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Page 1 of 23 Analytical Methods

1
2
3 1 Capillary Column Coated with Graphene Quantum Dots for
4
5 2 Gas Chromatographic Separation of Alkanes and Aromatic
6 3 Isomers
7
8 4 Xueyan Zhanga, Hongyun Jib, Xudong Zhangb, Zhen Wanga and Dan Xiao a, b, *
9 a
10
5 College of Chemistry, Sichuan University, Chengdu, 610064, P. R. China
b
6 College of Chemical Engineering, Sichuan University, Chengdu, 610065, P. R. China

Analytical Methods Accepted Manuscript

11
12
7 *Corresponding author：
13
8 E-mail: xiaodan@scu.edu.cn (Dan Xiao)
9 Tel: +86-28-85415029
14
10 Fax: +86-28-85416029
15
16 11 Abstract
17
18 12 Graphene Quantum Dots (GQDs) have potential to be an excellent stationary phase
19 13 because of its high surface area, adsorption affinities and rich functional groups. The
20 14 rich functional groups of GQDs can form hydrogen bonding and π-π electrostatic
21
22
15 stacking interactions with volatile aromatic compounds or unsaturated organic
23 16 compounds. Herein GQDs were explored as the stationary phase for gas
24 17 chromatographic capillary column separation of alkanes and aromatic isomers with
25
18 3-aminopropyldiethoxymethyl silane (3-AMDS) as coupling reagent. GQDs coated
26
27 19 capillary column exhibits high separation efficiency of ethylbenzene, styrene, xylene,
28 20 propylbenzene, alkanes, and dichlorobenzene isomers at low temperature. The elution
29 21 sequence of the analytes follows an increasing order of their boiling points, even for
30
31 22 p-dichlorobenzene and m-dichlorobenzene, which have close boiling points
32 23 (p-dichlorobenzene, 173.4 oC, m-dichlorobenzene, 173 oC). The separation behavior
33 24 of the column upon different organic substances is related to the van der Waals forces
34
35 25 or π-π interaction between the tested analytes and GQDs. Compared with the
36 26 commercial HP-5 and HP-innowax capillary columns, the GQDs allowed fast and
37 27 efficient separation of the analytes at low temperature without
38
39 28 temperature-programming. The relative standard deviations (RSD) of five replicate
40 29 separations for the tested analytes on GQDs coated capillary column were 0.1-1.6%,
41 30 0.7-4.0%, 0.8-8.5%, and 1.2-2.2% for retention time, peak area, peak height, half peak
42
43
31 width, respectively.
44 32 Keywords: Graphene quantum dots, Stationary phase, Gas chromatography,
45 33 Isomers, Separation.
46
34
47
48 35
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50
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52
53
54
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59 1
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 Analytical Methods Page 2 of 23

1
2
3 36 Introduction
4
37 Gas chromatography (GC), which is one of the most important separation
5
6 38 methods for volatile compounds, has been under intensive development in recent
7 39 years. The chromatographic column is the heart of gas chromatographic system. In
8 40 order to obtain a column with high separation efficiency and good reproducibility, the
9
10 41 stationary phases should have the characteristics of narrow size distribution, high

Analytical Methods Accepted Manuscript

11 42 surface area and thermal stability. Carbon based materials have long been used for the
12 43 adsorption and separation of volatile organic compounds 1. In the field of large carbon
13
14 44 materials, carbon nanoparticles have generated tremendous research excitement as gas
15 45 and liquid stationary phases because these nanoparticles possess a large
16 46 surface-to-volume ratio, they create unique opportunities for the exploitation of higher
17
18 47 performance separation techniques. In order to get the stationary phases which have
19 48 high resolution and selectivity, chromatographers have explored various carbon
20 49 based materials such as graphene 2, 3，carbon nanotubes 4-9 and fullerene 10 as the
21
22
50 adsorbents in GC. These carbon based materials, especially the carbon nanotubes,
23 51 have been widely used as stationary phases in gas chromatography because of its
24 52 exceptional features, namely high surface area, high aspect ratio and the ability to
25
53 provide π-π electrostatic stacking interaction with aromatic and unsaturated
26
27 54 compounds. Carbon nanotubes had been employed on the separation of standard
28 55 mixtures such as alkanes11, 12, alcohols8, 11, aromatic compounds8, 11, 12 and ketones11 ,
29 56 but bare carbon nanotubes were difficult to handle because they were insoluble in
30
31 57 most solvents. In order to optimize the separation effect as GC stationary phase, bare
32 58 carbon nanotubes should be often modified to get functionalized carbon nanotubes.
33 59 Graphene (G) has aroused great interest among the researchers because of its
34
35 60 excellent thermal properties, large adsorptivity affinities, ultra high surface area and
36 61 the large delocalized π-electron system. G has been demonstrated to be a promising
37 62 material for chromatographic separation 13 and extraction 14-17. Graphene oxide (GO),
38
39 63 a precursor of graphene, contains heavily oxygenated groups. The functional groups
40 64 of GO can be assembled onto many support surfaces. For example, an octadecylsilane
41 65 functionalized GO/silica stationary phase had been explored for the separation of
42
43
66 alkylbenzenes, amines and phenolic compounds in reversed-phase liquid
44 67 chromatography 18, 19. GQDs, which consist of a single atomic layer of nano-sized
45 68 graphite, possess most of the advantages of graphene and GO. Due to the existence of
46
69 hydroxyl, epoxy and carboxyl groups, GQDs show nice properties similar to those of
47
48 70 GO, such as excellent water solubility and hydrophilicity 20. What’s more,
49 71 supramolecular interaction (mainly the CH-π interaction), the π-π conjugated network
50 72 and surface groups offer abundant binding sites for the analytes. In recent years, G
51
52 73 and GO had been used for solid-phase microextraction of pyrethroid pesticides 21.
53 74 Besides, Qu and Gu had reported that GO could be used for gas chromatography 22.
54 75 However, the researches of GQDs had still mainly focused on its quantum
55
56 76 confinement , edge effects 23 and its application on photovoltaic devices, biosensing
57 77 and imaging 24. To the best of our knowledge, no recent survey showed an available
58
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Page 3 of 23 Analytical Methods

1
2
3 78 report on the utilization of GQDs as a stationary phase for gas chromatographic
4
79 separation, even though the high surface area, functional groups were advantageous to
5
6 80 the fabrication of GQDs coated capillary column by a dynamic coating method.
7 81 What’s more, reducing the particle size of stationary phase will improve mass transfer
8 82 in gas chromatography. Herein, we report the application of GQDs as an efficient
9
10 83 stationary phase for GC separation. The capillary wall coated with GQDs will

Analytical Methods Accepted Manuscript

11 84 increase the column’s phase ratio. GQDs were immobilized onto the capillary wall
12 85 using 3-aminopropyldiethoxymethyl silane as coupling reagent 25-27. The
13
14 86 chromatographic performance of capillary column coated with GQDs was evaluated
15 87 by alkanes and aromatic isomers.
16 88 Alkanes play significant roles in petroleum refining 28, while ethylbenzene (EB),
17
18 89 styrene, propylbenzene, dichlorobenzene and xylene isomers are important
19 90 constituents of raw chemicals in modern industry 29, 30. For instance, EB is
20 91 dehydrogenated to styrene for polystyrene, p-xylene is used as the reactant of poly
21
22
92 (ethylene terephthalate) (PET), and o-xylene is widely used to produce phthalic
23 93 anhydride. Propylbenzene and dichlorobenzene isomers are extensively applied as
24 94 industrial solvents or chemical materials in the production of pesticides, herbicid and
25
95 deodorant. Alkanes and aromatic isomers are usually separated for analytical purposes
26
27 96 on capillary column coated with metal-organic frameworks, which act as a molecular
28 97 sieve, but the diffusivities of these analytes are very low in the phase. So effective
29 98 method for the rapid gas chromatographic separation still needs to be optimized. The
30
31 99 stationary phases, such as diphenyl-phenyl polysiloxane 31, β-cyclodextrin 32, UIO-66
33
32 100 , gold nanoparticles 34 , imidazolium ionic polymer35 and carbon nanotubes 5, 8, 36
33 101 , have been successfully applied as GC separation, but high temperature 9, 35-37, long
34
35 102 analysis time 31, 38 or temperature-programming 6, 8 33, 39 are often needed.
36
37 103 In our work, GQDs were first investigated as a novel stationary phase for gas
38 104 chromatography separation of alkanes, EB, styrene, propylbenzene, dichlorobenzene
39 105 and xylene isomers. The capillary column coated with GQDs we prepared achieves a
40
41 106 good separation of these isomers, what’s more, it only needs short analysis time and
42 107 the separation temperature was low. The effects of temperature and injected mass of
43 108 analytes were also investigated.
44
45 109 Experimental
46 110 Chemicals and reagents
47 111 All chemicals and reagents were of analytical grade or above. Ultrapure water
48
49 112 (18.2 MΩ cm) was obtained from a Milli-Q water purification system (Millipore,
50 113 Bedford, MA, USA). Graphite powder was bought from Huayi Company (Shanghai,
51 114 China). Phosphorus pentoxide (P4O10), hydrogen peroxide (H2O2, 30%), sulfuric acid
52
53
115 (H2SO4, 98%), potassium permanganate (KMnO4, >99.5%), sodium hydroxide
54 116 (NaOH), hexane, heptane, octane, nonane, decane, acetone, ethylbenzene, styrene and
55 117 1, 3, 5-trimethylbenzene were purchased from Kelong Technological Co. (Sichuan,
56
118 China). Sec-, n-, isopentanol and o-, m-, p-dichlorobenzene were bought from
57
58 119 Shanghai Chemical Reagent Co. (Shanghai, China). Potassium peroxydisulfate
59 3
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 Analytical Methods Page 4 of 23

1
2
3 120 (K2S2O8, >99.5%), 2, 4-dimethylhexane and 3-methylheptane were obtained from
4
121 Sinopharm Chemical Reagent Co. (Shanghai, China). n- Propylbenzene,
5
6 122 isopropylbenzene, n-butylbenzene, sec-butylbenzene and tert-butylbenzene were
7 123 bought from Aladdin Chemistry Co. Ltd. (Shanghai, China). o-Xylene, m-xylene and
8 124 p-xylene were purchased from Tianjin Kermel Chemical Reagent (Tianjin, China).
9
10 125 Isooctane was from Tianjin Meilin Industry and Trade Co. (Tianjin, China). All the

Analytical Methods Accepted Manuscript

11 126 chemicals were used without further purification. 3-AMDS was purchased from
12 127 sigma (St. Louis, MO).
13
14 128 Instrumentation
15 129 The TEM images were conducted by a Hitachi H-800 electron microscope
16 130 operating at an acceleration voltage of 200 kV. The thermal gravimetric analysis
17
18 131 (TGA) was performed on a TA Q500 thermogravimetric analyzer (TA, USA) from
19 132 room temperature to 600 oC at a heating rate of 8 oC min-1 under nitrogen. SEM
20 133 images were performed by a Hitachi S-4800 ultra-high resolution field emission
21
22
134 scanning electron microscope (Tokyo, Japan) to investigate the inner wall of the
23 135 GQDs coated capillary column. X-ray photoelectron spectroscopy (XPS) spectra of
24 136 the samples were measured by a Kratos XSAM 800 system for observing chemical
25
137 composition and dispersion of species with a mono X-ray source Al Kα excitation
26
27 138 (1486.6 eV).
28 139 All separations were performed on a Fuli model 9790 series GC equipped with a
29 140 flame ionization detector (FID) (Shanghai, China). The data acquisition and
30
31 141 processing were controlled by N3000 chemstation software (Zhejiang University,
32 142 China). The carrier gas was nitrogen (99.999%). The injector temperature of the gas
33 143 chromatograph was set to 250 oC, and the temperature of FID was set to 290 oC. The
34
35 144 split ratio was 16:1. The commercial HP-5 (30 m, 0.32 mm i.d., 0.25 µm film
36 145 thickness) and HP-innowax (20 m, 0.32 mm i.d., 0.25 µm film thickness ) capillary
37 146 columns from Agilent Technologies were employed for comparison.
38
39 147 Synthesis of GQDs
40 148 GO was synthesized from natural graphite powder by a modified Hummers
41 149 method 40. In this work, GQDs were prepared according to literature procedure 41.
42
43
150 Briefly, GO (0.5 mg mL-1) was dispersed in deionized water with hydrogen peroxide
44 151 (0.05 mL) added to the solution, then the mixture was re-oxided for 1 h by ozone
45 152 which was produced by an OZ-7G Ozone Generator. After these procedures, the
46
153 mixture was transferred to a poly (tetrafluoroethylene) (Teflon)-lined autoclave (50
47
48 154 mL) and heated for 10 h at 200 oC. The products we got contained orange transparent
49 155 suspension and black sediments. The suspension was further filtered through a 0.22
50 156 µm microporous membrane to remove the large tracts of GO and the greenish yellow
51
52 157 fluorescent GQDs were obtained.
53 158 Capillary pretreatment and preparation of GQDs coated capillary
54
55
159 columns
56 160 A fused silica capillary (22 m long × 0.32 mm i.d.) (Yongnian Ruifeng Optic
57 161 Fiber Plant, Hebei, China) was treated according to the following recipe prior to
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Page 5 of 23 Analytical Methods

1
2
3 162 coating 22, 42: the capillary was washed sequentially with 1 M NaOH for 2 h, ultrapure
4
163 water for 30 min, 0.1 M HCl for 2 h, and ultrapure water until the outflow reached pH
5
6 164 7.0. Finally, the capillary was dried with a nitrogen purge at 120 oC overnight.
7 165 After drying with nitrogen, the capillary column was flushed with 3 mL
8 166 3-AMDS toluene solution (1 vol%) to modify the inner surface of the capillary
9
10 167 column through covalent interaction between hydroxy groups and 3-AMDS. The
capillary column was kept at 80 oC for 12 h and then flushed with nitrogen. The

Analytical Methods Accepted Manuscript

11 168
12 169 GQDs were coated onto the inner wall of the pretreated capillary by a dynamic
13
14 170 coating method as follows: The solution of GQDs in ethanol was filled with a plug
15 171 into the capillary column under N2, and then pushed through the column at a velocity
16 172 of 30 cm·min-1, leaving a wet coating layer on the inner wall of the capillary column.
17
18 173 In order to avoid acceleration of solution plug near the end of the column, a 1 m long
19 174 buffer tube (0.32 mm i.d.) was attached to the capillary column end as a restrictor.
20 175 After coating, the capillary column was settled for 2 h for conditioning under gaseous
21
22
176 N2. The procedure could be repeated to increase the surface coverage. Further
23 177 conditioning of the capillary column was carried out by employing a temperature
24 178 program including three steps: 50 oC for 180 min, ramp from 50 oC to 100 oC at a rate
25
179 of 1 oC·min-1 and 100 oC for 600 min.
26
27 180 Determination of McReynolds constants
28 181 As the most widely used system for evaluating the classification of novel
29 182 chromatographic stationary phases, McReynolds constants were commonly employed
30
31 183 to characterize the polarity of the stationary phases by choosing five probe
32 184 compounds, namely benzene, n-butanol, 2-pentanone, nitropropane and pyridine. The
33 185 respective constants of the five probe compounds were thought to evaluate various
34
35 186 interactions between the stationary phase and the analytes in a particular way: X
36 187 represents benzene, which is related to weak dispersion forces and the polarizability
37 188 character of the phase. Y is for n-butanol, which indicates the hydrogen-bonding
38
39 189 ability of the phase. Z represents 2-pentanone, whose behavior relates to the
40 190 polarizability and part of the dipolar character of the stationary phase. U refers to
41 191 nitropropane, which is related to the electron donor, electron acceptor and dipolar
42
43
192 character of the phase. S refers to pyridine, a strong proton acceptor and polar
44 193 molecule, which indicates the acidic character of the phase 43.
45 194 Results and discussion
46
47
195 Characterization of the synthesized GQDs and capillary column
48 196 coated with GQDs
49 197 Fig. 1A showed the TEM image of GQDs, and the inset in Fig. 1A was the
50 198 representative image of individual GQDs, which was high crystallinity. To investigate
51
52 199 the chemical composition variation of the GO before and after the treatment of ozone
53 200 and hydrothermal reaction, The XPS spectra were acquired. From Fig. 2A, we can see
54 201 that the four C1s peaks can be assigned to C=C/C-C, C-O, C=O, and O-C=O,
55
56 202 respectively. It was obvious that GQDs were functionalized with hydroxyl, carbonyl,
57 203 epoxy, and carboxylic acid groups, while the GO only contained C=C and C-O before
58
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 Analytical Methods Page 6 of 23

1
2
3 204 treatment. The TGA curve revealed that the GQDs were stable up to 100 oC (Fig. 1B).
4
205 Although it showed poor thermostability, we could still obtain good separation of
5
6 206 aromatic isomers under low temperature. Fig. S1 showed SEM images of the bare
7 207 fused silica capillary column. We could see that the inner surface of the bare silica
8 208 capillary column was smooth after the treatment of 1 M NaOH. After coating, the
9
10 209 inner surface of the fabricated open tubular column became roughened (Fig. 2B), it

Analytical Methods Accepted Manuscript

11 210 also indicated that GQDs were successfully immobilized onto the capillary column.
12 211 But the GQDs on the capillary wall were not evenly distributed. The column was
13
14 212 coated with GQDs in a thin film with an average thick of ≈50 nm.
15 213 Performance of GQDs coated capillary column for gas
16 214 chromatographic separation of alkanes, EB, styrene, xylene,
17
18 215 propylbenzene, dichlorobenzene isomers
19 216 In order to investigate the separation capability of GQDs coated capillary column,
20 217 we chose alkanes, EB, styrene, xylene, propylbenzene, dichlorobenzene isomers as
21
22
218 the tested analytes. The GQDs coated capillary column also exhibited good separation
23 219 with good precision (0.1-1.6%, 0.7-4.0%, 0.8-8.5%, and 1.2-2.2% ((RSD, n=5) for
24 220 retention time, peak area, peak height, and half peak width, respectively) (Table 1).
25
221 The gas chromatographic separation effect of GQDs coated capillary column
26
27 222 were examined by alkanes with a wide range of boiling points, because alkanes play
28 223 an important role in petroleum refining. We chose linear alkanes with the number of
29 224 carbon atoms over 6 (Fig. 3A) to evaluate the potential application of GQDs coated
30
31 225 capillary column. We successfully separated five alkanes within 5 min at low
32 226 temperature. The elution sequence of alkanes on GQDs capillary column followed the
33 227 order of boiling points, which was similar to the traditional stationary phase such as
34
35 228 (5%-phenyl)-methylpolysiloxane. The relatively stronger van der Waals interaction
36 229 between alkanes and the framework of GQDs made linear alkanes well separated
37 230 from each other.
38
39 231 Fig. 3B showed the separation of isooctane, n-octane, 3-methylheptane, and 2,
40 232 4-dimethylhexane on GQDs column at 40 oC. The column could efficiently separate
41 233 2, 4-dimethylhexane from 3-methylheptane at 40 oC. The elution sequence of the
42
43
234 octane isomers on GQDs coated capillary column followed the order of boiling points
44 235 (2,4-dimethylhexane, 109 oC, 3-methylheptane, 118 oC, n-octane, 125.8 oC). The
45 236 retention of alkanes on the capillary column mainly depended on their van der Waals
46
237 interactions with GQDs. The 2,4-dimethylhexane molecule, which had shorter linear
47
48 238 chain, had a weaker van der Waals interaction with GQDs, so it eluted faster than
49 239 3-methylheptane. The same trend was observed for 3-methylheptane and n-octane.
50 240 Our GQDs coated capillary column also exhibited high selectivity for the
51
52 241 separation of EB and styrene. Their separation was also achieved on GQDs coated
53 242 capillary column (Fig. 4A). EB and styrene were baseline separated with a selectivity
54 243 of 1.8 , indicating that the π-π interaction between the styrene and aromatic
55
56 244 framework walls of GQDs served an important function in the good separation.
57 245 Besides, we could also find the same elution order of EB and styrene on HP-5 (Fig.
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Page 7 of 23 Analytical Methods

1
2
3 246 S2) and HP-innowax (Fig. S3). On commercial HP-5 column, the selectivity of EB
4
247 and styrene was 1.3, lower than 1.8, which was obtained on GQDs coated capillary
5
6 248 column at 40 oC. In addition, compared with HP-5, the analysis time was greatly
7 249 shortened, so the GQDs column provided us an efficient approach to lower the
8 250 analysis time without sacrificing selectivity.
9
10 251 EB and xylene isomers play significant roles in air monitoring44 and blood
analysis45. However, the separation of EB and xylene isomers was a technical

Analytical Methods Accepted Manuscript

11 252
12 253 challenge due to the similarity of their boiling points and dimensions 28. In recent
13
14 254 years, they had been triumphantly separated by MIL-53(Al)46. Here, EB and xylene
15 255 isomers were also chosen to test the feasibility of GQDs coated capillary column in
16 256 gas chromatography. The chromatograms obtained on GQDs capillary column under
17
18 257 chromatographic conditions were shown in Fig. 4B and Fig. S4, indicating that the
19 258 p-xylene and m-xylene were eluted at equal retention time. The capillary column
20 259 coated with GQDs was also investigated for gas chromatographic separation of
21
22
260 dichlorobenzene, propylbenzene (Fig. 4C and 4D), butylbenzene and pentanol
23 261 isomers (Fig. 5). The column offered good separation for these isomers. The peak
24 262 symmetry of pentanol isomers was poor, indicating that pentanols showed strong
25
263 hydrogen bond interaction with GQDs.
26
27 264 Dichlorobenzene isomers showed stronger retention than propylbenzene, EB,
28 265 and xylene isomers, indicating that dichlorobenzene isomers had stronger interaction
29 266 with GQDs because of the polar character contributed by hydroxyl and carboxyl
30
31 267 groups, which enhanced the ability of polar affinity. The easier elution of p-xylene
32 268 could be attributed to its lower dipole moment compared to o-xylene. What’s more,
33 269 o-xylene had the strongest van der Waals interaction and the highest polarity (dipole
34
35 270 moment 0.54 D) among its four isomers. The dipole-induced hydrogen-bonding
36 271 provided by the interaction of acid sites and o-xylene also made contribution to the
37 272 good separation, so o-xylene was more strongly retained than EB and p-xylene. The
38
39 273 elution order of EB, xylene, propylbenzene and dichlorobenzene isomers is the same
40 274 for the commercial HP-5 (Fig. S2) and HP-innowax (Fig. S3) capillary columns.
41 275 Besides, the elution order of EB and xylene isomers on GQDs coated capillary
42
43
276 column follows the order of boiling points while MIL-10147 is not. On MIL-101
44 277 column, p-xylene, whose boiling point is higher than EB, elutes earlier than EB. The
45 278 reason of this phenomenon may be that pore-filling effect plays significant roles on
46
279 MIL-101 column while van der Waals makes great contribution on GQDs coated
47
48 280 capillary column.
49 281 In addition, the polarity of the column was expressed by McReynolds constants
50 282 at 100 oC. The values for the stationary phase of GQDs were obtained in the study
51
52 283 while the data for OV-22 and DB-5 were taken from the literature with the purpose of
53 284 making comparison48. The average polarity of the stationary phases was listed in
54 285 Table 2. It was found that the polarity of GQDs coated capillary column was 161，
55
56 286 higher than DB-5 (64) but lower than OV-22 (215), so the polarity of GQDs
57 287 stationary phase was moderate. The McReynolds constant for proton donor (Y,
58
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1
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3 288 n-butanol) was higher than others, indicating that the hydrogen bond interaction is
4
289 strong between the stationary phase and analytes.
5
6 290 The good resolution, precision, and selectivity for the separation of alkanes, EB,
7 291 styrene, xylene, propylbenzene and dichlorobenzene isomers made the GQDs a
8 292 promising candidate of GC stationary phase. An increase in analyte mass resulted in a
9
10 293 linear increase of the chromatographic peak areas of aromatic isomers (Fig. 6), but

Analytical Methods Accepted Manuscript

11 294 almost no change occurred in retention time (Fig. S5). The features of the GQDs
12 295 coated capillary column offered us its potential application in the aromatic isomers’
13
14 296 qualitative and quantitative analysis.
15 297 HP-5 capillary column is an excellent nonpolar column which is coated with
16 298 (5%-phenyl)-methylpolysiloxane. In our work, the commercial HP-5 capillary column
17
18 299 is employed for comparison to demonstate the separation performance of GQDs
19 300 coated capillary column. The elution time of alkanes and aromatic isomers on HP-5
20 301 capillary column is long, 57 min for EB, and 42 min for o-dichlorobenzene (Fig.S2C
21
22
302 and S2F). But on GQDs coated capillary column, they only need a short time within 9
23 303 min (Fig. 4) to obtain a good separation. Besides, the isothermal separation is done
24 304 at a temperature of no higher than 60 oC, far below the boiling points of the higher
25
305 boiling analytes in the mixture, while high temperature is often needed on commercial
26
27 306 HP-5 capillary column. What’s more, because of the existence of epoxy, hydroxyl,
28 307 carboxyl groups, GQDs column shows some characteristics of polar column, the
29 308 commercial HP-innowax column is also used for comparison. In Fig.S3, it is found
30
31 309 that the elution sequence of alkanes and aromatic isomers on HP-innowax is the same
32 310 as the GQDs and HP-5 capillary columns, but high temperature and long analysis time
33 311 are also inevitable. The above results show that GQDs coated capillary column offers
34
35 312 us an other way to separate alkanes and aromatic isomers in a short analysis time
36 313 without the process of temperature-programming.
37 314 In order to further explore the thermodynamics of the separation, a temperature
38
39 315 range of 40-90 oC was measured to investigate the separation of xylene,
40 316 propylbenzene, dichlorobenzene, styrene and EB isomers. When the column
41 317 temperature increased, the retention time of analytes on GQDs coated capillary
42
43
318 column gradually decreased (Fig. 7). The phenomenon indicated that the separation
44 319 processes were exothermic49. Besides, the selectivity and resolution followed the
45 320 same trends as the plots of retention time against the increase of temperature (Fig. 8
46
321 and Fig. S6).
47
48 322 The good linearity of the van’t Hoff plots for the separation of substituted
49 323 aromatics (Fig. 9) demonstrated that interaction mechanism remained unchanged in
50 324 the studied temperature range. The values of △H and △S obtained from the van’t
51
52 325 Hoff plots were summed up in Table 3. More negative △H and more positive △S
53 326 should be beneficial to the transfer of the solute from the mobile phase to the
54 327 stationary phase, resulting in stronger retention of the analytes. Thus, we could come
55
56 328 to the conclusion that the separation of isomers was a complex balance of
57 329 thermodynamic and kinetic factors.
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1
2
3 330 Conclusion
4
331 In conclusion, we have not only demonstrated the feasibility of GQDs as a
5
6 332 promising stationary phase for the GC separation of styrene, EB and xylene,
7 333 propylbenzene and dichlorobenzene isomers with high resolution, good selectivity
8 334 and reproducibility, but also offered excellent feature for the separation of linear and
9
10 335 branched alkanes. They can be separated within 9 min at low temperature without the

Analytical Methods Accepted Manuscript

11 336 process of temperature-programming. Compared with the separation of these analytes
12 337 on commercial HP-5 and HP-innowax capillary columns, the GQDs coated capillary
13
14 338 column offered us a fast separation method at low temperature.
15 339 3-Aminopropyldiethoxymethyl silane, the coupling reagent between GQDs and the
16 340 fused silica capillary column, makes GQDs firmly immobilized onto the inner surface
17
18 341 of the capillary column. The presence of aromatic rings, rich functional groups and
19 342 high surface areas makes GQDs very promising for effective application and
20 343 separation in high-resolution capillary gas chromatography.
21
22 344 Acknowledgments
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24
345 The authors are grateful to the Natural Science Foundation of China (Grant
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26 346 21177090, 21275104) for supporting this work.
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28 347 References
29
30 348 1. E. Matisova and S. Skrabakova, J. Chromatogr. A, 1995, 707, 145-179.
31 349 2. V. K. Ponnusamy and J.-F. Jen, J. Chromatogr. A, 2011, 1218, 6861-6868.
32
33 350 3. H. Zhang and H. K. Lee, Anal. Chim. Acta, 2012, 742, 67-73.
34 351 4. A. Safavi, N. Maleki and M. M. Doroodmand, Anal. Chim. Acta, 2010, 675,
35 352 207-212.
36
37
353 5. C. Saridara and S. Mitra, Anal. Chem., 2005, 77, 7094-7097.
38 354 6. M. Karwa and S. Mitra, Anal. Chem., 2006, 78, 2064-2070.
39 355 7. L.-M. Yuan, C.-X. Ren, L. Li, P. Ai, Z.-H. Yan, M. Zi and Z.-Y. Li, Anal.
40
356 Chem., 2006, 78, 6384-6390.
41
42 357 8. C. M. Hussain, C. Saridara and S. Mitra, Anal. Chem., 2010, 82, 5184-5188.
43 358 9. Q. Li and D. Yuan, J. Chromatogr. A, 2003, 1003, 203-209.
44
359 10. P. F. Fang, Z. R. Zeng, J. H. Fan and Y. Y. Chen, J. Chromatogr. A, 2000,
45
46 360 867, 177-185.
47 361 11. A. Speltini, D. Merli, D. Dondi, G. Paganini and A. Profumo, Anal.Bioanal.
48 362 Chem., 2012, 403, 1157-1165.
49
50 363 12. A. Speltini, D. Merli, E. Quartarone and A. Profumo, J.Chromatogr. A, 2010,
51 364 1217, 2918-2924.
52 365 13. M.-M. Wang and X.-P. Yan, Anal. Chem., 2011, 84, 39-44.
53
54 366 14. W. Zhang, J. Zhang, T. Bao, W. Zhou, J. Meng and Z. Chen, Anal. Chem.,
55 367 2013, 85, 6846-6854.
56 368 15. M. Sun, R. Tang, Q. Wu, C. Wang and Z. Wang, Anal. Methods, 2013, 5,
57
58 369 5694-5700.
59 9
60
 Analytical Methods Page 10 of 23

1
2
3 370 16. G. Zhao, S. Song, C. Wang, Q. Wu and Z. Wang, Anal. Methods, 2011, 3,
4
371 2929-2935.
5
6 372 17. J. Feng, H. Qiu, X. Liu, S. Jiang , TrAC Trends Anal Chem, 2013, 46, 44-58.
7 373 18. X. Liang, S. Wang, S. Liu, X. Liu and S. Jiang, J. Sep. Sci., 2012, 35,
8 374 2003-2009.
9
10 375 19. M. Zhang and H. Qiu, TrAC Trends Anal. Chem., 2015, 65, 107-121.

Analytical Methods Accepted Manuscript

11 376 20. G. I. Titelman, V. Gelman, S. Bron, R. L. Khalfin, Y. Cohen and H.
12 377 Bianco-Peled, Carbon, 2005, 43, 641-649.
13
14 378 21. J. M. Chen, J. Zou, J. B. Zeng, X. H. Song, J. J. Ji, Y. R. Wang, J. Ha and X.
15 379 Chen, Anal. Chim. Acta, 2010, 678, 44-49.
16 380 22. Q. S. Qu, Y. Q. Shen, C. H. Gu, Z. L. Gu, Q. Gu, C. Y. Wang and X. Y. Hu,
17
18 381 Anal. Chim. Acta, 2012, 757, 83-87.
19 382 23. L. A. Ponomarenko, F. Schedin, M. I. Katsnelson, R. Yang, E. W. Hill, K. S.
20 383 Novoselov and A. K. Geim, Science, 2008, 320, 356-358.
21
22
384 24. Y. Li, Y. Hu, Y. Zhao, G. Shi, L. Deng, Y. Hou and L. Qu, Adv. Mater., 2011,
23 385 23, 776-780.
24 386 25. D. R. Dreyer, S. Park, C. W. Bielawski and R. S. Ruoff, Chem. Soc. Rev.,
25
387 2010, 39, 228-240.
26
27 388 26. Q. Liu, J. Shi, J. Sun, T. Wang, L. Zeng and G. Jiang, Angew. Chem. Int. Ed.
28 389 2011, 50, 5913-5917.
29 390 27. S. Song, R. Chu, J. Zhou, S. Yang and J. Zhang, J.Phys. Chem. C, 2008, 112,
30
31 391 3805-3810.
32 392 28. L. I. Devriese, L. Cools, A. Aerts, J. A. Martens, G. V. Baron and J. F. M.
33 393 Denayer, Adv. Funct. Mater., 2007, 17, 3911-3917.
34
35 394 29. L. Alaerts, M. Maes, P. A. Jacobs, J. F. M. Denayer and D. E. De Vos, Phys.
36 395 Chem. Chem. Phys., 2008, 10, 2979-2985.
37 396 30. C.-X. Yang, S.-S. Liu, H.-F. Wang, S.-W. Wang and X.-P. Yan, Analyst,
38
39 397 2012, 137, 133-139.
40 398 31. p. Zhao, S. Teng, M. Yu, N. Niu, X. He and B. Wu, Anal. Methods, 2014,
41 399 DOI: 10.1039/C4AY01928H.
42
43
400 32. Y.-M. Liu, P. Gordon, S. Green and J. V. Sweedler, Anal. Chim. Acta, 2000,
44 401 420, 81-88.
45 402 33. N. Chang and X.-P. Yan, J. Chromatogr. A, 2012, 1257, 116-124.
46
403 34. G. M. Gross, D. A. Nelson, J. W. Grate and R. E. Synovec, Anal. Chem.,
47
48 404 2003, 75, 4558-4564.
49 405 35. W.-Y. Ho, Y.-N. Hsieh, W.-C. Lin, C. L. Kao, P.-C. Huang, C.-F. Yeh, C.-Y.
50 406 Pan and C.-H. Kuei, Anal. Methods, 2010, 2, 455-457.
51
52 407 36. D. Merli, A. Speltini, D. Ravelli, E. Quartarone, L. Costa and A. Profumo, J.
53 408 Chromatogr. A, 2010, 1217, 7275-7281.
54 409 37. Z. Y. Gu and X. P. Yan, Angew. Chem. Int. Ed., 2010, 49, 1477-1480.
55
56 410 38. A. V. Herrera-Herrera, M. Á. González-Curbelo, J. Hernández-Borges and M.
57 411 Á. Rodríguez-Delgado, Anal. Chim. Acta, 2012, 734, 1-30.
58
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4
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5
6 414 40. L.-L. Li, K.-P. Liu, G.-H. Yang, C.-M. Wang, J.-R. Zhang and J.-J. Zhu, Adv.
7 415 Funct. Mater., 2011, 21, 869-878.
8 416 41. F. Yang, M. Zhao, B. Zheng, D. Xiao, L. Wu and Y. Guo, J. Mater. Chem.,
9
10 417 2012, 22, 25471-25479.

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11 418 42. Q. Qu, C. Gu and X. Hu, Anal. Chem., 2012, 84, 8880-8890.
12 419 43. A. Berthod, E. Y. Zhou, K. Le and D. W. Armstrong, Anal. Chem., 1995, 67,
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14 420 849-857.
15 421 44. N. Yassaa, E. Brancaleoni, M. Frattoni and P. Ciccioli, Chemosphere, 2006,
16 422 63, 502-508.
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18 423 45. H. Hattori, M. Iwai, S. Kurono, T. Yamada, K. Watanabe-Suzuki, A. Ishii, H.
19 424 Seno and O. Suzuki, J.Chromatogr. B, 1998, 718, 285-289.
20 425 46. W. De Malsche, S. Van der Perre, S. Silverans, M. Maes, D. E. De Vos, F.
21
22
426 Lynen and J. F. Denayer, Micropor. Mesopor. Mat., 2012, 162, 1-5.
23 427 47. Z.-Y. Gu and X.-P. Yan, Angew. Chem. Int. Ed., 2010, 49, 1477-1480.
24 428 48. W. McReynolds, J. Chromatogr. Sci., 1970, 8, 685-691.
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429 49. Z.-L. Fang, S.-R. Zheng, J.-B. Tan, S.-L. Cai, J. Fan, X. Yan and W.-G.
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27 430 Zhang, J.Chromatogr. A, 2013, 1285, 132-138.
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29 RSD (%) (n=5)
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31 Analyte Retention time Peak area Peak height W1/2
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33 EB 1.3 1.5 1.8 2.1
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35 Styrene 1.6 2.4 1.1 2.2
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37 EB 0.7 1.4 1.1 2.1
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p-Xylene 0.8 1.3 0.8 1.7
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42 o-Xylene 0.8 2.4 0.9 1.8
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44 Isopropylbenzene 0.2 1.4 6.0 1.2
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46 n-Propylbenzene 0.1 1.2 7.0 1.2
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48 1,3,5-Trimethylbenzene 0.1 0.9 8.5 1.7
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50 m-Dichlorobenzene 1.3 0.7 2.3 1.8
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52 p-Dichlorobenzene 1.3 3.1 1.0 1.5
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54 o-Dichlorobenzene 1.2 4.0 3.3 1.6
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57 431 Table 1 Precision for five replicate separation of aromatic isomers on the GQDs coated capillary
58 432 column.
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6 DB-5(ref.48) 27 66 71 93 63 64
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9 OV-22(ref.48) 160 188 191 283 253 215
10 433 Table 2 McReynolds constants and average polarity of GQDs and other kinds of columns at 100

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Analyte -△H (kJ mol-1) -△S (J mol-1K-1) R2
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15 EB 37.9 ± 0.1 92.3 ± 0.4 0.99986
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17 Styrene 40.1 ± 0.2 94.4 ± 0.5 0.99984
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19 EB 37.6 ± 0.2 91.3 ± 0.5 0.99990
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21 p-Xylene 38.4 ± 0.2 93.0 ± 0.5 0.99988
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23 o-Xylene 39.1 ± 0.1 93.0 ± 0.4 0.99992
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25 Isopropylbenzene 40.6 ± 0.3 95.8 ± 0.8 0.99978
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34 p-Dichlorobenzene 45.0 ± 0.3 99.9 ± 0.8 0.99984
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36 o-Dichlorobenzene 45.7 ± 0.3 99.8 ± 1.0 0.99978
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45 439 TGA curve of the prepared GQDs.
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50 442 capillary column; (b) the SEM image of the GQDs coated capillary column, (c) SEM image of the
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53 444 Fig. 3 Gas chromatograms on the GQDs coated capillary column (22 m long × 0.32 mm i.d.) at
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3 448 Fig. 4 Gas chromatograms on the GQDs coated capillary column (22 m long × 0.32 mm i.d.) for
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7 451 n-propylbenzene and 1,3,5-trimethylbenzene under a N2 flow rate of 0.7 mL min-1 at 60 oC; (D)
8 452 m-dichlorobenzene, p-dichlorobenzene, o-dichlorobenzene under a N2 flow rate of 0.7 mL min-1 at
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12 454 Fig. 5 Chromatograms on the GQDs coated capillary (22 m × 0.32 mm i.d.) for GC separation
13 455 of (A) n-pentanol and its branched isomers under a N2 flow of 0.7 mL min-1 using a temperature
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16 457 flow of 0.7 mL min-1 at 50 ℃.
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