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<article article-type="research-article" dtd-version="1.3" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:lang="en"><front><journal-meta><journal-id journal-id-type="publisher-id">najo</journal-id><journal-title-group><journal-title xml:lang="en">Nanosystems: Physics, Chemistry, Mathematics</journal-title><trans-title-group xml:lang="ru"><trans-title>Наносистемы: физика, химия, математика</trans-title></trans-title-group></journal-title-group><issn pub-type="ppub">2220-8054</issn><issn pub-type="epub">2305-7971</issn><publisher><publisher-name>Университет ИТМО</publisher-name></publisher></journal-meta><article-meta><article-id custom-type="elpub" pub-id-type="custom">najo-1152</article-id><article-categories><subj-group subj-group-type="heading"><subject>Research Article</subject></subj-group><subj-group subj-group-type="section-heading" xml:lang="en"><subject>PHYSICS</subject></subj-group><subj-group subj-group-type="section-heading" xml:lang="ru"><subject>ФИЗИКА</subject></subj-group></article-categories><title-group><article-title>Nanoscale reduced-graphene-oxide origin of shungite in light of neutron scattering</article-title><trans-title-group xml:lang="ru"><trans-title></trans-title></trans-title-group></title-group><contrib-group><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="western" xml:lang="en"><surname>Sheka</surname><given-names>E. F.</given-names></name></name-alternatives><bio xml:lang="en"><p>Moscow</p></bio><email xlink:type="simple">sheka@icp.ac.ru</email><xref ref-type="aff" rid="aff-1"/></contrib><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="western" xml:lang="en"><surname>Rozhkova</surname><given-names>N. N.</given-names></name></name-alternatives><bio xml:lang="en"><p>Petrozavodsk</p></bio><email xlink:type="simple">rozhkova@krc.karelia.ru</email><xref ref-type="aff" rid="aff-2"/></contrib><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="western" xml:lang="en"><surname>Hołderna-Natkaniec</surname><given-names>K.</given-names></name></name-alternatives><bio xml:lang="en"><p>Poznan</p></bio><xref ref-type="aff" rid="aff-3"/></contrib><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="western" xml:lang="en"><surname>Natkaniec</surname><given-names>I.</given-names></name></name-alternatives><bio xml:lang="en"><p>Poznan, Poland</p><p>Dubna, Russia</p></bio><email xlink:type="simple">inat@jinr.ru</email><xref ref-type="aff" rid="aff-4"/></contrib></contrib-group><aff xml:lang="en" id="aff-1"><institution>Faculty of Physics, Mathematics and Natural Sciences, Peoples’ Friendship University of Russia</institution><country>Russian Federation</country></aff><aff xml:lang="en" id="aff-2"><institution>Institute of Geology, Karelian Research Centre RAS</institution><country>Russian Federation</country></aff><aff xml:lang="en" id="aff-3"><institution>Faculty of Physics, Adam Mickiewicz University</institution><country>Poland</country></aff><aff xml:lang="en" id="aff-4"><institution>Faculty of Physics, Adam Mickiewicz University; Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research</institution><country>Russian Federation</country></aff><pub-date pub-type="collection"><year>2014</year></pub-date><pub-date pub-type="epub"><day>18</day><month>08</month><year>2025</year></pub-date><volume>5</volume><issue>5</issue><fpage>659</fpage><lpage>676</lpage><permissions><copyright-statement>Copyright &amp;#x00A9; Sheka E.F., Rozhkova N.N., Hołderna-Natkaniec K., Natkaniec I., 2025</copyright-statement><copyright-year>2025</copyright-year><copyright-holder xml:lang="ru">Sheka E.F., Rozhkova N.N., Hołderna-Natkaniec K., Natkaniec I.</copyright-holder><copyright-holder xml:lang="en">Sheka E.F., Rozhkova N.N., Hołderna-Natkaniec K., Natkaniec I.</copyright-holder><license xml:lang="ru" license-type="creative-commons-attribution" xlink:href="https://creativecommons.org/licenses/by/4.0/" xlink:type="simple"><license-p>Данная работа распространяется под лицензией Creative Commons Attribution 4.0.</license-p></license><license xml:lang="en" license-type="creative-commons-attribution" xlink:href="https://creativecommons.org/licenses/by/4.0/" xlink:type="simple"><license-p>This work is licensed under a Creative Commons Attribution 4.0 License.</license-p></license></permissions><self-uri xlink:href="https://nanojournal.ifmo.ru/jour/article/view/1152">https://nanojournal.ifmo.ru/jour/article/view/1152</self-uri><abstract><p>New concept of shungite carbon exhibits this raw material as a multi-level fractal structure of nanosize fragments of reduced graphene oxide (rGO) (Int. J. Smart Nano Mat. 1, 1, 2014). The natural rGO deposits turn out to be quite challenging for the current graphene technology. Once consistent with all the block of the available geological and physicochemical data obtained during the last few decades, the concept nonetheless needs a direct conﬁrmation in terms of the current graphene science. The ﬁrst such acknowledgement has been received just recently when studying photoluminescence (PL) of shungite dispersions (JETP 118, 735, 2014). A close similarity of PL spectra of aqueous dispersion of shungite and those of synthetic graphene quantum dots of the rGO origin has been established. The current paper presents the next direct conﬁrmation provided with neutron scattering. Elastic neutron diﬀraction and inelastic neutron scattering have left no doubts concerning both graphene-like conﬁguration and chemical composition of basic structural elements of shungite attributing the latter to rGO nanosize sheets with an average ∼6:0.1:2 (C:O:H) atomic content ratio per one benzenoid unit. The experimental data are supplemented with quantum chemical calculations that allowed suggesting a clear vision of the shungite structure at its ﬁrst fractal levels.</p></abstract><kwd-group xml:lang="en"><kwd>shungite</kwd><kwd>natural nanoscale reduced graphene oxide</kwd><kwd>multi-stage reduction of graphene oxide</kwd><kwd>retained water</kwd><kwd>elastic and inelastic neutron scattering</kwd><kwd>quantum chemical calculations</kwd></kwd-group><funding-group><funding-statement xml:lang="en">The authors greatly appreciates financial support of RSF grants 14-08-91376 (E. Sh.) and 13-03-00422 (N.R.) as well as the Basic Research Program, RAS, Earth Sciences Section- 5. The grants of the Polish Plenipotentiary in JINR for the modernization project of the NERA spectrometer in 2007–2012 are gratefully acknowledged.</funding-statement></funding-group></article-meta></front><back><ref-list><title>References</title><ref id="cit1"><label>1</label><citation-alternatives><mixed-citation xml:lang="ru">Luo J., Kim J., Huang J. Material processing of chemically modiﬁed graphene: Some challenges and solutions. J. Acc Chem. Res., 46, P. 2225–2234 (2013).</mixed-citation><mixed-citation xml:lang="en">Luo J., Kim J., Huang J. Material processing of chemically modiﬁed graphene: Some challenges and solutions. J. Acc Chem. Res., 46, P. 2225–2234 (2013).</mixed-citation></citation-alternatives></ref><ref id="cit2"><label>2</label><citation-alternatives><mixed-citation xml:lang="ru">Chua C.K., Pumera M. Chemical reduction of graphene oxide: a synthetic chemistry viewpoint. Chem. Soc. Rev., 43, P. 291–312 (2014).</mixed-citation><mixed-citation xml:lang="en">Chua C.K., Pumera M. Chemical reduction of graphene oxide: a synthetic chemistry viewpoint. Chem. Soc. Rev., 43, P. 291–312 (2014).</mixed-citation></citation-alternatives></ref><ref id="cit3"><label>3</label><citation-alternatives><mixed-citation xml:lang="ru">Sheka E.F., Rozhkova N.N. Shungite as the natural pantry of nanoscale reduced graphene oxide Int. J. Smart Nano Mat., 5, P. 1–16 (2014).</mixed-citation><mixed-citation xml:lang="en">Sheka E.F., Rozhkova N.N. Shungite as the natural pantry of nanoscale reduced graphene oxide Int. J. Smart Nano Mat., 5, P. 1–16 (2014).</mixed-citation></citation-alternatives></ref><ref id="cit4"><label>4</label><citation-alternatives><mixed-citation xml:lang="ru">Rozhkova N.N. Shungite Nanocarbon (in Russ). Karelian Research Centre of RAS, Petrozavodsk (2011).</mixed-citation><mixed-citation xml:lang="en">Rozhkova N.N. Shungite Nanocarbon (in Russ). Karelian Research Centre of RAS, Petrozavodsk (2011).</mixed-citation></citation-alternatives></ref><ref id="cit5"><label>5</label><citation-alternatives><mixed-citation xml:lang="ru">Rozhkova N.N. Aggregation and stabilization of shungite carbon nanoparticles. Russ J Gen Chem, 83, P. 2676–2685 (2013).</mixed-citation><mixed-citation xml:lang="en">Rozhkova N.N. Aggregation and stabilization of shungite carbon nanoparticles. Russ J Gen Chem, 83, P. 2676–2685 (2013).</mixed-citation></citation-alternatives></ref><ref id="cit6"><label>6</label><citation-alternatives><mixed-citation xml:lang="ru">Razbirin B.S., Rozhkova N.N., Sheka E.F., et. al. Fractals of graphene quantum dots in photoluminescence of shungite. J. Exp.Theor. Phys., 118, P. 735–746 (2014).</mixed-citation><mixed-citation xml:lang="en">Razbirin B.S., Rozhkova N.N., Sheka E.F., et. al. Fractals of graphene quantum dots in photoluminescence of shungite. J. Exp.Theor. Phys., 118, P. 735–746 (2014).</mixed-citation></citation-alternatives></ref><ref id="cit7"><label>7</label><citation-alternatives><mixed-citation xml:lang="ru">Razbirin B.S., Rozhkova N.N., Sheka E.F. Photonics of shungite quantum dots arXiv:1406.1703v1 [condmat.mtrl-sci] (2014).</mixed-citation><mixed-citation xml:lang="en">Razbirin B.S., Rozhkova N.N., Sheka E.F. Photonics of shungite quantum dots arXiv:1406.1703v1 [condmat.mtrl-sci] (2014).</mixed-citation></citation-alternatives></ref><ref id="cit8"><label>8</label><citation-alternatives><mixed-citation xml:lang="ru">Li L., Wu G., Yang G., Peng J., Zhao, Zhu J.J. Focusing on luminescent graphene quantum dots: current status and future perspectives. Nanoscale, 5, P. 4015–4039 (2013).</mixed-citation><mixed-citation xml:lang="en">Li L., Wu G., Yang G., Peng J., Zhao, Zhu J.J. Focusing on luminescent graphene quantum dots: current status and future perspectives. Nanoscale, 5, P. 4015–4039 (2013).</mixed-citation></citation-alternatives></ref><ref id="cit9"><label>9</label><citation-alternatives><mixed-citation xml:lang="ru">Sheka E.F., Natkaniec I., Rozhkova N.N., HoldernaNatkaniec K. Neutron scattering study of reduced graphene oxide of natural origin. JETP Lett., 118, P. 735–746 (2014).</mixed-citation><mixed-citation xml:lang="en">Sheka E.F., Natkaniec I., Rozhkova N.N., HoldernaNatkaniec K. Neutron scattering study of reduced graphene oxide of natural origin. JETP Lett., 118, P. 735–746 (2014).</mixed-citation></citation-alternatives></ref><ref id="cit10"><label>10</label><citation-alternatives><mixed-citation xml:lang="ru">Rozhkova N.N., Gribanov A.V., Khodorkovskii M.A. Water mediated modiﬁcation of structure and physical chemical properties of nanocarbons. Diam. Rel. Mat., 16, P. 2104–2108 (2007).</mixed-citation><mixed-citation xml:lang="en">Rozhkova N.N., Gribanov A.V., Khodorkovskii M.A. Water mediated modiﬁcation of structure and physical chemical properties of nanocarbons. Diam. Rel. Mat., 16, P. 2104–2108 (2007).</mixed-citation></citation-alternatives></ref><ref id="cit11"><label>11</label><citation-alternatives><mixed-citation xml:lang="ru">Natkaniec I., Bragin S.I., Brankowski J., Mayer J. NERA spectrometer at IBR2 in Proc ICANS XII Meeting, Abington 1993, RAL Report 94-025 I: 89–85 (1994).</mixed-citation><mixed-citation xml:lang="en">Natkaniec I., Bragin S.I., Brankowski J., Mayer J. NERA spectrometer at IBR2 in Proc ICANS XII Meeting, Abington 1993, RAL Report 94-025 I: 89–85 (1994).</mixed-citation></citation-alternatives></ref><ref id="cit12"><label>12</label><citation-alternatives><mixed-citation xml:lang="ru">Opalev S.V., Belenkov E.A. Experimental study of changing graphite structure under milling. (in Russ.) Izvestiya Chelyabinskogo Nauchnogo Centra, 3, P. 27–30 (2004).</mixed-citation><mixed-citation xml:lang="en">Opalev S.V., Belenkov E.A. Experimental study of changing graphite structure under milling. (in Russ.) Izvestiya Chelyabinskogo Nauchnogo Centra, 3, P. 27–30 (2004).</mixed-citation></citation-alternatives></ref><ref id="cit13"><label>13</label><citation-alternatives><mixed-citation xml:lang="ru">Emel’yanova G.I., Gorlenko L.E., Rozhkova N.N. et. al. Eﬀect of the conditions of structure formation on the physicochemical properties of ozonated shungites. Russ. J. Phys. Chem. A, 84, P. 1376–1381 (2010).</mixed-citation><mixed-citation xml:lang="en">Emel’yanova G.I., Gorlenko L.E., Rozhkova N.N. et. al. Eﬀect of the conditions of structure formation on the physicochemical properties of ozonated shungites. Russ. J. Phys. Chem. A, 84, P. 1376–1381 (2010).</mixed-citation></citation-alternatives></ref><ref id="cit14"><label>14</label><citation-alternatives><mixed-citation xml:lang="ru">Kovalevski V.V., Buseck P.R., Cowley J.M. Comparison of carbon in shungite rocks to other natural carbons: An X-ray and TEM study Carbon, 39, P. 243–256 (2001).</mixed-citation><mixed-citation xml:lang="en">Kovalevski V.V., Buseck P.R., Cowley J.M. Comparison of carbon in shungite rocks to other natural carbons: An X-ray and TEM study Carbon, 39, P. 243–256 (2001).</mixed-citation></citation-alternatives></ref><ref id="cit15"><label>15</label><citation-alternatives><mixed-citation xml:lang="ru">Bokhenkov E.L., Natkaniec I., Sheka E.F. Determination of the density of phonon states of naphthalene crystal from inelastic incoherent neutron scattering. J. Exp. Theor. Phys., 43, P. 536–545 (1976).</mixed-citation><mixed-citation xml:lang="en">Bokhenkov E.L., Natkaniec I., Sheka E.F. Determination of the density of phonon states of naphthalene crystal from inelastic incoherent neutron scattering. J. Exp. Theor. Phys., 43, P. 536–545 (1976).</mixed-citation></citation-alternatives></ref><ref id="cit16"><label>16</label><citation-alternatives><mixed-citation xml:lang="ru">Hall P.G., Pidduck A., Wright C.J. Inelastic neutron scattering by water adsorbed on silica. J. Colloid. Interface Sci., 79, P. 339–344 (1981).</mixed-citation><mixed-citation xml:lang="en">Hall P.G., Pidduck A., Wright C.J. Inelastic neutron scattering by water adsorbed on silica. J. Colloid. Interface Sci., 79, P. 339–344 (1981).</mixed-citation></citation-alternatives></ref><ref id="cit17"><label>17</label><citation-alternatives><mixed-citation xml:lang="ru">Sheka E.F., Khavryutchenko V.D., Markichev I.V. Technological polymorphism of disperse amorphous silicas: inelastic neutron scattering and computer modeling Russ. Chem. Rev., 64, P. 389–414 (1995).</mixed-citation><mixed-citation xml:lang="en">Sheka E.F., Khavryutchenko V.D., Markichev I.V. Technological polymorphism of disperse amorphous silicas: inelastic neutron scattering and computer modeling Russ. Chem. Rev., 64, P. 389–414 (1995).</mixed-citation></citation-alternatives></ref><ref id="cit18"><label>18</label><citation-alternatives><mixed-citation xml:lang="ru">Crupi V., Majolino D., Migliardo P., Venuti V. Neutron scattering study and dynamic properties of hydrogen-bonded liquids in mesoscopic conﬁnement. 1. The water case. J. Phys. Chem. B, 106, P. 10884– 10894 (2002).</mixed-citation><mixed-citation xml:lang="en">Crupi V., Majolino D., Migliardo P., Venuti V. Neutron scattering study and dynamic properties of hydrogen-bonded liquids in mesoscopic conﬁnement. 1. The water case. J. Phys. Chem. B, 106, P. 10884– 10894 (2002).</mixed-citation></citation-alternatives></ref><ref id="cit19"><label>19</label><citation-alternatives><mixed-citation xml:lang="ru">Buchsteiner A., Lerf A., Pieper J. Water dynamics in graphite oxide investigated with neutron scattering. J. Phys. Chem. B, 110, P. 22328–22338 (2006).</mixed-citation><mixed-citation xml:lang="en">Buchsteiner A., Lerf A., Pieper J. Water dynamics in graphite oxide investigated with neutron scattering. J. Phys. Chem. B, 110, P. 22328–22338 (2006).</mixed-citation></citation-alternatives></ref><ref id="cit20"><label>20</label><citation-alternatives><mixed-citation xml:lang="ru">Corsaro C., Crupi V., Majolino D. et. al. Inelastic neutron scattering study of water in hydrated LTA-type zeolites. J. Phys. Chem. A, 110, P. 1190–1195 (2006).</mixed-citation><mixed-citation xml:lang="en">Corsaro C., Crupi V., Majolino D. et. al. Inelastic neutron scattering study of water in hydrated LTA-type zeolites. J. Phys. Chem. A, 110, P. 1190–1195 (2006).</mixed-citation></citation-alternatives></ref><ref id="cit21"><label>21</label><citation-alternatives><mixed-citation xml:lang="ru">Natkaniec I., Sheka E.F., Drubicki K. et. al. arXiv:1411.xxxx [cond-mat.mtrl-sci] (2014).</mixed-citation><mixed-citation xml:lang="en">Natkaniec I., Sheka E.F., Drubicki K. et. al. arXiv:1411.xxxx [cond-mat.mtrl-sci] (2014).</mixed-citation></citation-alternatives></ref><ref id="cit22"><label>22</label><citation-alternatives><mixed-citation xml:lang="ru">Bertrand C.E., Zhang Y., Chen S.H. Deeply-cooled water under strong conﬁnement: neutron scattering investigations and the liquid–liquid critical point hypothesis. Phys. Chem. Chem. Phys., 15, P. 721–745 (2013).</mixed-citation><mixed-citation xml:lang="en">Bertrand C.E., Zhang Y., Chen S.H. Deeply-cooled water under strong conﬁnement: neutron scattering investigations and the liquid–liquid critical point hypothesis. Phys. Chem. Chem. Phys., 15, P. 721–745 (2013).</mixed-citation></citation-alternatives></ref><ref id="cit23"><label>23</label><citation-alternatives><mixed-citation xml:lang="ru">Avdeev M.V., Tropin T.V., Aksenov V.L. et. al. Pore structures in shungites as revealed by small-angle neutron scattering Carbon. 44, P. 954–961 (2006).</mixed-citation><mixed-citation xml:lang="en">Avdeev M.V., Tropin T.V., Aksenov V.L. et. al. Pore structures in shungites as revealed by small-angle neutron scattering Carbon. 44, P. 954–961 (2006).</mixed-citation></citation-alternatives></ref><ref id="cit24"><label>24</label><citation-alternatives><mixed-citation xml:lang="ru">Sheka E.F., Popova N.A. Molecular theory of graphene oxide. Phys. Chem. Chem. Phys., 15, P. 13304– 13322 (2013).</mixed-citation><mixed-citation xml:lang="en">Sheka E.F., Popova N.A. Molecular theory of graphene oxide. Phys. Chem. Chem. Phys., 15, P. 13304– 13322 (2013).</mixed-citation></citation-alternatives></ref><ref id="cit25"><label>25</label><citation-alternatives><mixed-citation xml:lang="ru">Golubev E.A. Private communication.</mixed-citation><mixed-citation xml:lang="en">Golubev E.A. Private communication.</mixed-citation></citation-alternatives></ref><ref id="cit26"><label>26</label><citation-alternatives><mixed-citation xml:lang="ru">Druzbicki K., Natkaniec I. Vibrational properties of water retained in graphene oxide. Chem. Phys. Lett., 600, P. 106–111 (2014).</mixed-citation><mixed-citation xml:lang="en">Druzbicki K., Natkaniec I. Vibrational properties of water retained in graphene oxide. Chem. Phys. Lett., 600, P. 106–111 (2014).</mixed-citation></citation-alternatives></ref><ref id="cit27"><label>27</label><citation-alternatives><mixed-citation xml:lang="ru">Sheka E.F. Computational strategy for graphene: Insight from odd electrons correlation Int. J. Quant. Chem., 112, P. 3076–3090 (2012).</mixed-citation><mixed-citation xml:lang="en">Sheka E.F. Computational strategy for graphene: Insight from odd electrons correlation Int. J. Quant. Chem., 112, P. 3076–3090 (2012).</mixed-citation></citation-alternatives></ref><ref id="cit28"><label>28</label><citation-alternatives><mixed-citation xml:lang="ru">Xu Z., Bando Y., Liu L. et. al. Electrical conductivity, chemistry, and bonding alternations under graphene oxide to graphene transition as revealed by in situ TEM. ACS Nano, 5, P. 4401–4406 (2011).</mixed-citation><mixed-citation xml:lang="en">Xu Z., Bando Y., Liu L. et. al. Electrical conductivity, chemistry, and bonding alternations under graphene oxide to graphene transition as revealed by in situ TEM. ACS Nano, 5, P. 4401–4406 (2011).</mixed-citation></citation-alternatives></ref><ref id="cit29"><label>29</label><citation-alternatives><mixed-citation xml:lang="ru">Tkachev S.V., Buslaeva E.Yu., Naumkin A.V. et. al. Reduced graphene oxide Inorg. Mater., 48, P. 796– 802 (2011).</mixed-citation><mixed-citation xml:lang="en">Tkachev S.V., Buslaeva E.Yu., Naumkin A.V. et. al. Reduced graphene oxide Inorg. Mater., 48, P. 796– 802 (2011).</mixed-citation></citation-alternatives></ref><ref id="cit30"><label>30</label><citation-alternatives><mixed-citation xml:lang="ru">Stobinski L. www.nanomaterials.pl (2014).</mixed-citation><mixed-citation xml:lang="en">Stobinski L. www.nanomaterials.pl (2014).</mixed-citation></citation-alternatives></ref><ref id="cit31"><label>31</label><citation-alternatives><mixed-citation xml:lang="ru">Sheka E.F., Popova N.A. Odd-electron molecular theory of the graphene hydrogenation. J. Mol. Mod., 18, P. 3751–3768 (2012).</mixed-citation><mixed-citation xml:lang="en">Sheka E.F., Popova N.A. Odd-electron molecular theory of the graphene hydrogenation. J. Mol. Mod., 18, P. 3751–3768 (2012).</mixed-citation></citation-alternatives></ref></ref-list><fn-group><fn fn-type="conflict"><p>The authors declare that there are no conflicts of interest present.</p></fn></fn-group></back></article>
