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Adsorption of small gas molecules on transition metal (Fe, Ni and Co, Cu) doped
graphene: A systematic DFT study

Jiaming Ni, Mildred Quintana, Shaoxian Song

PII: S1386-9477(19)31094-X
DOI: https://doi.org/10.1016/j.physe.2019.113768
Reference: PHYSE 113768

To appear in: Physica E: Low-dimensional Systems and Nanostructures

Received Date: 23 July 2019

Revised Date: 28 September 2019
Accepted Date: 6 October 2019

Please cite this article as: J. Ni, M. Quintana, S. Song, Adsorption of small gas molecules on transition
metal (Fe, Ni and Co, Cu) doped graphene: A systematic DFT study, Physica E: Low-dimensional
Systems and Nanostructures (2019), doi: https://doi.org/10.1016/j.physe.2019.113768.

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1 Adsorption of small gas molecules on transition metal (Fe, Ni

2 and Co, Cu) doped graphene: A systematic DFT Study

3 Jiaming Ni 1,2, Mildred Quintana 1,3* Shaoxian Song 4,5,

1
4 CICSaB, Universidad Autónoma de San Luis Potosí, Av. Sierra Leona 550,

5 San Luis Potosi, C.P. 78210, Mexico

2
： School of Resources and Environmental Engineering, Wuhan University of

7 Technology, Luoshi Road 122, Wuhan, Hubei, 430070, China

3
8 Facultad de Ciencias, Universidad Autónoma de San Luis Potosí, Av.

9 Parque Chapultepec 1570, San Luis Potosi, C.P. 78210, Mexico

4
10 Hubei Key Laboratory of Mineral Resources Processing and Environment,

11 Wuhan University of Technology, Luoshi Road 122, Wuhan, Hubei, 430070,

12 China
5
13 Hubei Provincial Collaborative Innovation Center for High Efficient

14 Utilization of Vanadium Resources, Wuhan University of Technology,

15 Luoshi Road 122, Wuhan, Hubei, 430070, China

1： * Corresponding author E-mail: mildred.quintana@uaslp.mx

17 Abstract We predict the CO2, NO, NO2 and SO2 gas molecule absorption

18 and sensing performance of transition metal (Fe, Ni, Co and Cu) doped

19 graphene by a systematic density functional theory (DFT) study. Our results

20 demonstrate that graphene doped with different transition metal atoms

21 produces completely different adsorption behaviors of small gas molecules

22 originated from changes in the electronic structure of the systems under

23 strain. Graphene doped with Fe atoms was the best platform for sensing NO2

24 gas molecules (NO2/Fe-MG). The NO2/Fe-MG system showed the best

25 adsorption rate, the higher charge transfer and the shortest distance between

2： the graphene platform and the gas molecule of all the calculated systems. As

27 the strain increases, the adsorption energy and charge transfer decreases. So

28 the NO2 gas molecule adsorption properties of Fe-MG without strain would

29 help in guiding experimentalists to develop better materials based on

30 graphene for efficient gas detection or sensing applications.

31 Key words: DFT; graphene; band gap; DOS; adsorption energy; strain; gas

32 molecule absorption;

33 1. Introduction

34 The sensing of molecules is a very active research field in many

35 different areas, as for example biosensors, gas sensors, chemical sensors,

3： humidity sensors, optics sensors, pressure sensors, etc [1-5]. In particular,

37 gas sensors present limitations in measuring very low conductivities,

38 achieving long-time stabilities under extreme environmental conditions, and

39 increasing adsorption capacities [6-9]. In this direction, nano-materials, due

40 to their industrial applications, have been studied by many researchers

41 [10,11]. Graphene with two-dimensional crystal structure has attracted great

42 attention due to its good mechanical, chemical and electrical properties [12].

43 Graphene also presents great adsorption capacity due to its high specific

44 surface area [13-16]. Graphene is a zero-n gap semiconductor without

45 magnetism. However, in adsorbed or doped graphene with other materials or

4： atoms the band gap is opened obtaining in some cases a magnetic material

47 [17-22]. Therefore, graphene has a promising future in nano electronic

48 devices such as gas sensor [23-29]. For example, Nashenia F et al. [30]

49 studied the adsorption of O2 gas molecules on transition metal (Fe-, Co-, Ni-,

50 Ru-, Rh-, Pd-, OS-, Ir- and Pt-)-doped graphene structures. Later, authors

51 show how this process alters the sensing of toxic-gases (carbon monoxide,

52 hydrogen fluoride, etc.). Muhammad Ali et al. [31] reported that C vacancy

53 graphene is able to chemisorb NO, NO2 and O3 gas molecules, and the

54 chemisorption of NO2 lead to high sensor response compared to that of NO

55 and O3 gas molecules. Chieh-Szu Huang et al. [32] reported the gas

5： adsorption on the novel two-dimensional material borophene of the polar

57 gases NH3, NO, NO2, and CO gas molecules. Authors established the

58 favorable adsorption sites and geometries on the borophene substrates.

59 According to the previous articles, the defects present on the graphene

：0 surface increased the adsorption ability of gas molecule than that observed

：1 on intrinsic graphene. For this reason, we doped graphene with transition

：2 metal (Fe, Co, Ni and Cu) for the further adsorption of CO2, NO, NO2 and

：3 SO2 gas molecules. In this work we study transition metal doped graphene as

：4 a model surface for the sensing of CO2, NO, NO2 and SO2 gas molecules.

：5 The calculation of the band gap, density of states (DOS) and charge transfer

：： was performed using density functional theory (DFT).

：7 2. Theory and Simulation

：8 The mono vacancy graphene was calculated using a 4 x 4 super crystal

：9 package. Mono-vacancy graphene lacking of a carbon atom in intact

70 graphene was confined in a space of 12 carbon atoms. In order to determine

71 the influence of transition metal doping, we compared pure graphene and

72 defected graphene to find out the different characteristics of the doping

73 elements and the structure and adsorption properties of the adsorption of

74 CO2, NO, NO2 and SO2 gas molecules. The electron exchange correlation

75 energy function was used the generalized gradient approximation (GGA) to

7： Perdew-Wang-91 (PW-91) for describe the interaction between electrons

77 [33,34]. The reciprocal space was sampled with dense grids of 4 × 4 × 1

78 k-points in the Brillouin Zone (BZ) and Methfessel-Paxton smearing of

79 0.005Ha. The cutoff energy was 340 eV with self consistence-field (SCF)
80 converged of 1.0×10-5 eV, and all the atomic structures were relaxed

81 until the total energy and the Hellmann-Feynman forces converged to

82 1.0×10-5eV and 0.05eV/Å [35,36]. The Brillouin zone integral path

83 used in this paper was GKFG. First, it started from G to reach K point,

84 then from point K to point F, and finally from point F to point G, thus

85 completing the integral calculation in Brillouin zone.

8： We calculated the adsorption energy (Ea) of adsorbed systems, which

87 was defined as Eq.:

88 Ea=Egraphene+gasmolecule-(Egraphene+Egasmolecule) (1)

89 Where Egraphene+gas molecule was the total energy of graphene adsorbed

90 system, Egraphene was the energy of graphene, and Egas molecule was the energy

91 of a gas molecule. All energies were calculated for optimized atomic

92 structures. We had investigated the charge transfer by using Mulliken's

93 population analysis.

94 3. Result and Discussion

 95

9： Figure. 1 (a) The structure of pure graphene. (b) The structure of M (Fe, Ni, Co and Cu)

97 doped mono-vacancy graphene. (c) The structure of different gas molecules adsorbed on

98 M (Fe, Ni, Co and Cu) doped mono-vacancy graphene.

99 As shown in the Figure. 1, We put four kinds of gas molecules on the

100 X-MG and optimized the structure of the four gas molecules with the same

101 vertical distance from the graphene plane, and Figure. 1(b) shows the doping

102 site and the structure of MG.

103
104

105

10：

107 Figure. 2 The optimized structures of the CO2, NO, NO2 and SO2 gas molecule adsorbed

108 on monolayer M-MG, where M = Fi, Ni, Co or Cu.

109 Figure. 2 shows the most stable configuration for the CO2, NO, NO2

110 and SO2 gas molecules adsorbed on monolayer graphene. The transition

111 metals are stably linked to the graphene surface. The height of all transition
112 metals to monolayer graphene vary from -1.06 Å to 1.53 Å, where the height

113 of the graphene sheet was determined by the average height of the remaining

114 39 C atoms in the stable structure, and the four nearest C atoms protruding

115 from graphene. In contrast, Fe atom was rised, Ni and Cu atom were both

11： sunken downward, and Co had convex and concave adsorption for different

117 gases. We calculated the bond lengths of M-C, which were longer than those

118 of C-C bond length. Because of the strong adsorption between transition

119 metal atoms with a larger radius and C atoms, the transition metal atoms

120 were forced to move away from the surface of graphene, lead to the

121 graphene structure table was not on a plane. In the four transition metals

122 doping, it showed that Fe atom form covalent bonds with each gas molecule,

123 while the others had weak physical adsorption.

124

125 Figure. 3. Adsorption energies, shortest atomic distances between gas molecule and

12： X-MG, and charge transfers.

127 The adsorption energy of CO2, NO, NO2 and SO2 gas molecules on

128 M-MG, the adsorption distances and the charge transfers were shown in

129 Figure. 3. NO2 gas molecule has the best effect on M-MG. The adsorption

130 energy of NO2 gas molecule is about -2.06 eV to -2.57 eV, which is much

131 higher than the other gas molecules and better than previous work [37,38].

132 It was 1.2 times of the adsorption energy of SO2/M-MG gas molecule

133 (-0.89 eV to -1.19 eV), 3 times of the adsorption energy of CO2/M-MG

134 (-0.87 eV to -1.47 eV) and 6 times of the adsorption energy of NO/M-MG

135 (-0.68 eV to -1.23 eV). In charge transfer, gas molecule contributes 0.21 –
13： 0.28 e to the Fe-MG monolayer, Fe atom doped MG presents higher charge

137 transfer for gas molecules. Fe atoms occupy the highest number of electron

138 transfer in all element doping and very prominent. Fe doped graphene

139 presented the lowest molecular distance and most stable for the four dopant

140 elements. It could be seen that for a gas molecule adsorbed system, there is

141 a relationship between the adsorption energy and the equilibrium adsorption

142 distance, the larger the adsorption energy, the shorter the equilibrium

143 adsorption distance. Therefore, the interaction between gas molecules and

144 Fe-doped graphene was the strongest.

145 3.1 Small gas molecules on transition metal (Fe, Ni, Co and Cu) doped

14： graphene

147 3.11 CO2 gas molecule adsorption on M-MG monolayer

148 The DOS and the electrostatic potential for different transition metal

149 doping are shown in Fig. 4. For Fe and Co doping only one peak at -6 eV are

150 observed, while for Ni and Cu doping two or more peak at -6 eV, -5 eV and

151 -2.5 eV, are observed for the interaction with CO2 gas molecules and

152 graphene. The electrostatic potential, around the O atom is negative-the

153 particles with positive charge interact strongly and easily close to it, and the

154 electrostatic potential around the transition metal atom and C atom is

155 positive. Therefore, it could be confirmed that the adsorption properties and
15： the CO2 gas molecule adsorption on Fe-MG, Co-MG is mainly base in

157 chemisorption.

158

159 Figure. 4 The electrostatic potential of structure and DOS of CO2, M-MG and CO2/

1：0 M-MG.

1：1 3.12 NO gas molecule adsorption on the M-MG monolayer

1：2 As shown in Figure. 5, the DOS is basically similarly to the previously

1：3 described, it has different some peak after adsorption in different gas

1：4 molecule. Between -5 eV and 0 eV, the excepted signals for the Fe doping

1：5 appears, the peaks of other elements are relatively large and have

1：： outstanding performance. Between all the metal doping, only Fe and

1：7 graphene form covalent bonds, this is probably as consequence of the higher

1：8 oxidation of the iron atom. The electrostatic potential around the O atom and

1：9 N atom are negative, while the particles with positive charge interact

170 strongly and easily close to it, and the electrostatic potential around the

171 transition metal atom was positive.

172

173 Figure. 5 The electrostatic potential of structure and DOS of NO, M-MG and NO/ M-MG.
174
175 3.13 NO2 gas molecule adsorption on the M-MG monolayer

17： As shown in Figure. 6, the highest wave peaks are concentrated below

177 the Fermi level -10 eV to 0 eV, and there are several wavelet peaks above 0

178 eV and two large peaks in NO2/Fe-MG around -7.5 eV and -2.5 eV. In the

179 same system, the covalent bonds are formed between the molecules of

180 NO2/M-MG, and there are strong peaks of NO2 gas molecule in these two

181 places. The electrostatic potential around the O atom is negative, then the

182 particles with positive charge interact strongly with it and are located close

183 to it, the electrostatic potential around the transition metal atom is positive.

184 The color around the Fe atom was obviously darker, indicating that the

185 electron accumulation is also more intense.

18：

187 Fig. 6 The electrostatic potential of structure and DOS of NO2, M-MG and NO2/ M-MG.
188
189 3.14 SO2 gas molecule adsorption on the M-MG monolayer

190 The DOS is shown in Fig. 7 for different transition metal doping, it

191 could be seen that SO2 gas molecule adsorption on the M-MG monolayer

192 presents six peaks value, the peak was -6 eV, -5 eV, -2.5 eV -2 eV, 3 eV and

193 4 eV which contribute for the SO2 gas molecule and the monolayer M-MG.

194 The SO2 gas molecule adsorption on different metal-doped graphene, and

195 the adsorbed connection bond is different, which also show an effect on the

19： DOS. The electrostatic potential around the O atom is negative, then the

197 particles with positive charge strongly interact with it, and the electrostatic

198 potential around the transition metal atom and S atom is positive. Therefore,

199 it could be confirmed that the adsorption properties and the SO2 gas

200 molecule adsorption on the Fe-MG is mainly based on a chemisorption

201 process.
202

203 Figure. 7 The electrostatic potential of structure and DOS of SO2, M-MG and SO2/

204 M-MG.

205
20： 3.2 Enhancement of NO2 sensing performance by strain engineering

207

208 Figure. 8 The change curves of Ea (blue), Rd (red) and dFe-N (black) accompany with

209 strain in NO2/strained-Fe/MG systems. The insert presents the charge transfer of the

210 NO2/strained- Fe/MG systems.

211 To confirm that the adsorption strength could be tuned by the

212 application of strain on monolayer, the adsorption of NO2 gas molecule onto

213 the strained Fe/MG monolayer was calculated, in which four typical strained

214 states (0% to 8%) along a, b, c-direction were implemented [39].

215 Figure. 8 shown the changes in a few parameters caused by strain,

21： including the distance between Fe atom and N atom (dFe-N), adsorption

217 energy (Ea) and the rate of change of distance between Fe atom and N atom

218 (Rd). The Rd was defined as:

219 Rd =| d′Fe-N - dFe-N| /( dFe-N ) (3)

220 where dFe-N and d′Fe-N are the distance between N atom and Fe atom of

221 Fe/MG monolayer before and after adsorption of NO2, respectively.

222 As shown in Figure 8, Ea (blue line) of NO2 gas molecule/strained-

223 Fe/MG monolayer system briefly decreased with the rising strain from 0% to

224 8%. As observed, a charge transfer occurs (the upper right corner of Figure.

225 8) systematically enhanced with increasing strain, going from -0.283 e at 0%

22： strain to -0.213 e at 8% strain according to Mulliken charge analysis. It was

227 cleared that adsorption strength of NO2 gas molecule on Fe/MG monolayer

228 could be reduced by the application of strain, thus the performance of NO2

229 gas molecule sensor based on strained Fe/MG monolayer could also be

230 weaken.
231 4. Conclusion

232 In this work, the geometrical structure and adsorption properties of

233 different gas molecule (CO2, NO, NO2 and SO2) adsorbed on different

234 transition metal doped monolayer graphene were calculated by first

235 principles study. The adsorption energy of transition metal doping was

23： obviously stronger than that of the pristine graphene in charge transfer.

237 Firstly, the adsorption energy of transition metal doping was about -6 eV,

238 which was much higher than other gas molecule adsorption. Secondly, under

239 the doping of transition metal atom, the doping of Fe atom had the best

240 adsorption energy, the charge transfer and the distance between molecules

241 was the best. As the strain increases from 0% to 8%, the absolute value of Ea

242 increases from 2.52 eV to 1.73 eV, and the charge transfer vary from -0.286

243 e to -0.213 e, indicating that strain has a bad effect on graphene adsorption.

244 In conclusion, Fe doped graphene was the most suitable gas sensor for NO2

245 gas molecules without strain.

24： Acknowledgements

247 Authors thank the Marcos Moshinsky Foundation A.C. for economical

248 support. Jiaming Ni thanks to CONACYT for the scholarship number

249 935434. The Research Fund Program of Key Laboratory of Rare Mineral,

250 Ministry of Land and Resources (KLRM-KF201802) are gratefully

251 acknowledged. We also thank the College of Materials Science and

252 Engineering, Anhui University of Science and Technology, for its assistance

253 with the MS simulations.

254 Competing interests

255 The authors declare that they have no competing interests.

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3：9 HIGHLIGHT
370 1) Transition metal (Fe, Co, Ni, and Cu)-doped monolayer

371 graphene are investigated.

372 2) Doped graphene significantly enhanced adsorption and sensing of

373 small gas molecules, especially for NO2 gas molecules.

374 3) Introduced nd orbital impurity states of transition metals on the

375 graphene lattice play an important role for gas adsorption and activation.

37：
377
1. The transition metal (Fe, Co, Ni, and Cu)-doped monolayer

graphene are investigated, and the transition metal-doped monolayer

graphene should be stable.

2. Embedded TMs can significantly enhanced adsorption

and activation of small gas molecules, especially with NO2 gas molecule.

3. Introduced nd orbital impurity states of TMs play an important role

for gas adsorption and activation.

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

The authors declare that they have no known competing financial interests or personal relationships that
could have appeared to influence the work reported in this paper.