KAIST

Distinguished Professor Ryong Ryoo of the Chemistry Department at KAIST, who is also the Director of the Center for Nanomaterials and Carbon Materials at the Institute for Basic Science (IBS), and his research team have recently published their research results entitled "Lanthanum-catalysed Synthesis of Microporous 3D Graphene-like Carbons in a Zeolite Template" on June 29, 2016 in Nature on a new method to synthesize carbons having graphene structures with 3D periodic micropores, a trait resulted from using a zeolite as a template for the synthesis. The research team expects this technology to find a range of useful applications such as in batteries and catalysts.

Graphene, an allotrope of carbon, which was discovered more than a decade ago, has led to myriad research that seeks to unlock its vast potential. Zeolites, commonly used microporous solid catalysts in the petrochemical industry, have recently attracted attention in the field of material science as a template for carbon synthesis. Zeolites’ individual crystal is distinguished by its unique 1 nanometer (nm)-size pore structures. These structures facilitate the accommodation of carbon nanotubes inside zeolites. In their paper, the research team showed that these nanoporous systems are an ideal template for the carbon synthesis of three-dimensional (3D) graphene architecture, but zeolite pores are too small to accommodate bulky molecular compounds like polyaromatic and furfuryl alcohol that are often used in carbon synthesis. Small molecules like ethylene and acetylene can be used as a carbon source to achieve successful carbonization within zeolite pores, but it comes at a great cost. The high temperatures required for the synthesis cause reactions of carbons being deposited randomly on the external surfaces of zeolites as well as their internal pore walls, resulting in coke deposition and consequently, causing serious diffusion limitations in the zeolite pores.

 The team from the IBS Center for Nanomaterials and Carbon Materials solved this conundrum with a novel approach. First author Dr. KIM Kyoungsoo explains: “The zeolite-template carbon synthesis has existed for a long time, but the problem with temperatures has foiled many scientists from extracting their full potential. Here, our team sought to find the answer by embedding lanthanum ions (La³⁺), a silvery-white metal element, in zeolite pores. This lowers the temperature required for the carbonization of ethylene or acetylene. Graphene-like sp² carbon structures can be selectively formed inside the zeolite template, without carbon deposition at the external surfaces. After the zeolite template is removed, the carbon framework exhibits the electrical conductivity two orders of magnitude higher than amorphous mesoporous carbon, which is a pretty astonishing result. This highly efficient synthesis strategy based on the lanthanum ions renders the carbon framework to be formed in pores with a less than 1 nm diameter, just like as easily reproducible as in mesoporous templates. This provides a general method to synthesize carbon nanostructures with various topologies corresponding to the template zeolite pore topologies, such as FAU, EMT, beta, LTL, MFI, and LTA. Also, all the synthesis can be readily scaled up, which is important for practical applications in areas of batteries, fuel storage, and other zeolite-like catalyst supports.”

The research team began their experiment by utilizing La³⁺ ions. Dr. KIM elucidates why this silvery-white element proved so beneficial to the team, “La³⁺ ions are unreducible under carbonization process condition, so they can stay inside the zeolite pores instead of moving to the outer zeolite surface in the form of reduced metal particles. Within the pores, they can stabilize ethylene and the pyrocondensation intermediately to form a carbon framework in zeolites.”

In order to test this hypothesis, the team compared the amount of carbon deposited in La³⁺-containing form of Y zeolite (LaY) sample against a host of other samples such as NaY and HY. The experimental results indicate that all the LaY, NaY, and HY zeolite samples show rapid carbon deposition at 800°C. However, as the temperature decreases, there appears to be a dramatic difference between the different ionic forms of zeolites. At 600°C, the LaY zeolite is still active as a carbon deposition template. In contrast, both NaY and HY lose their carbon deposition functions almost completely.

The results, according to their paper published in Nature, highlight a catalytic effect of lanthanum for carbonization. By making graphene with 3D periodic nanoporous architectures, it promises a wide range of useful applications such as in batteries and catalysts but due to the lack of efficient synthetic strategies, such applications have not yet been successful. By taking advantage of the pore-selective carbon filling at decreased temperatures, the synthesis can readily be scaled up for studies requiring bulk quantities of carbon, in particular high electrical conductivity, which is a highly sought aspect for the production of batteries.

YouTube Link: https://youtu.be/lkNiHiB8lBk

Image 1: (Top to Bottom) Zeolite Template: Microporous Aluminosilicate; Zeolite ion exchanged with La3⁺ ions in aqueous solution; and Zeolite Template with La3⁺ ions

Image 2: (Top to Bottom) Catalytic carbonization progressed at La3+ ions-exchanged sites using ethylene as a carbon precursor. Carbon is highlighted in grey; Zeolite template removed in an acid solution (HF/ HCl); Microporous 3D graphene-like carbon