Odkryto nową formę węgla – „Otwiera zupełnie nowe możliwości”
![Odkryto nową formę węgla – „Otwiera zupełnie nowe możliwości”](https://oen.pl/wp-content/uploads/2023/02/Carbon-Element-Concept-770x470.jpg)
![Koncepcja elementu węglowego](https://oen.pl/wp-content/uploads/2023/02/Odkryto-nowa-forme-wegla-–-„Otwiera-zupelnie-nowe-mozliwosci.jpg)
Zespół przewiduje potencjalne zastosowania tej nowej formy węgla w pozyskiwaniu, przetwarzaniu i magazynowaniu energii, katalizowaniu produkcji chemikaliów oraz oddzielaniu jonów lub gazów molekularnych.
Nowatorska forma węgla powstaje w wyniku ogrzewania fulerenów z azotkiem litu.
Najbardziej rozpoznawalnymi formami węgla są grafit i diament, jednak istnieją inne unikalne alotropy węgla w nanoskali, takie jak[{” attribute=””>graphene and fullerenes. These are sp2 hybridized carbon structures with either zero (flat-shaped) or positive (sphere-shaped) curvatures.
Meanwhile, sp2 hybridized carbon with negative curvature, called “schwarzite”, has been proposed theoretically, and its discovery has been a dream of some scientists in the field of carbon materials. It has been learned that carbon can be templated into some of the periodic pores of certain zeolites via vapor deposition but the templating is incomplete due to some pores simply being too narrow. This has thwarted making carbon schwartzites by templating routes.
Recently, a team of researchers from the Center for Multidimensional Carbon Materials within the Institute for Basic Science (IBS), South Korea led by Director Rodney Ruoff and his colleagues at the University of Science and Technology of China led by Professor Yanwu Zhu, reported a discovery of a new form of carbon.
![Carbon Microstructure Characterization](https://oen.pl/wp-content/uploads/2023/02/1676274108_729_Odkryto-nowa-forme-wegla-–-„Otwiera-zupelnie-nowe-mozliwosci.jpg 663w,https://scitechdaily.com/images/Carbon-Microstructure-Characterization-259x400.jpg 259w,https://scitechdaily.com/images/Carbon-Microstructure-Characterization-768x1187.jpg 768w,https://scitechdaily.com/images/Carbon-Microstructure-Characterization-994x1536.jpg 994w,https://scitechdaily.com/images/Carbon-Microstructure-Characterization-1325x2048.jpg 1325w,https://scitechdaily.com/images/Carbon-Microstructure-Characterization.jpg 1496w)
a) TEM image of the original C60 particles. b) Enlarged view with a FFT in the inset. c) High-resolution image showing the spacings of the (111) (0.81 nm) and (220) planes (0.49 nm) of fcc C60. d) Typical TEM image of LOPC particles. e) Enlarged view and FFT. f) High-resolution image showing deformed and connected cages in the LOPC crystal. g) Typical TEM image of polymer crystal particles. h) Enlarged view and FFT. i) High-resolution image showing individual C60 cages with center-to-center distances labeled in the polymer crystal; the suggested structure is shown by the orange-colored overlayers in c, f and i for each carbon. j) Neutron PDF for the original C60, LOPC, and the polymer crystal. Distances are labeled for the major peaks below 0.7 nm, which is the diameter of a C60 cage. Green arrows indicate the changes of peak positions and intensities in LOPC and polymer crystal, compared to the original C60. Credit: Institute for Basic Science
Zhu who led the USCT team said, “Professor Ruoff explained his interest in the triply periodic minimal surfaces that were described by the mathematician Schwartz, and how trivalently bonded carbon can in principle yield identical structures at the mathematical constructs. These are now referred to as “carbon schwarzite” structures, and that also can be called “negative curvature carbon”. I told him years ago that this was an exciting research topic and that it might be possible to find ways to collaborate on his suggestion.”
This new form of carbon was produced using C60 fullerene (buckminsterfullerene, also called “buckyball molecules”) powder, as base material. The C60 was mixed with α-Li3N (“alpha lithium nitride”) and then heated to moderate temperatures while holding at one atmosphere of pressure. It was learned that the α-Li3N catalyzed the breaking of some of the carbon-carbon bonds in C60, and new C-C bonds were then formed with neighboring C60 molecules through electron transfer to the C60 molecules.
Ruoff said, “In this particular effort, Prof. Zhu and team at USTC used a potent electron transfer agent (α-Li3N) to drive the formation of a new type of carbon by starting with crystalline fullerene.”
![Carbon Morphological and Structural Characterizations](https://oen.pl/wp-content/uploads/2023/02/1676274108_149_Odkryto-nowa-forme-wegla-–-„Otwiera-zupelnie-nowe-mozliwosci.jpg 777w,https://scitechdaily.com/images/Carbon-Morphological-and-Structural-Characterizations-400x321.jpg 400w,https://scitechdaily.com/images/Carbon-Morphological-and-Structural-Characterizations-768x616.jpg 768w,https://scitechdaily.com/images/Carbon-Morphological-and-Structural-Characterizations.jpg 1137w)
a) Atomic structure models, optical and SEM images. b) Cu Kα (λ = 0.15418 nm) X-ray diffraction patterns with simulation for LOPC, based on the proposed atomic structure model. AU, arbitrary units. c) X-ray diffraction patterns of LOPCs, with the temperature indicated by LOPC-550 etc. for samples prepared at different temperatures. d) Raman spectra for the original C60, LOPC, and the polymer crystal. e) 13C MAS-SSNMR spectra. The pink line shows the Lorentz fit of peaks for the polymer crystal; *indicates the spin side bands. f) Low-pressure Ar (87.3 K) adsorption/desorption isotherms and (inset) pore-size distribution (calculated by using a slit pore with a DFT equilibrium model) for LOPCs, with specific surface area values (m2 g−1) labeled above each of the isotherm curves. Credit: Institute for Basic Science
Professor Zhu and team named their new carbon, ‘long-range ordered porous carbon’ (LOPC).
LOPC consists of ‘broken C60 cages’ that are connected with long-range periodicity. That is, the broken C60 cages are each still centered on the lattice sites of the face-centered cubic lattice, but they have been “opened” to a degree and formed bonds with each other. This is a somewhat unusual situation – there is still long-range periodic order of a certain type, but not every broken C60 cage is identical to its neighbors.
It was found that the formation of the LOPC occurred under narrow temperatures and carbon/Li3N ratio conditions. Heating up to 550 oC with a 5:1 ratio between carbon and Li3N causes partial destruction (breaking of some C-C bonds) of the buckyballs, which resulted in the discovery of the “broken C60 cage” structure that is found in the LOPC.
A milder temperature of 480 oC or lower level of Li3N does not damage the buckyballs, which instead join together to form a “C60 polymer crystal”. This crystal decomposes back to individual buckyballs upon reheating. Meanwhile, adding too much Li3N or a harsher temperature above 600 oC resulted in the complete disintegration of the buckyballs.
![Carbon Simulations and In Situ MAS SSNMR](https://oen.pl/wp-content/uploads/2023/02/1676274109_259_Odkryto-nowa-forme-wegla-–-„Otwiera-zupelnie-nowe-mozliwosci.jpg 757w,https://scitechdaily.com/images/Carbon-Simulations-and-In-Situ-MAS-SSNMR-296x400.jpg 296w,https://scitechdaily.com/images/Carbon-Simulations-and-In-Situ-MAS-SSNMR-768x1038.jpg 768w,https://scitechdaily.com/images/Carbon-Simulations-and-In-Situ-MAS-SSNMR.jpg 977w)
a) Potential energy surface of fcc C60 expressed with Steinhardt-type order parameter (OP). According to the geometric characteristics of the carbons obtained, five distinct regions are circled to guide the eye, and the representative structures are listed for four of these: (A) fcc C60, (B) polymer crystal composed of 1D fullerene polymer chains, (C) polymer crystal composed of 2D fullerene polymer network, (D) polymer crystal composed of 2D fullerene polymer network with rings as connection, (E) 1D peanut-shaped tube with intertube polymerization, (F) open-caged peanut-shaped tube, (G) 3D connected graphene-like structure, (H) 2D curved graphene-like structure, (I) 2H graphite, and (J) residual carbyne. b) 13C chemical shift spectra depending on temperature, obtained from in situ MAS-SSNMR data while heating 500 mg C60 with 100 mg α-Li3N. c) Calculated reaction energy path of 2+2 polymerization of two isolated C60 cages without Li adsorption (‘0 Li’), with one Li atom adsorbed near the sp3 bonding site (‘1 Li near’) or one Li atom adsorbed far from the sp3 bonding (‘1 Li far’). Credit: Institute for Basic Science
This new carbon was characterized by a variety of methods, and (indeed) its characterization was not easy because of the variety of slightly different ‘broken C60 cages’ that nonetheless maintain their positions in a standard face-centered cubic crystal lattice. X-ray diffraction, Raman spectroscopy, magic-angle spinning solid-state nuclear magnetic resonance spectroscopy, aberration-corrected transmission electron microscopy, and neutron scattering were used to derive an understanding of the structure of this new form of carbon. Numerical simulations based on a neural network type of modeling, combined with the experimental methods mentioned above, show that LOPC is a metastable structure produced during the transformation from ‘fullerene-type’ to ‘graphene-type’ carbons.
The “carbon K-edge near-edge X-ray absorption fine structure” data shows a higher degree of delocalization of electrons in LOPC than in C60. The electrical conductivity is found to be 1.17 × 10−2 S cm−1 at room temperature, and conduction at a temperature of less than 30 Kelvin seems to be a combination of metallic-like transport over short distances punctuated by carrier hopping. Knowing these electrical properties is important for elucidating what possible applications there might be for such a new type of carbon.
Ruoff notes, “While this beautiful new type of carbon has many fascinating features, it is not a carbon schwarzite, so that experimental challenge still remains on the horizon! Indeed, this carbon is something different and unique – it opens up entirely new possibilities in new directions for carbon materials.”
![Carbon DOS, NEXAFS and Electrical Conductivity Measurements](https://oen.pl/wp-content/uploads/2023/02/1676274110_58_Odkryto-nowa-forme-wegla-–-„Otwiera-zupelnie-nowe-mozliwosci.jpg 777w,https://scitechdaily.com/images/Carbon-DOS-NEXAFS-and-Electrical-Conductivity-Measurements-400x388.jpg 400w,https://scitechdaily.com/images/Carbon-DOS-NEXAFS-and-Electrical-Conductivity-Measurements-768x746.jpg 768w,https://scitechdaily.com/images/Carbon-DOS-NEXAFS-and-Electrical-Conductivity-Measurements.jpg 1536w)
a) Density of states. b) Carbon K-edge NEXAFS spectra. Insets show the simulated final-state molecular orbitals of the excited atoms for the first prominent peak (284.4 eV for the original C60, 285.0 eV for LOPC, or 284.2 eV for the polymer crystal). Atoms marked blue are excited atoms (isovalue = 0.02). c) Direct current voltage–current curves of three membranes made by mixing each carbon with 5 wt% polytetrafluoroethylene. Inset shows an enlarged view of the ordinate. Electrical conductivities calculated from the curves are 2.44 × 10−9 S cm−1, 7.39 × 10−8 S cm−1, and 1.17 × 10−2 S cm−1, for the original C60, polymer crystal, and LOPC, respectively. d) Resistivity testing for the LOPCs, graphite powder, and rGO powder. The inset shows the change of g value with the annealing temperature of the LOPC. Credit: Institute for Basic Science
The preparation of LOPC paves the way for the discovery of other crystalline carbons starting from C60(s) – and perhaps from other fullerenes like C70, C76, C84, and so on. Other exciting options would be including another element. This can be done by starting with the “endohedral” fullerenes such as [email protected] C60gdzie M może być pierwiastkiem takim jak lantan lub wiele innych, który jest zamknięty w całkowicie węglowej klatce fulerenowej.
Zespół widzi możliwe zastosowania w pozyskiwaniu, przetwarzaniu i magazynowaniu energii; w katalizie do wytwarzania produktów chemicznych; oraz do oddzielania jonów lub gazów cząsteczkowych. Ważny aspekt podkreślono również w ich Natura artykułem jest skalowalność syntezy. Zhu zauważa, że można go łatwo skalować do skali kilogramowej, a przy ciągłych procesach produkcyjnych możliwe jest osiągnięcie produkcji na skalę tonową.
„Yanwu zaprosił mnie do przyłączenia się do tych wysiłków po początkowym sukcesie w syntezie i obiecujących początkowych krokach w ich projekcie, i na szczęście byłem w stanie przedstawić kilka pomocnych sugestii na temat trwającej nauki i zakończenia tego badania, które jest teraz opublikowane w Natura. Uznanie za syntezę i praktyczne badania eksperymentalne jest w całości zasługą Yanwu i jego zespołu. Z przyjemnością udzielałem porad na określone tematy, w tym analiz, które należy przeprowadzić i tego, czego można się z nich dowiedzieć” — zauważa Ruoff. „Współpraca z kolegami to jedna z przyjemności uprawiania nauki. Tematem była tutaj nowa forma węgla, idealnie wpisująca się w interesy naszego kierowanego przeze mnie centrum CMCM, które mieści się w UNIST. Dlatego przystąpiłem do współpracy z podekscytowaniem i wielką chęcią spróbowania wnieść swój wkład w pożyteczny sposób!”
Zhu powiedział: „Profesor Ruoff jest legendarnym naukowcem zajmującym się materiałami węglowymi, a także po prostu ogólnie. Byłem stypendystą podoktoranckim w jego grupie badawczej przez 3 lata i 3 miesiące iw ciągu tych lat nauczyłem się od niego bardzo dużo o tym, jak uprawiać nauki podstawowe. Rzeczywiście, moje ostatnie lata jako postdoc spędziłem na codziennym, bardzo bliskim dialogu z nim na temat pracy, która ostatecznie została opublikowana w Nauka, który dotyczył również trójwartościowego węgla związanego na bazie grafenopodobnych arkuszy. Ja i mój zespół byliśmy bardzo szczęśliwi, że przyłączył się do naszych wysiłków i wniósł ogromny wkład w naukę, którą opisaliśmy w naszym artykule opublikowanym w Natura”.
Odniesienie: „Porowate węgle z C60 uporządkowane z dalekiego zasięgu” autorstwa Fei Pan, Kun Ni, Tao Xu, Huaican Chen, Yusong Wang, Ke Gong, Cai Liu, Xin Li, Miao-Ling Lin, Shengyuan Li, Xia Wang, Wensheng Yan, Wen Yin, Ping-Heng Tan, Litao Sun, Dapeng Yu, Rodney S. Ruoff i Yanwu Zhu, 11 stycznia 2023 r., Natura.
DOI: 10.1038/s41586-022-05532-0
Badanie zostało sfinansowane przez Institute for Basic Science.