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On the hydrogen storage performance of Cu-doped and Cu-decorated graphene quantum dots: a computational study

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Abstract

Hydrogen gas is a promising renewable energy source. The hydrogen storage performance of two differently modified graphene surfaces, particularly Cu-doped and Cu-decorated circumcoronene (CC), is investigated using density functional theory, 6-311G* basis set and Bader's quantum theory of atoms in molecules (QTAIM). It is found that the Cu-doped CC is able to bind three H2 molecules on one Cu atom, while the Cu-decorated CC is able to bind up to five H2 molecules on one Cu atom. Changes in the topology of charge density upon the H2 adsorption are evaluated under the formalism of QTAIM analysis. The QTAIM analysis of bond critical points as well as the density of states analysis show that the interaction between Cu and adsorbed H2 molecules can be considered as a physisorption (a van der Waals type interaction). Overall, the results presented in this study point out that the Cu-decorated graphene surfaces are more suitable potential candidates for hydrogen storage than the Cu-doped ones. Furthermore, the inclusion of diffuse functions in the basis set is critically considered.

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References

  1. Novoselov KS, Geim AK, Morozov SV et al (2004) Electric field effect in atomically thin carbon films. Science 306:666–669. https://doi.org/10.1126/science.1102896

    Article  CAS  PubMed  Google Scholar 

  2. Pykal M, Jurecka P, Karlicky F, Otyepka M (2016) Modelling of graphene functionalization. Phys Chem Chem Phys 18:6351–6372. https://doi.org/10.1039/C5CP03599F

    Article  CAS  PubMed  Google Scholar 

  3. Schedin F, Geim A, Morozov SV et al (2007) Detection of individual gas molecules adsorbed on graphene. Nat Mater 6:652–655. https://doi.org/10.1038/nmat1967

    Article  CAS  PubMed  Google Scholar 

  4. Yang W, Ratinac KR, Ringer SR et al (2010) Carbon nanomaterials in biosensors: should you use nanotubes or graphene. Angew Chemie Int Ed 49:2114–2138. https://doi.org/10.1002/anie.200903463

    Article  CAS  Google Scholar 

  5. Liu Y, Dong X, Chen P (2012) Biological and chemical sensors based on graphene materials. Chem Soc Rev 41:2283–2307. https://doi.org/10.1039/c1cs15270j

    Article  CAS  PubMed  Google Scholar 

  6. Rodrigo D, Limaj O, Janner D et al (2015) Mid-infrared plasmonic biosensing with graphene. Science 349:165–168. https://doi.org/10.1126/science.aab2051

    Article  CAS  PubMed  Google Scholar 

  7. Ambrosi A, Chua CK, Bonanni A, Pumera M (2014) Electrochemistry of graphene and related materials. Chem Rev 114:7150–7188. https://doi.org/10.1021/cr500023c

    Article  CAS  PubMed  Google Scholar 

  8. Lv R, Terrones M (2012) Towards new graphene materials: Doped graphene sheets and nanoribbons. Mater Lett 78:209–218. https://doi.org/10.1016/j.matlet.2012.04.033

    Article  CAS  Google Scholar 

  9. Zhou M, Lu Y-H, Cai Y-Q et al (2011) Adsorption of gas molecules on transition metal embedded graphene: a search for high-performance graphene-based catalysts and gas sensors. Nanotechnology 22:385502. https://doi.org/10.1088/0957-4484/22/38/385502

    Article  CAS  PubMed  Google Scholar 

  10. Düzenli D (2016) A comparative density functional study of hydrogen peroxide adsorption and activation on the graphene surface doped with N, B, S, Pd, Pt, Au, Ag and Cu Atoms. J Phys Chem C 120:20149–20157. https://doi.org/10.1021/acs.jpcc.6b06131

    Article  CAS  Google Scholar 

  11. Wu P, Du P, Zhang H, Cai C (2013) Microscopic effects of the bonding configuration of nitrogen-doped graphene on its reactivity toward hydrogen peroxide reduction reaction. Phys Chem Chem Phys 15:6920. https://doi.org/10.1039/c3cp50900a

    Article  CAS  PubMed  Google Scholar 

  12. Liu S, Huang S (2017) Theoretical insights into the activation of O2 by Pt single atom and Pt4 nanocluster on functionalized graphene support: Critical role of Pt positive polarized charges. Carbon N Y 115:11–17. https://doi.org/10.1016/j.carbon.2016.12.094

    Article  CAS  Google Scholar 

  13. Mohammadi-Manesh E, Vaezzadeh M, Saeidi M (2015a) Cu- and CuO-decorated graphene as a nanosensor for H2S detection at room temperature. Surf Sci 636:36–41. https://doi.org/10.1016/j.susc.2015.02.002

    Article  CAS  Google Scholar 

  14. Mohammadi-Manesh E, Vaezzadeh M, Saeidi M (2015b) Theoretical study on electronic structure and electrical conductance at room temperature of Cu2O-GS nanosensors and detection of H2S gas. Comput Mater Sci 97:181–185. https://doi.org/10.1016/j.commatsci.2014.10.043

    Article  CAS  Google Scholar 

  15. Maaghoul Z, Fazileh F, Kakemam J (2015) A DFT study of formaldehyde adsorption on functionalized graphene nanoribbons. Phys E Low Dimens Syst Nanostructures 66:176–180. https://doi.org/10.1016/j.physe.2014.08.015

    Article  CAS  Google Scholar 

  16. Rad AS (2015) First principles study of Al-doped graphene as nanostructure adsorbent for NO 2 and N 2 O : DFT calculations. Appl Surf Sci j 357:1217–1224

    Article  CAS  Google Scholar 

  17. Wanno B, Tabtimsai C (2014) A DFT investigation of CO adsorption on VIIIB transition metal-doped graphene sheets. Superlattices Microstruct 67:110–117. https://doi.org/10.1016/j.spmi.2013.12.025

    Article  CAS  Google Scholar 

  18. Dai J, Yuan J, Giannozzi P (2009) Gas adsorption on graphene doped with B, N, Al and S: s theoretical study. Appl Phys Lett 95:232105. https://doi.org/10.1063/1.3272008

    Article  CAS  Google Scholar 

  19. Zhou L, Shen F, Tian X et al (2013) Stable Cu2O nanocrystals grown on functionalized graphene sheets and room temperature H2S gas sensing with ultrahigh sensitivity. Nanoscale 5:1564. https://doi.org/10.1039/c2nr33164k

    Article  CAS  PubMed  Google Scholar 

  20. Malček M, Cordeiro MNDS (2018) A DFT and QTAIM study of the adsorption of organic molecules over the copper-doped coronene and circumcoronene. Phys E Low-Dimens Syst Nanostructures 95:59–70. https://doi.org/10.1016/j.physe.2017.09.004

    Article  CAS  Google Scholar 

  21. Janani K, John Thiruvadigal D (2017) Chemical functionalization and edge doping of zigzag graphene nanoribbon with L-(+)-leucine and group IB elements—A DFT study. Appl Surf Sci 418:406–413. https://doi.org/10.1016/j.apsusc.2017.02.192

    Article  CAS  Google Scholar 

  22. Malček M, Bučinský L, Teixeira F, Cordeiro MNDS (2018) Detection of simple inorganic and organic molecules over Cu-decorated circumcoronene: a combined DFT and QTAIM study. Phys Chem Chem Phys 20:16021–16032. https://doi.org/10.1039/c8cp02035c

    Article  CAS  PubMed  Google Scholar 

  23. Bosch-Navarro C, Rourke JP, Wilson NR (2016) Controlled electrochemical and electroless deposition of noble metal nanoparticles on graphene. RSC Adv 6:73790–73796. https://doi.org/10.1039/C6RA14836K

    Article  CAS  Google Scholar 

  24. Feng X, Lv P, Sun W et al (2017) Reduced graphene oxide-supported Cu nanoparticles for the selective oxidation of benzyl alcohol to aldehyde with molecular oxygen. Catal Commun 99:105–109. https://doi.org/10.1016/j.catcom.2017.05.013

    Article  CAS  Google Scholar 

  25. Bayev VG, Fedotova JA, Kasiuk JV et al (2018) CVD graphene sheets electrochemically decorated with “core-shell” Co/CoO nanoparticles. Appl Surf Sci 440:1252–1260. https://doi.org/10.1016/j.apsusc.2018.01.245

    Article  CAS  Google Scholar 

  26. Durán GM, Benavidez TE, Contento AM et al (2017) Analysis of penicillamine using Cu-modified graphene quantum dots synthesized from uric acid as single precursor. J Pharm Anal 7:324–331. https://doi.org/10.1016/j.jpha.2017.07.002

    Article  PubMed  PubMed Central  Google Scholar 

  27. Lonkar SP, Deshmukh YS, Abdala AA (2015) Recent advances in chemical modifications of graphene. Nano Res 8:1039–1074. https://doi.org/10.1007/s12274-014-0622-9

    Article  CAS  Google Scholar 

  28. Lin L, Zhou W, Gao R et al (2017) Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts. Nat Publ Gr 544:80–83. https://doi.org/10.1038/nature21672

    Article  CAS  Google Scholar 

  29. Xiang C, Li A, Yang S et al (2019) Enhanced hydrogen storage performance of graphene nano fl akes doped with Cr atoms : a DFT. RSC Adv 9:25690–25696. https://doi.org/10.1039/c9ra04589a

    Article  CAS  Google Scholar 

  30. Tabtimsai C, Rakrai W, Wanno B (2017) Hydrogen adsorption on graphene sheets doped with group 8B transition metal : a DFT investigation. Vaccum 139:101–108. https://doi.org/10.1016/j.vacuum.2017.02.013

    Article  CAS  Google Scholar 

  31. Zhou Y, Chu W, Jing F et al (2017) Applied Surface Science Enhanced hydrogen storage on Li-doped defective graphene with B substitution : a DFT study . Appl Surf Sci 410:166–176. https://doi.org/10.1016/j.apsusc.2017.03.057

    Article  CAS  Google Scholar 

  32. Wang L, Chen X, Du H et al (2018) First-principles investigation on hydrogen storage performance of Li, Na and K decorated borophene. Appl Surf Sci 427:1030–1037. https://doi.org/10.1016/j.apsusc.2017.08.126

    Article  CAS  Google Scholar 

  33. Yang S, Lan Z, Xu H et al (2018) A first-principles study on hydrogen sensing properties of pristine and Mo-doped graphene. Int J Nanotechnol 2018:1–5. https://doi.org/10.1155/2018/2031805

    Article  CAS  Google Scholar 

  34. Faye O, Eduok U, Szpunar J et al (2017) Hydrogen storage on bare Cu atom and Cu-functionalized boron-doped graphene: a first principles study. Int J Hydrog Energy 42:4233–4243. https://doi.org/10.1016/j.ijhydene.2016.10.031

    Article  CAS  Google Scholar 

  35. Faye O, Szpunar JA, Szpunar B, Chedikh A (2017) Hydrogen adsorption and storage on Palladium—functionalized graphene with NH-dopant : a first principles calculation. Appl Surf Sci 392:362–374. https://doi.org/10.1016/j.apsusc.2016.09.032

    Article  CAS  Google Scholar 

  36. Ruiz ME, Garcia-Prieto J, Novaro O (1984) Theoretical studies of photoexcited state Cu atom reactions. I. excited state responsible for H2 capture. J Chem Phys 80:1529–1534. https://doi.org/10.1063/1.446902

    Article  CAS  Google Scholar 

  37. Bader RFW (1990) Atoms in molecules: a quantum theory. Oxford university press, Oxford

    Google Scholar 

  38. Colherinhas G, Fileti EE, Chaban VV (2015a) The band gap of graphene is efficiently tuned by monovalent ions. J Phys Chem Lett 6:302–307. https://doi.org/10.1021/jz502601z

    Article  CAS  PubMed  Google Scholar 

  39. Colherinhas G, Fileti EE, Chaban VV (2015b) Can inorganic salts tune electronic properties. Phys Chem Chem Phys 17:17413–17420. https://doi.org/10.1039/C5CP02083B

    Article  CAS  PubMed  Google Scholar 

  40. Colherinhas G, Fileti EE, Chaban VV (2016) Potential energy surface of excited semiconductors: graphene quantum dot and BODIPY. Chem Phys 474:1–6. https://doi.org/10.1016/j.chemphys.2016.05.011

    Article  CAS  Google Scholar 

  41. Zhu C, Yang G (2016) Insights from the adsorption of halide ions on graphene materials. Chem Phys Chem 17:2482–2488. https://doi.org/10.1002/cphc.201600271

    Article  CAS  PubMed  Google Scholar 

  42. Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098–3100

    Article  CAS  Google Scholar 

  43. Lee C, Yang W, Parr RG (1988) Development of the colic-salvetti correlation-energy formula into a functional of the electron D. Phys Rev B 37:785–789

    Article  CAS  Google Scholar 

  44. Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652. https://doi.org/10.1063/1.464913

    Article  CAS  Google Scholar 

  45. Vosko SH, Wilk L, Nusair M (1980) Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis. Can J Phys 58:1200–1211. https://doi.org/10.1139/p80-159

    Article  CAS  Google Scholar 

  46. Grimme S (2006) Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem 27:1787–1799. https://doi.org/10.1002/jcc

    Article  CAS  PubMed  Google Scholar 

  47. Krishnan R, Binkley JS, Seeger R, Pople JA (1980) Self-consistent molecular orbital methods. XX. a basis set for correlated wave functions. J Chem Phys 72:650–654

    Article  CAS  Google Scholar 

  48. McLean AD, Chandler GS (1980) Contracted Gaussian basis sets for molecular calculations. I. second row atoms, Z=11–18. J Chem Phys 72:5639–5648

    Article  CAS  Google Scholar 

  49. Wachters AJH (1970) Gaussian basis set for molecular wavefunctions containing third-row atoms. J Chem Phys 52:1033–1036

    Article  CAS  Google Scholar 

  50. Sousa SF, Fernandes PA, Ramos MJ (2007) General performance of density functionals. J Phys Chem A 111:10439–10452. https://doi.org/10.1021/jp0734474

    Article  CAS  PubMed  Google Scholar 

  51. Ramalho JPP, Gomes JRB, Illas F (2013) Accounting for van der Waals interactions between adsorbates and surfaces in density functional theory based calculations: selected examples. RSC Adv 3:13085–13100. https://doi.org/10.1039/c3ra40713f

    Article  CAS  Google Scholar 

  52. Grimme S, Hansen A, Brandenburg JG, Bannwarth C (2016) Dispersion-corrected mean-field electronic structure methods. Chem Rev 116:5105–5154. https://doi.org/10.1021/acs.chemrev.5b00533

    Article  CAS  PubMed  Google Scholar 

  53. Mollenhauer D, Brieger C, Voloshina E, Paulus B (2015) Performance of dispersion-corrected DFT for the weak interaction between aromatic molecules and extended carbon-based systems. J Phys Chem C 119:1898–1904. https://doi.org/10.1021/jp5113312

    Article  CAS  Google Scholar 

  54. Le D, Kara A, Schroder E et al (2012) Physisorption of nucleobases on graphene: a comparative van der Waals study. J Phys Condens Matter 24:424210. https://doi.org/10.1088/0953-8984/24/42/424210

    Article  CAS  PubMed  Google Scholar 

  55. Frisch MJ, Trucks GW, Schlegel HB, et al. (2009) Gaussian 09, Revision D.01

  56. Keith TA AIMAll, version 14.04.17; TK Gristmill software: Overland Park, KS, 2014 (aim.tkgristmill.com)

  57. O’Boyle NM, Tenderholt AL, Langner KM (2008) cclib: a library for package-independent computational chemistry algorithms. J Comput Chem 29:839–845. https://doi.org/10.1002/jcc.20823

    Article  CAS  PubMed  Google Scholar 

  58. Flükiger P, Lüthi HP, Sortmann S, Weber J “MOLEKEL 4.3.” Swiss center for scientific computing: Manno, Switzerland 2002

  59. Clark T, Chandrasekhar J, Spitznagel GW, Schleyer PVR (1983) Efficient diffuse function—augmented basis sets for anion calculations. III.* The 3–21 + G basis set for first-row. J Comp Chem 4:294–301. https://doi.org/10.1002/jcc.540040303

    Article  CAS  Google Scholar 

  60. Boys SF, Bernardi F (1970) The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Mol Phys 19:553–566. https://doi.org/10.1080/00268977000101561

    Article  CAS  Google Scholar 

  61. Bacskay GB (1952) A quadritically convergent hartree-fock (QC-SCF) method. Application to open shell orbital optimization and coupled perturbed hartree-fock calculations. Chem Phys 65:383–396. https://doi.org/10.1016/0301-0104(82)85211-7

    Article  Google Scholar 

  62. Luna-Garcia H, Ramirez-Solis A, Castillo S (2002) Ab initio studies of the reactions of Cu (2 S, 2 D and 2 P) with SiH 4 and GeH 4. J Chem Phys 116:928–935. https://doi.org/10.1063/1.1427713

    Article  CAS  Google Scholar 

  63. Bhagi-Damodaran A, Michael MA, Zhu Q et al (2017) Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases. Nat Chem 9:257–263. https://doi.org/10.1038/nchem.2643

    Article  CAS  PubMed  Google Scholar 

  64. López CS, de Lera ÁR (2011) Bond ellipticity as a measure of electron delocalization in structure and reactivity. Curr Org Chem 15:3576–3593. https://doi.org/10.2174/138527211797636228

    Article  Google Scholar 

  65. Bader RFW, Stephens ME (1975) Spatial localization of the electronic pair and number distributions in molecules. J Am Chem Soc 97:7391–7399. https://doi.org/10.1021/ja00859a001

    Article  CAS  Google Scholar 

  66. Afonin AV, Vashchenko AV, Sigalov MV (2016) Estimating the energy of intramolecular hydrogen bonds from 1 H NMR and QTAIM calculations. Org Biomol Chem 14:11199–11211. https://doi.org/10.1039/C6OB01604A

    Article  CAS  PubMed  Google Scholar 

  67. Arslancan S, Herrera B, Lamsabhi AM (2020) On the nature of the interaction of copper hydride and halide with substituted ethylene and acetylene. J Mol Model 26:61. https://doi.org/10.1007/s00894-020-4320-0

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

This work received financial support from Slovak Grant Agencies APVV (contracts No. APVV-15-0079, APVV-15-0053, APVV-19-0024 and APVV-19-0087) and VEGA (contracts No. 1/0139/20 and 1/0466/18). We are also grateful to the HPC center at the Slovak university of technology in Bratislava, which is a part of the Slovak infrastructure of high performance computing (SIVVP project, ITMS code 26230120002, funded by the European region development funds) for the computational time and resources made available. To all financing sources the authors are greatly indebted.

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  1. Faculty of Chemical and Food Technology, Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Radlinského 9, 812 37, Bratislava, Slovak Republic

    Michal Malček & Lukáš Bučinský

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Published as part of the topical collection of articles from the 17th edition of the Central European Symposium on Theoretical Chemistry (CESTC 2019) in Austria

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Malček, M., Bučinský, L. On the hydrogen storage performance of Cu-doped and Cu-decorated graphene quantum dots: a computational study. Theor Chem Acc 139, 167 (2020). https://doi.org/10.1007/s00214-020-02680-2

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