Modulation of charge in C<sub>9</sub>N<sub>4</sub> monolayer for a high-capacity hydrogen storage as a switchable strategy

doi:10.1007/s11467-023-1385-0

Front. Phys.

2024, Vol. 19

Issue (4) : 43208 https://doi.org/10.1007/s11467-023-1385-0

Modulation of charge in C₉N₄ monolayer for a high-capacity hydrogen storage as a switchable strategy

Lin Ju¹(

), Junxian Liu², Minghui Wang¹, Shenbo Yang³, Shuli Liu¹

¹. School of Physics and Electric Engineering, Anyang Normal University, Anyang 455000, China
². School of Mechanical, Medical and Process Engineering, Queensland University of Technology, Brisbane QLD 4001, Australia
³. Hongzhiwei Technology (Shanghai) Co. Ltd., 1599 Xinjinqiao Road, Pudong, Shanghai 201206, China

Download: PDF(4491 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Developing advanced hydrogen storage materials with high capacity and efficient reversibility is a crucial aspect for utilizing hydrogen source as a promising alternate to fossil fuels. In this paper, we have systematically investigated the hydrogen storage properties of neutral and negatively charged C₉N₄ monolayer based on density functional theory (DFT). Our foundings indicate that injecting additional electrons into the adsorbent significantly boosts the adsorption capacity of C₉N₄ monolayer to H₂ molecules. The gravimetric density of negatively charged C₉N₄ monolayer can reach up to 10.80 wt% when fully covered with hydrogen. Unlike other hydrogen storage methods, the storage and release processes happen automatically upon introducing or removing extra electrons. Moreover, these operations can be easily adjusted through activating or deactivating the charging voltage. As a result, the method is easily reversible and has tunable kinetics without requiring particular activators. Significantly, C₉N₄ is proved to be a suitable candidate for efficient electron injection/release due to its well electrical conductivity. Our work can serve as a valuable guide in the quest for a novel category of materials for hydrogen storage with high capacity.

Keywords hydrogen storage C₉N₄ monolayer charge modulation density functional theory

Corresponding Author(s): Lin Ju

Issue Date: 08 March 2024

Cite this article:

Lin Ju,Junxian Liu,Minghui Wang, et al. Modulation of charge in C₉N₄ monolayer for a high-capacity hydrogen storage as a switchable strategy[J]. Front. Phys. , 2024, 19(4): 43208.

URL:

https://academic.hep.com.cn/fop/EN/10.1007/s11467-023-1385-0
https://academic.hep.com.cn/fop/EN/Y2024/V19/I4/43208

Fig.1 (a) Top and side views of a reconstructed C₉N₄ monolayer. The N and C atoms are symbolized by the blue and grey balls correspondingly. (b) Electron localization functions. (c) The electronic band structure and (d) the projected density of states, relative to the Fermi level, which is represented by the blue dashed line.

Fig.2 (a) AIMD simulations on total energy for C₉N₄ monolayer for 5 ps with a time step of 1 fs at 500 K. (b) The corresponding temperature for each step.

Fig.3 Top and side views of the lowest-energy configurations of (a) neutral and (b) 3e^? charged C₉N₄ monolayers with a H₂ molecule absorbed on them, respectively. The blue, grey and white balls represent N, C, and H atoms, respectively. The adsorption distance, which is apart from the barycenter of the adsorbed H₂ molecule to the surface of the C₉N₄ monolayer, is marked out in the figure.

Fig.4 (a) The charge density difference for the adsorption system, constructed by a H₂ molecule adsorbing on 3e^? negatively charged C₉N₄. Yellow and cyan regions refer to the electron-rich and -deficient areas, respectively. The isosurface value is 7 × 10^?4 e/au. (b) The H s-orbital from the adsorbed H₂, before and after the introduction of three electrons, with the dashed line being the Fermi energy level.

Fig.5 (a) The H?H bond length, (b) vertical distance from H₂ to C₉N₄, (c) induced dipole moment of H₂ molecule and (d) adsorption energy as well as their corresponding fittings, with respect to the amount of charge introduced (Q). Q could represent the valence of C₉N₄ monolayer. R² is the correlation coefficient.

Fig.6 Reversible energy cycle diagram of C₉N₄ monolayer adsorbing and releasing an H₂ molecule through introducing and removing electrons.

Fig.7 Average adsorption energy of H₂ on the (a) 3e^?, (c) 4e^?, and (e) 5e^? negatively charged C₉N₄ monolayer with different coverage. Top and side views of the lowest-energy configuration of (b) 3e^?, (d) 4e^?, and (f) 5e^? negatively charged C₉N₄ at full hydrogen coverage.

1	Tollefson J. . Hydrogen vehicles: Fuel of the future. Nature, 2010, 464(7293): 1262 https://doi.org/10.1038/4641262a
2	Schlapbach L. , Züttel A. . Hydrogen-storage materials for mobile applications. Nature, 2001, 414(6861): 353 https://doi.org/10.1038/35104634
3	Schüth F. , Bogdanović B. , Felderhoff M. . Light metal hydrides and complex hydrides for hydrogen storage. Chem. Commun. (Camb.), 2004, 2249(20): 2249 https://doi.org/10.1039/B406522K
4	Ding F. , I. Yakobson B. . Challenges in hydrogen adsorptions: From physisorption to chemisorption. Front. Phys., 2011, 6(2): 142 https://doi.org/10.1007/s11467-011-0171-6
5	Zhou X. , Zhou J. , Sun Q. . Tripyrrylmethane based 2D porous structure for hydrogen storage. Front. Phys., 2011, 6(2): 220 https://doi.org/10.1007/s11467-011-0176-1
6	Li J. , Furuta T. , Goto H. , Ohashi T. , Fujiwara Y. , Yip S. . Theoretical evaluation of hydrogen storage capacity in pure carbon nanostructures. J. Chem. Phys., 2003, 119(4): 2376 https://doi.org/10.1063/1.1582831
7	Jena P. . Materials for hydrogen storage: Past, present, and future. J. Phys. Chem. Lett., 2011, 2(3): 206 https://doi.org/10.1021/jz1015372
8	Wang L. , T. Yang R. . New sorbents for hydrogen storage by hydrogen spillover – a review. Energy Environ. Sci., 2008, 1(2): 268 https://doi.org/10.1039/b807957a
9	Song L. , Jiang C. , Liu S. , Jiao C. , Si X. , Wang S. , Li F. , Zhang J. , Sun L. , Xu F. , Huang F. . Progress in improving thermodynamics and kinetics of new hydrogen storage materials. Front. Phys., 2011, 6(2): 151 https://doi.org/10.1007/s11467-011-0175-2
10	Zhang H.Li X.Tang Y., DFT study of dihydrogen interactions with lithium containing organic complexes C4H4−mLim and C5H5−mLim (m = 1, 2), Front. Phys. 6(2), 231 (2011)
11	Yoon M. , Yang S. , Hicke C. , Wang E. , Geohegan D. , Zhang Z. . Calcium as the superior coating metal in functionalization of carbon fullerenes for high-capacity hydrogen storage. Phys. Rev. Lett., 2008, 100(20): 206806 https://doi.org/10.1103/PhysRevLett.100.206806
12	Sun Q. , Jena P. , Wang Q. , Marquez M. . First-principles study of hydrogen storage on Li12C60. J. Am. Chem. Soc., 2006, 128(30): 9741 https://doi.org/10.1021/ja058330c
13	H. Cheng Y. , Y. Zhang C. , Ren J. , Y. Tong K. . Hydrogen storage in Li-doped fullerene-intercalated hexagonal boron nitrogen layers. Front. Phys., 2016, 11(5): 113101 https://doi.org/10.1007/s11467-016-0559-4
14	Zhang Z. , Li J. , Jiang Q. . Density functional theory calculations of the metal-doped carbon nanostructures as hydrogen storage systems under electric fields: A review. Front. Phys., 2011, 6(2): 162 https://doi.org/10.1007/s11467-011-0174-3
15	Zhao Y. , H. Kim Y. , Dillon A. , Heben M. , Zhang S. . Hydrogen storage in novel organometallic buckyballs. Phys. Rev. Lett., 2005, 94(15): 155504 https://doi.org/10.1103/PhysRevLett.94.155504
16	K. Kong X. , W. Chen Q. , Y. Lun Z. . The influence of N‐doped carbon materials on supported Pd: Enhanced hydrogen storage and oxygen reduction performance. ChemPhysChem, 2014, 15(2): 344 https://doi.org/10.1002/cphc.201300907
17	Li S. , Zhao H. , Jena P. . Ti-doped nano-porous graphene: A material for hydrogen storage and sensor. Front. Phys., 2011, 6(2): 204 https://doi.org/10.1007/s11467-011-0178-z
18	Sun Q. , Wang Q. , Jena P. , Kawazoe Y. . Clustering of Ti on a C60 surface and its effect on hydrogen storage. J. Am. Chem. Soc., 2005, 127(42): 14582 https://doi.org/10.1021/ja0550125
19	Zhang Y. , Dai H. . Formation of metal nanowires on suspended single-walled carbon nanotubes. Appl. Phys. Lett., 2000, 77(19): 3015 https://doi.org/10.1063/1.1324731
20	Fu Q. , Yuan L. , Luo Y. , Yang J. . Exploring at nanoscale from first principles. Front. Phys. China, 2009, 4(3): 256 https://doi.org/10.1007/s11467-009-0057-z
21	Yoon M. , Yang S. , Wang E. , Zhang Z. . Charged fullerenes as high-capacity hydrogen storage media. Proc. Natl. Acad. Sci. USA, 2007, 7(9): 2578
22	Niu J. , Rao B. , Jena P. . Binding of hydrogen molecules by a transition-metal ion. Phys. Rev. Lett., 1992, 68(15): 2277 https://doi.org/10.1103/PhysRevLett.68.2277
23	Zhou J. , Wang Q. , Sun Q. , Jena P. , Chen X. . Electric field enhanced hydrogen storage on polarizable materials substrates. Proc. Natl. Acad. Sci. USA, 2010, 107(7): 2801 https://doi.org/10.1073/pnas.0905571107
24	Cheng H.C. Zheng J., Ab initio study of anisotropic mechanical and electronic properties of strained carbon−nitride nanosheet with interlayer bonding, Front. Phys. 16(4), 43505 (2021)
25	Ma Z. , Zhuang J. , Zhang X. , Zhou Z. . SiP monolayers: New 2D structures of group IV–V compounds for visible-light photohydrolytic catalysts. Front. Phys., 2018, 13(3): 138104 https://doi.org/10.1007/s11467-018-0760-8
26	Gao Q. , L. Wang H. , F. Zhang L. , L. Hu S. , P. Hu Z. . Computational study on the half-metallicity in transition metal–oxide-incorporated 2D g-C3N4 nanosheets. Front. Phys., 2018, 13(3): 138108 https://doi.org/10.1007/s11467-018-0754-6
27	Ju L. , Liu C. , Shi L. , Sun L. . The high-speed channel made of metal for interfacial charge transfer in Z-scheme g-C3N4/MoS2 water-splitting photocatalyst. Mater. Res. Express, 2019, 6(11): 115545 https://doi.org/10.1088/2053-1591/ab509c
28	He C. , H. Zhang J. , X. Zhang W. , T. Li T. . Type-II InSe/g-C3N4 heterostructure as a high-efficiency oxygen evolution reaction catalyst for photoelectrochemical water splitting. J. Phys. Chem. Lett., 2019, 10(11): 3122 https://doi.org/10.1021/acs.jpclett.9b00909
29	Liu J.Cheng B.Yu J., A new understanding of the photocatalytic mechanism of the direct Z-scheme g-C3N4/TiO2 heterostructure, Phys. Chem. Chem. Phys. 18(45), 31175 (2016)
30	Zhang G. , Zhang M. , Ye X. , Qiu X. , Lin S. , Wang X. . Iodine modified carbon nitride semiconductors as visible light photocatalysts for hydrogen evolution. Adv. Mater., 2014, 26(5): 805 https://doi.org/10.1002/adma.201303611
31	Sun J. , Zhang J. , Zhang M. , Antonietti M. , Fu X. , Wang X. . Bioinspired hollow semiconductor nanospheres as photosynthetic nanoparticles. Nat. Commun., 2012, 3(1): 1139 https://doi.org/10.1038/ncomms2152
32	Ye X. , Cui Y. , Wang X. . Ferrocene‐modified carbon nitride for direct oxidation of benzene to phenol with visible light. ChemSusChem, 2014, 7(3): 738 https://doi.org/10.1002/cssc.201301128
33	Zhang J. , Chen Y. , Wang X. . Two-dimensional covalent carbon nitride nanosheets: Synthesis, functionalization, and applications. Energy Environ. Sci., 2015, 8(11): 3092 https://doi.org/10.1039/C5EE01895A
34	P. Kaur S. , Hussain T. , Kaewmaraya T. , J. D. Kumar T. . Reversible hydrogen storage tendency of light-metal (Li/Na/K) decorated carbon nitride (C9N4) monolayer. Int. J. Hydrogen Energy, 2023, 48(67): 26301 https://doi.org/10.1016/j.ijhydene.2023.03.141
35	Huang J. , Zhou C. , Duan X. . Li decorated C9N4 monolayer as a potential material for hydrogen storage. Int. J. Hydrogen Energy, 2021, 46(65): 32929 https://doi.org/10.1016/j.ijhydene.2021.07.126
36	Tan X. , Kou L. , A. Tahini H. , C. Smith S. . Charge modulation in graphitic carbon nitride as a switchable approach to high‐capacity hydrogen storage. ChemSusChem, 2015, 8(21): 3626 https://doi.org/10.1002/cssc.201501082
37	E. Blöchl P. . Projector augmented-wave method. Phys. Rev. B, 1994, 50(24): 17953 https://doi.org/10.1103/PhysRevB.50.17953
38	P. Perdew J. , Wang Y. . Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B, 1992, 45(23): 13244 https://doi.org/10.1103/PhysRevB.45.13244
39	Heyd J. , E. Scuseria G. , Ernzerhof M. . Hybrid functionals based on a screened Coulomb potential. J. Chem. Phys., 2003, 118(18): 8207 https://doi.org/10.1063/1.1564060
40	Grimme S. . Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem., 2006, 27(15): 1787 https://doi.org/10.1002/jcc.20495
41	Liu S. , Yin H. , F. Liu P. . Strain-dependent electronic and mechanical properties in one-dimensional topological insulator Nb4SiTe4. Phys. Rev. B, 2023, 108(4): 045411 https://doi.org/10.1103/PhysRevB.108.045411
42	Ju L. , Ma Y. , Tan X. , Kou L. . Controllable electrocatalytic to photocatalytic conversion in ferroelectric heterostructures. J. Am. Chem. Soc., 2023, 145(48): 26393 https://doi.org/10.1021/jacs.3c10271
43	Mortazavi B. , Shahrokhi M. , V. Shapeev A. , Rabczuk T. , Zhuang X. . Prediction of C7N6 and C9N4: Stable and strong porous carbon-nitride nanosheets with attractive electronic and optical properties. J. Mater. Chem. C, 2019, 7(35): 10908 https://doi.org/10.1039/C9TC03513C
44	Yoon M. , Yang S. , Wang E. , Zhang Z. . Charged fullerenes as high-capacity hydrogen storage media. Nano Lett., 2007, 7(9): 2578 https://doi.org/10.1021/nl070809a
45	Liu Y. , Ren L. , He Y. , P. Cheng H. . Titanium-decorated graphene for high-capacity hydrogen storage studied by density functional simulations. J. Phys.: Condens. Matter, 2010, 22(44): 445301 https://doi.org/10.1088/0953-8984/22/44/445301
46	Bi L. , Miao Z. , Ge Y. , Liu Z. , Xu Y. , Yin J. , Huang X. , Wang Y. , Yang Z. . Density functional theory study on hydrogen storage capacity of metal-embedded penta-octa-graphene. Int. J. Hydrogen Energy, 2022, 47(76): 32552 https://doi.org/10.1016/j.ijhydene.2022.07.134
47	Khossossi N. , Benhouria Y. , R. Naqvi S. , K. Panda P. , Essaoudi I. , Ainane A. , Ahuja R. . Hydrogen storage characteristics of Li and Na decorated 2D boron phosphide. Sustain. Energy Fuels, 2020, 4(9): 4538 https://doi.org/10.1039/D0SE00709A
48	Haldar S. , Mukherjee S. , V. Singh C. , storage in Li Hydrogen . Na and Ca decorated and defective borophene: A first principles study. RSC Adv., 2018, 8(37): 20748 https://doi.org/10.1039/C7RA12512G

[1]

fop-21385-OF-julin_suppl_1

Download

[1]	B. Li, D. Vretenar, T. Nikšić, J. Zhao, P. W. Zhao, J. Meng. Generalized time-dependent generator coordinate method for induced fission dynamics[J]. Front. Phys. , 2024, 19(4): 44201-.
[2]	Qingyun Zhou, Yusheng Hou, Tianshu Lai. Electronic properties and tunability in graphene/3D-InP mixed-dimensional van der Waals heterostructure[J]. Front. Phys. , 2023, 18(2): 23301-.
[3]	Qingquan Kong, Xuguang An, Lin Huang, Xiaolian Wang, Wei Feng, Siyao Qiu, Qingyuan Wang, Chenghua Sun. A DFT study of Ti₃C₂O₂ MXenes quantum dots supported on single layer graphene: Electronic structure and hydrogen evolution performance[J]. Front. Phys. , 2021, 16(5): 53506-.
[4]	Zhaobo Zhou, Shijun Yuan, Jinlan Wang. Theoretical progress on direct Z-scheme photocatalysis of two-dimensional heterostructures[J]. Front. Phys. , 2021, 16(4): 43203-.
[5]	Sadegh Imani Yengejeh, William Wen, Yun Wang. Mechanical properties of lateral transition metal dichalcogenide heterostructures[J]. Front. Phys. , 2021, 16(1): 13502-.
[6]	Zhi-Yue Zheng, Yu-Hao Pan, Teng-Fei Pei, Rui Xu, Kun-Qi Xu, Le Lei, Sabir Hussain, Xiao-Jun Liu, Li-Hong Bao, Hong-Jun Gao, Wei Ji, Zhi-Hai Cheng. Local probe of the interlayer coupling strength of few-layers SnSe by contact-resonance atomic force microscopy[J]. Front. Phys. , 2020, 15(6): 63505-.
[7]	Thomas Pope, Werner Hofer. Exact orbital-free kinetic energy functional for general many-electron systems[J]. Front. Phys. , 2020, 15(2): 23603-.
[8]	Xue-Hui Xiao, De-Fang Duan, Yan-Bin Ma, Hui Xie, Hao Song, Da Li, Fu-Bo Tian, Bing-Bing Liu, Hong-Yu Yu, Tian Cui. Ab initio studies of copper hydrides under high pressure[J]. Front. Phys. , 2019, 14(4): 43601-.
[9]	Jing-Hua Feng (冯景华), Geng Li (李庚), Xiang-Fei Meng (孟祥飞), Xiao-Dong Jian (菅晓东), Zhen-Hong Dai (戴振宏), Yin-Chang Zhao (赵银昌), Zhen Zhou (周震). Computationally predicting spin semiconductors and half metals from doped phosphorene monolayers[J]. Front. Phys. , 2019, 14(4): 43604-.
[10]	Thomas Pope, Werner Hofer. A two-density approach to the general many-body problem and a proof of principle for small atoms and molecules[J]. Front. Phys. , 2019, 14(2): 23604-.
[11]	Jian Li (李剑), J. Meng (孟杰). Nuclear magnetic moments in covariant density functional theory[J]. Front. Phys. , 2018, 13(6): 132109-.
[12]	Ya-Hui Mao, Li-Fu Zhang, Hui-Li Wang, Huan Shan, Xiao-Fang Zhai, Zhen-Peng Hu, Ai-Di Zhao, Bing Wang. Epitaxial growth of highly strained antimonene on Ag(111)[J]. Front. Phys. , 2018, 13(3): 138106-.
[13]	Longjuan Kong, Kehui Wu, Lan Chen. Recent progress on borophene: Growth and structures[J]. Front. Phys. , 2018, 13(3): 138105-.
[14]	Huaze Shen, Mohan Chen, Zhaoru Sun, Limei Xu, Enge Wang, Xifan Wu. Signature of the hydrogen-bonded environment of liquid water in X-ray emission spectra from first-principles calculations[J]. Front. Phys. , 2018, 13(1): 138204-.
[15]	Yi-Han Cheng,Chuan-Yu Zhang,Juan Ren,Kai-Yu Tong. Hydrogen storage in Li-doped fullerene-intercalated hexagonal boron nitrogen layers[J]. Front. Phys. , 2016, 11(5): 113101-.

Viewed

Full text

Abstract

Cited

Shared

Discussed