Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template

Abstract

Three-dimensional graphene architectures with periodic nanopores—reminiscent of zeolite frameworks—are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure1,2,3,4,5,6. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures7,8,9,10,11,12,13,14,15. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst supports.

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Figure 1: Electron-density map of the supercage of zeolite FAU after carbon deposition.
Figure 2: Structures of 3D graphene-like microporous carbons.
Figure 3: Carbon from a 1D-channel LTL zeolite, and from a small-pore LTA zeolite.

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Acknowledgements

This work was supported by IBS-R004-D1. The authors thank D. Ahn at the Pohang Accelerator Laboratory (PLS) for discussions on powder XRD measurements. X-ray crystallography was carried out with help from D. Moon at PLS and H. J. Lee at Korea Basic Science Institute.

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Contributions

R.R. selected metal-ion catalysts intuitively, initiated single-crystal investigation, and led the project. K.K. led the synthesis and characterization work, with T.L. and Y.K. Y.S. carried out NMR measurements. J.S. and J.K.P. carried out electrochemical analysis. H.L. and J.Y.P. analysed the electrical conductivity of the carbon product. S.J.C. and T.L. carried out the X-ray crystallography. H.I. investigated the mechanism of carbon formation. R.R. and K.K. wrote the manuscript.

Corresponding author

Correspondence to Ryong Ryoo.

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The authors declare no competing financial interests.

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Nature thanks P. de Jongh, L. Solovyov and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Extended data figures and tables

Extended Data Figure 1 Carbon deposition in zeolite FAU plotted as a function of temperature, with various ion exchanges.

The zeolites LaY, NaY and HY were heated to the temperatures indicated under a dry N2 flow, using a vertically placed, fused quartz reactor equipped with a fritted disk. Subsequently, a mixture of ethylene gas, N2 and steam was passed through the zeolite bed for 1 hour. The amount of carbon deposited at each temperature was measured by thermogravimetry. At 600 °C, the La3+-ion-exchanged zeolite had been deposited with 20 times more carbon than had HY or NaY.

Extended Data Figure 2 Carbon deposition in La3+-ion-exchanged FAU zeolite at 600 °C.

a, The amount of carbon was measured as a function of time, using thermogravimetric analysis equipment built in the carbon deposition rig. The plotted result indicates that the carbon content in LaY becomes saturated at ~0.3 g g−1 of zeolite. b, A TEM image of LaY zeolite after 250 min of carbon deposition, showing apparently no carbon deposition on external surfaces.

Extended Data Figure 3 Magic-angle spinning solid-state 13C NMR spectra of the carbon framework formed within zeolite LaY.

The NMR spectra were recorded with various spinning rates on a Brucker Avance III HD 400WB NMR spectrometer operated at 100.61 MHz for 13C. All spectra were obtained with a 4-μs pulse, a 10-s relaxation delay, and 1,000 acquisitions. Asterisks indicate spinning sidebands for a given spinning rate. The spectra for carbon obtained at 600 °C exhibit two peaks with chemical shift at 123 p.p.m. and 129 p.p.m. The peak at 123 p.p.m. can be assigned to six-membered-ring sp2 carbon; the peak at 129 p.p.m. can be attributed to five- or seven-membered rings that have smaller C–C–C angles in the conjugated sp2 carbon system24. No other peaks (assignable to sp3 or sp carbons) were detected in the NMR spectra of sample prepared with 99% 13C-isotope-enriched ethylene. The final carbon product, liberated from zeolite after heat treatment at 850 °C, has an additional weak peak at around 180 p.p.m., corresponding to oxygen functional groups.

Extended Data Figure 4 X-ray crystallographic analysis of the carbon structure formed in a single crystal of La3+-ion-exchanged zeolite FAU.

Carbon atomic positions were determined through least-square refinement of the distances, using a difference Fourier method (see Methods for details). To cope with a complex system having high static disorder of atomic positions, we assumed that all carbon atoms had the same thermal parameter in the refinement procedure. The refinement result indicates that atomic positions in pore necks (yellow rectangle) have high static disorders over a zeolite crystal. That is, the determined positions can be regarded as overlapped carbon positions over many identical pore necks. This result, using constraints, may not yet provide an accurate structural solution.

Extended Data Figure 5 Thermal stability of carbon samples.

The top three curves are derivative thermogravimetric curves for the carbons synthesized using different lanthanum-ion-exchanged zeolites. Thermogravimetry was carried out by increasing the temperature to 700 °C, with a ramping rate of 3 °C min−1, under air flow (60 ml min−1). We compared these thermogravimetric data with the results obtained using the mesoporous carbon CMK-3 (which has an amorphous structure), a commercial graphene product (purchased from Graphene Laboratories Inc.), and a beta-zeolite-templated carbon sample that was prepared following a two-step carbonization method13 (bottom three curves). These data indicate that carbon samples obtained from lanthanum-ion-exchanged zeolites can have distinctively high thermal stability, compared with amorphous carbons. Notably, the beta-templated carbon exhibited high thermal stability in air, like graphene.

Extended Data Figure 6 Raman spectra of LaY-templated carbon and graphite.

The spectra were recorded on a Horiba Jobin Yvon ARAMIS spectrometer with a laser excitation wavelength of 514 nm. The G- and D-bands are located at 1,598 cm−1 and 1,341 cm−1, respectively. The G-band of LaY-templated carbon appears at a higher wavenumber than that of graphite; such a strong upshift indicates nanosized single graphene layers26. The broad D-band is attributed to bond disorder, for instance because of the presence of five- or seven-membered carbon rings in the curved carbon structure41.

Extended Data Figure 7 Topographical images of LaY-templated carbon and CMK-3 mesoporous carbon on an Au (111) substrate.

a, LaY-templated carbon; b, CMK-3 mesoporous carbon. The current–voltage curves shown in Fig. 2f were measured on the cross-marked areas. The images were taken using an Agilent 5500 atomic force microscope in air, using a Pt/Ir-coated tip (see Methods).

Extended Data Figure 8 Effect of ion exchange on carbon synthesis using the 1D-channel LTL zeolite.

a, SEM image of LTL zeolite. b, SEM image of carbon liberated from La3+-ion-exchanged LTL zeolite. c, SEM image of carbon from H+-ion-exchanged LTL zeolite. For carbon synthesis using La3+-ion-exchanged zeolite, acetylene gas was used as the carbon source at 500 °C; the remainder of the protocol is as described in the Methods. For the H+-ion-exchanged zeolite, carbon deposition was tested at various temperatures between 500 °C and 700 °C. However, synthesis using this H+ zeolite failed.

Extended Data Figure 9 Scaling up the carbon-deposition process.

a, Photograph of the carbonization rig for large-batch synthesis; inset, the plug-flow reactor filled with a thick bed of carbon–zeolite composite (about 40 g). From this apparatus, we could obtain about 10 g of batch carbon products in a single preparation. bd, TEM images of the carbon products synthesized from zeolites FAU (b), EMT (c) and beta (d). e, XRD patterns of the carbons, confirming their highly ordered structure. These results indicate that the product quality from the 10-g batch synthesis is the same as that from the 0.15-g batch.

Extended Data Table 1 Data collection and refinement statistics for X-ray diffraction analysis

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Kim, K., Lee, T., Kwon, Y. et al. Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template. Nature 535, 131–135 (2016). https://doi.org/10.1038/nature18284

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