Izvestiya of Saratov University.

Physics

ISSN 1817-3020 (Print)
ISSN 2542-193X (Online)

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Muratov D. G., Kozhitov L. V., Zaporotskova I. V., Popkova A. V., Zorin A. V., Tarala V. A., Boroznina N. P., Boroznin S. V. Effect of IR pyrolysis temperature on the structure and properties of metal–carbon composites based on CoMn-ZIF bimetallic zeolite-like frameworks. Izvestiya of Saratov University. Physics , 2026, vol. 26, iss. 3, pp. 357-376. DOI: 10.18500/1817-3020-2026-26-3-357-376, EDN: PWIPBZ

This is an open access article distributed under the terms of Creative Commons Attribution 4.0 International License (CC-BY 4.0).
Published online: 
30.09.2026
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Russian
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Nanotechnologies, nanomaterials and metamaterials
Article type: 
Article
UDC: 
53.043
DOI: 
10.18500/1817-3020-2026-26-3-357-376
EDN: 
PWIPBZ

Effect of IR pyrolysis temperature on the structure and properties of metal–carbon composites based on CoMn-ZIF bimetallic zeolite-like frameworks

Autors: 
Muratov Dmitriy G., National University of Science and Technology MISIS
Kozhitov Lev V., National University of Science and Technology MISIS
Zaporotskova Irina Vladimirovna, Volgograd State University
Popkova Alena V., Research Institute NPO «LUCH», JSC
Zorin Artem V., National University of Science and Technology MISIS
Tarala Vitaliy Alekseevich, North Caucasus Federal University
Boroznina Natalya P., Volgograd State University
Boroznin Sergey V., Volgograd State University
Abstract: 

Background and Objectives: Zeolitic imidazolate frameworks (ZIFs), particularly ZIF-67, serve as promising precursors for composite nanomaterials (Metal-organic frameworks, MOFs) across various applications due to their unique combination of crystalline architecture, mesoporosity, high specific surface area (1200–1800 m2/g), nitrogen-containing organic ligands, and catalytically active metal centers. This study investigates nanocomposites derived from Mn-substituted ZIF-67 (CoMn-ZIF). A comprehensive analytical approach combining X-ray diffraction electron microscopy, and Raman spectroscopy is employed to characterize the structure and composition of these nanocomposites. However, interpreting Raman spectroscopy data for MOF-derived nanocomposites presents significant methodological challenges: conventional Raman scattering analysis approaches fail to account for the multiphase nature of composites formed at pyrolysis temperatures near the MOF decomposition point, as well as the presence of residual MOF fragments and metallic nanophases, leading to contradictory results. To determine the effect of IR pyrolysis temperature on the structure, morphology, and composition of nanocomposites derived from Mn-substituted ZIF-67 (CoMn-ZIF). Materials and Methods: This work proposes a Raman spectra deconvolution scheme for MOF-derived materials aimed at resolving apparent discrepancies between Raman analysis, X-ray phase analysis, and scanning electron microscopy(SEM) data. The core concept of the proposed approach is to treat the nanocomposites as porous carbon materials comprising a graphite-like phase with a specific defect density, amorphous poorly structured carbon with sp2 and sp3 bonding, metals and oxides, as well as carbon atomic configurations characteristic of imidazolate metal-organic frameworks. Results: Metal-carbon composites obtained via IR pyrolysis of Mn-substituted ZIF-67 at 500–700°C (CoMn-ZIF-T, Co : Mn = 90 : 10) have been investigated. Deconvolution of Raman spectra (130–1000 cm–1 and 1000–1800 cm–1) has revealed the evolution of carbon phases, oxide components (C3O4, MnOx), and residual MOF-related vibrational modes. It has been shown that increasing the pyrolysis temperature promotes the carbonization of the MOF organic component, leading to near-complete transformation of the imidazolate framework into graphite-like carbon, alongside the reduction of cobalt from Co3O4 to its metallic state, while manganese remains present as MnO2. SEM studies and energy-dispersive X-ray spectroscopy (EDS) have confirmed the formation of a hierarchical porous morphology with macro- and mesopores, which correlates well with the Raman spectroscopy results. Electrochemical measurements on symmetric supercapacitor cells in 6 M KOH-electrolyte have revealed a maximum specific capacitance of 336 F/g at optimal pyrolysis temperature of 600°C, attributed to synergistic coupling of double-layer capacitance from the high-porosity carbon matrix and pseudocapacitance from transition metal nanoparticles. Conclusion: The proposed Raman analysis approach has demonstrated a high degree of correlation with XRD and SEM results, enabling its application for the characterization of various MOF-derived pyrolysis products. Electrochemical property assessments demonstrate the high potential of ZIF-67-derived materials as efficient electrode materials for energy storage devices.

Key words: 
zeolite imidazolate frameworks (ZIF-67)
pyrolysis
metal-carbon composites
Raman scattering
electrochemical capacity
N-doped carbon
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Received: 
21.05.2026
Accepted: 
03.07.2026
Published: 
30.09.2026
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