Crystalline diamond nanotherad from biomass materials

New research from a team of scientists led by Drs. Kuo Li and Haiyan Zheng from Center for High Pressure Science and Technology Advanced Research (HPSTAR) reported the first synthesize of a three-dimensional crystalline carbon nanothread (CNThs) from a biomass precursor, 2,5-furandicarboxylic acid (FDCA), through [4+2] Diels-Alder reactions. The crystalline CNTh shows excellent electrochemical performance as an anode material of a lithium battery. This work is published in the Journal of the American Chemical Society (DOI: 10.1021/jacs.2c08914).

Carbon nanothread (CNTh) is a one-dimensional diamond material which has high tensile strength and bending modulus. In 2015, scientists synthesized the CNTh for the first time via pressure-induced polymerization of benzene. Later, starting from various aromatic molecules, a series of CNThs were synthesized. However, how to improve the atomical intra-and interthread ordering is a longstanding question for CNTh.

(FDCA) is one of the top-12 value-added chemicals from sugar and widely applied in chemical industry. “Comparing to benzene, it has fewer possible bonding routes which will help to improve the homogeneity of the CNThs. Besides, its aligned π-π stacking and intermolecular H-bonding in its structure is also critical to obtain the crystalline diamond nanothread. Therefore, the 2,5-furandicarboxylic acid is a better precursor material for CNTh,” said Dr. Kuo Li.

In this work, the scientists synthesis the atomically ordered crystalline CNTh with uniform syn-configuration (all the oxygens on one side) by compressing FDCA at ~12 GPa. With the exceptional long-range ordering in the product, they determined the precise crystal structure directly from the X-ray diffraction, showing an obvious contrast to the previously reports of CNThs. The combination spectroscopy and theoretical simulation show that the FDCA experienced continuous [4+2] Diels-Alder reactions along the stacking direction to form CNTh. Benefiting from the abundant carbonyl groups, the poly-FDCA CNTh has a high specific capacity, excellent coulombic efficiency and rate performance as an anode material of Li-battery.

"The reaction pressure of ~ 12GPa is relatively low, expected for scalable synthesis,” said Dr. Xuan Wang, the lead author of the study. “And this is the first time to use the biomass compounds to synthesize the diamond carbon nanothread materials. We believe our study will provide a new route to synthesis advanced functional carbon materials," added Dr. Haiyan Zheng.