(Nanocarbons Division Poster Award, 3rd Place) Investigating the Impact of Reaction and Carbonization Variables on ZIF-67 and Its Energy Storage Properties
Authors: Ranković Maja , Janošević Ležaić Aleksandra , Gavrilov Nemanja , Pasti Igor A. , Bajuk-Bogdanović Danica , Nedić Vasiljević Bojana , Savić Marjetka , Ćirić-Marjanović Gordana 
Published: August 2024

Metal-organic frameworks (MOFs), with their exceptional properties such as high surface area, well-defined pores, and diverse chemical functionalities, have garnered widespread attention in scientific and industrial domains [1-2]. Among these, zeolitic imidazolate frameworks (ZIFs), known for their chemical and thermal stability, are extensively explored for applications ranging from catalysis and gas adsorption to electronic devices and sensors.

By employing a novel hydrothermal method in aqueous solutions at room temperature, ZIF-67 nanocrystals were successfully synthesized, eliminating the need for toxic organic solvents and reducing overall costs. The resulting materials demonstrated notable efficiency in energy storage. To address the increasing demand for scalable synthesis methods, the study investigated the impact of reaction scale, reaction time, and reaction mixture dilution on the yield, morphology, and molecular structure of ZIF-67. The optimized conditions increased the production yield to 83%, surpassing the reported 75%. The subsequent carbonization process under three different regimes (800 °C, 800 °C with 3h ramp, 900 °C) resulted in materials exhibiting promising energy storage capabilities, with capacitance values reaching 81 F g−1 at a low sweep rate of 5 mV s−1. The carbonization yield showed a decrease with increasing carbonization time and temperature, and capacitance values were influenced by the presence of cobalt in the material.

A slightly higher specific surface area of sample C-800 is reflected in the slightly higher capacitance values over all sweep rates indicating that specific surface area plays a role in the behavior of here synthesized materials. Capacitance is invariant at higher sweep rates (above 20mV s-1) which can be an indication that a part of the material surface, at macro- and mesopores, is highly responsive and highly conductive. At lower sweep rates micropores become available, due to prolonged time for ion insertion, which increases the capacitance that is unavailable at higher sweep rates. The highest percentage rise in capacitance is also seen in sample C-800 as its micropore volume, 40% of its total volume, is the highest among the samples investigated.

Specifically, considering only the carbon part, the specific capacitance reached 176 F g−1, comparable to literature values for MOF-derived carbons [3]. The study suggests that dissolution of cobalt could enhance the material's capacitance behavior, opening avenues for further improvement in energy storage applications. This transformative approach addresses challenges associated with escalating energy demands and showcases the potential of ZIF-67-derived materials in electrochemical applications.

Acknowledgement

This research was supported by the Science Fund of the Republic of Serbia, grant number 7750219, Advanced Conducting Polymer-Based Materials for Electrochemical Energy Conversion and Storage, Sensors and Environmental Protection-AdConPolyMat (IDEAS programme)

References:

[1] O.M. Yaghi, M. O’Keeffe, N.W. Ockwig, H.K. Chae, M. Eddaoudi, J. Kim, Nature 423 (2003) 705–714.

[2] S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem., Int. Ed. 43 (2004) 2334–2375.

[3] I.A. Khan, A. Badshah, I. Khan, D. Zhao, M. A. Nadeem, Microporous and Mesoporous Mat. 253 (2017) 169-176