%
23120
18
Comparison of Toluene Oxidation Catalyst Activity of H-GN with Other Reported Catalysts
Table S5. Results obtained from previous studies on toluene oxidation catalysts
Catalyst
Support
Temp Pressure
(oC)
(atm)
Selectivity
Oxidant Conv %
Benzyl
Benzalde
Benzoic
Benzyl
Alcohol %
-hyde %
Acid %
Benzoate %
TON
Ref.
Hemin
Graphene 60
1
O2
50.14
2.59
3.13
94.28
-
4170
S4
Cu-Mn
-
190
10
O2
21.6
1.6
9.2
73.7
13.6
8
S5
Cu-Fe
Al2O3
190
10
O2
25.4
1.0
27.4
71.6
-
74
S6
MnCO3
-
190
10
O2
25.0
5.3
9.7
80.8
-
50
S7
CoSBA-15
-
80
1
TBHP
8.0
-
64.0
-
-
103
S8
Cr
Silicalite
80
1
TBHP
18.4
5.2
23.3
25.7
-
-
S9
Au-Pd
Carbon
160
10
O2
50.8
0.1
1.1
4.5
94.3
3300
S10
Au-Pd
TiO2
160
10
O2
24.1
0.5
1.2
2.8
95.5
1570
S10
Mn(TF5PP)Cl -
20
1
H2O2
26.0
3.0
-
55.0
-
-
S11
(FeIIITPP)Cl
Chitosan
190
6
Air
5.5
50.3
40.4
9.3
-
6130000 S12
Fe(TPFPP)Cl
-
120
1
O2
0.4
33.3
66.7
-
-
1200
S13
19
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21
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