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Biswa Nath Bhadra, [Rabindra Nath Acharyya](https://orcid.org/0000-0002-5439-8937), [Sabina Shahi](https://orcid.org/0000-0002-9198-2470), [Katsuhiko Ariga](https://orcid.org/0000-0002-2445-2955), [Lok Kumar Shrestha](https://orcid.org/0000-0003-2680-6291)

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[Metal–organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction](https://mdr.nims.go.jp/datasets/fba2d759-67e3-4f1b-8cb5-a180c9614c6b)

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Metal–organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reductionJournal ofMaterials Chemistry APAPEROpen Access Article. Published on 10 April 2026. Downloaded on 5/22/2026 7:59:59 AM.  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.View Article OnlineView Journal  | View IssueMetal–organic fraResearch Center for Materials NanoarchiMaterials Science (NIMS), 1-1 Namiki, Tsubbhadra1981@gmail; ARIGA.Katsuhiko@ngo.jpbInstitute Charles Gerhardt Montpellier (ICScientique (CNRS), Montpellier, 34095, FrcGraduate School of Science and TechnologyTsukuba, Ibaraki 305-8573, JapandDepartment of Advanced Materials Science,University of Tokyo, 5-1-5 Kashiwanoha, KaeDepartment of Materials Science, Institute oTsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki† These authors contributed equally.Cite this: J. Mater. Chem. A, 2026, 14,19423Received 26th February 2026Accepted 9th April 2026DOI: 10.1039/d6ta01685ersc.li/materials-aThis journal is © The Royal Society oamework on fullerene (MOFOF)derived Co-anchored hierarchical carbonnanocomposite for catalytic nitroarene reductionBiswa Nath Bhadra,*ab Rabindra Nath Acharyya, †ac Sabina Shahi, †acKatsuhiko Ariga *ad and Lok Kumar Shrestha *aeThe catalytic reduction of nitroarenes to anilines is vital in industrial and environmental chemistry for theproduction of pharmaceuticals, dyes, agrochemicals, and polymers. However, traditional catalysts oftenstruggle with issues related to activity, stability, and reusability. This study introduces a novel method forsynthesizing a Co-anchored hierarchical carbon nanocomposite derived from a newly architectedmetal–organic framework (MOF) on fullerene (MOFOF) composite. The method involves in situ growthof MOF (ZIF-67) on a surface-modified self-assembled fullerene nanotube (FNTox) with varying Co2+/C60ratios (0.5, 1.0, 1.5, and 2.0), followed by pyrolysis under a nitrogen atmosphere. The resultingnanohybrids, particularly Co@HC-1.0 derived from MOFOF-1.0 with a Co2+/C60 ratio of 1.0,demonstrated exceptional catalytic performance for nitroarene reduction, exhibiting high activity andreusability. Characterization techniques, including SEM, XRD, Raman spectroscopy, and nitrogen sorptionisotherms, confirmed the structural and morphological stability of the composites. The Co@HC-1.0catalyst demonstrated superior, highly competitive catalytic performance, achieving a reaction rateconstant of 9.25 × 10−1 min−1 and a TOF of 486 h−1, with significant retention of performance acrossmultiple cycles, highlighting its potential for various synthetic applications.1. IntroductionStudies have conrmed that nitroarenes are highly detrimentalto human health and the environment, and thus have beendesignated a priority contaminant by the Agency of Environ-mental Protection.1–4 These toxic nitroarenes or nitrophenolscan be readily converted to aromatic amines/phenols via cata-lytic reduction.4–7 Consequently, catalytic reduction of nitroar-enes to anilines is critical for both environmental and industrialconcerns, playing a pivotal role in the synthesis of pharma-ceuticals, dyes, agrochemicals, and polymers.8–10 However,traditional catalysts oen encounter limitations in activity,stability, and reusability, necessitating the development oftectonics (MANA), National Institute forkuba, Ibaraki 305-0044, Japan. E-mail:ims.go.jp; SHRESTHA.Lokkumar@nims.GM), Centre National de la Rechercheance, University of Tsukuba, 1-1-1 Tennodai,Graduate School of Frontier Sciences, Theshiwa, Chiba 277-8561, Japanf Pure and Applied Sciences, University of305-8573, Japanf Chemistry 2026advanced catalytic materials to overcome these challenges. Inthis context, carbon-based nanocomposites have attractedsignicant attention due to their high surface area, excellentthermal stability, and tunable porosity.Cobalt (Co) is a transition metal known for its excellentcatalytic activity and ability to facilitate various redox reactions,especially when incorporated into an appropriate supportmaterial.11–14 Cobalt supported on a carbon matrix can enhancethe catalyst's overall performance by providing active sites forcatalytic reactions and improving the material's electronicconductivity. The synergy between cobalt and carbon materialsyields highly efficient and durable catalysts. The fabrication ofCo-doped carbon nanocomposites involves several critical stepsto ensure uniform dispersion of cobalt nanoparticles within thecarbon matrix and to develop a hierarchical structure thatmaximizes catalytic efficiency. Design and synthesis of an idealcarbon-cobalt precursor composition is one of the most criticalsteps toward obtaining a cobalt-anchored hierarchical carbonnanocomposite with outstanding catalytic properties.Metal–organic frameworks (MOFs) are interesting materialswith unique properties, and their combination with variousmaterials has shown promise across many elds.15–25 In addi-tion, MOFs and their composites are used as precursors toproduce functional carbon materials with signicant potentialfor applications in energy storage, catalysis, and environmentalremediation.26–34 To date, cobalt-based MOFs or MOFJ. Mater. Chem. A, 2026, 14, 19423–19431 | 19423http://crossmark.crossref.org/dialog/?doi=10.1039/d6ta01685e&domain=pdf&date_stamp=2026-05-19http://orcid.org/0000-0002-5439-8937http://orcid.org/0000-0002-9198-2470http://orcid.org/0000-0002-2445-2955http://orcid.org/0000-0003-2680-6291http://creativecommons.org/licenses/by/3.0/http://creativecommons.org/licenses/by/3.0/https://doi.org/10.1039/d6ta01685ehttps://pubs.rsc.org/en/journals/journal/TAhttps://pubs.rsc.org/en/journals/journal/TA?issueid=TA014030Journal of Materials Chemistry A PaperOpen Access Article. Published on 10 April 2026. Downloaded on 5/22/2026 7:59:59 AM.  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.View Article Onlinecomposites have shown promise for producing fascinatingmetallic cobalt-anchored carbons.35–40 However, ongoingresearch focuses on engineering new precursor compositions tocreate metallic cobalt-anchored hybrid carbons with highlyfascinating physicochemical features, including porosity anddispersion, leading to enhanced catalytic and fascinatingelectrochemical and magnetic properties, even with low cobaltloading. For example, ZIF-67 (a typical cobalt MOF) and itscomposites were found to be effective precursors for cobalt-decorated carbon nanocomposites used in various catalyticreactions.36–40 Besides, fullerene nanostructures can be trans-formed into unique carbonaceous materials featuring porousarchitectures enriched in defective and graphitic walls throughthe removal of organic components and structural rearrange-ment during high-temperature treatment.41–46 Therefore,combining the advantages of ZIF-67 and fullerenes intoa composite material offers strong potential for producingadvanced carbon nanomaterials with unique properties andfunctionalities aer high-temperature carbonization.Owing to the complementary physicochemical properties offullerene and ZIF-67, the resulting material represents the rstexample of a Co-anchored nanohybrid supported on twodistinct carbon matrices. Consequently, the composite exhibitssuperior catalytic activity and selectivity compared to existingcatalysts, underscoring its strong potential for diverse syntheticand catalytic applications.This paper presents a novel method for synthesizinga carbon nanocomposite derived from MOFOF, followed by aninvestigation of its catalytic performance in the reduction ofnitroarenes and thorough material characterization. Unlikeconventional ZIF-67-derived carbons, the present MOFOFapproach uniquely integrates fullerene nanotubes asa secondary carbon scaffold, resulting in a dual-carbon hierar-chical framework. This distinctive architecture enablesimproved dispersion of Co nanoparticles, controlled particlesize, and enhanced electronic interactions among Co, N-dopedcarbon, and graphitic domains, features that are not attainablein traditional single-precursor MOF-derived carbons. Due to thefascinating structure and physicochemical properties offullerene and MOF (ZIF-67), the resulting carbon compositerepresents the rst example of a Co-anchored nanohybridsupported on two distinct carbon matrices. Consequently, thecomposite exhibits superior catalytic activity and selectivitycompared to existing catalysts, underscoring its strong poten-tial for diverse synthetic and catalytic applications.Fig. 1 SEM images of (a) FNT, (b) FNTox, (c) MOFOF-0.5, (d) MOFOF-1.0, (e) MOFOF-1.5 and (f) MOFOF-2.0.2. Experimental2.1 Materials and methodsThe materials used in this study were sourced from commercialsuppliers and used without additional purication. The SIcomprehensively covers the materials list, FNT synthesismethodology, surface modication techniques, carbonizationprocedures, characterization methods, and the protocol forconducting catalytic tests.19424 | J. Mater. Chem. A, 2026, 14, 19423–194313. Results and discussion3.1 Synthesis and structural characterizationsFig. 1 illustrates the scanning electron micrographs (SEM) ofthe FNT, acid-treated FNT (FNTox), and MOFOFs with fourdifferent compositions. The SEM images (Fig. 1a and b) of FNTand FNTox show the morphological stability of FNT underultrasonic treatment in a strong acidmixture of HNO3/H2SO4 (1/1). The morphology of the FNTox remained unchanged, witha slight destruction of some particles even aer the successfuldecoration of the ZIF-67 onto the surface of the FNTox. Fig. 1c–f,the SEM images, depict almost perfect growth of the ZIF-67particles with uniform distribution onto the FNTox, indicatingsuccessful assembly of ZIF-67 on FNT composites with differentZIF-67 and fullerene ratios. As expected, the density of ZIF-67particles can be well controlled; for example, it increased withincreasing the ZIF-67 precursor ratio. The TEM images (Fig. S1)of the selected MOFOF-1.0 conrmed the perfect incorporationof the ZIF-67 particles both into the hole and surface of theFNTox.The dried FNTox, pZIF-67, MOFOF-0.5, MOFOF-1.0, MOFOF-1.5, and MOFOF-2.0 materials underwent pyrolysis at 800 °C for4 hours under N2 ow. Subsequently, the resultant materials(excluding FNTox-derived carbon (FDC)) underwent HF etching(0.2 M) at 60 °C for 12 hours to eliminate soluble impurities(e.g., isolated Co species). This process yielded Co@HC-0.5,Co@HC-1.0, Co@HC-1.5, and Co@HC-2.0 carbon nano-hybrids with a consistent gross yield of 22–25 wt% of theprecursor materials. Conversely, Co@ZDC (i.e., carbonizedpZIF-67) exhibited a yield of approximately 15 wt% aer the HFwashing.Fig. 2a presents the XRD patterns of FNTox, ZIF-67, andMOFOF-1.0 (the representative composite). The presence ofThis journal is © The Royal Society of Chemistry 2026http://creativecommons.org/licenses/by/3.0/http://creativecommons.org/licenses/by/3.0/https://doi.org/10.1039/d6ta01685eFig. 2 (a) XRD patterns of FNTox, ZIF-67 and MOFOF-1.0; (b) XRDpatterns of Co@HC-0.5, Co@HC-1.0, Co@HC-1.5, and Co@HC-2.0materials and (c) Raman spectra of Co@HC-0.5, Co@HC-1.0, Co@HC-1.5, and Co@HC-2.0 materials.Fig. 3 (a) Nitrogen adsorption–desorption isotherms of Co@HC-0.5,Co@HC-1.0, Co@HC-1.5, and Co@HC-2.0 materials, (b) respectivepore size distribution and the Barrett–Joyner–Halenda (BJH) model,and (c) corresponding pore size distribution profile obtained pore sizePaper Journal of Materials Chemistry AOpen Access Article. Published on 10 April 2026. Downloaded on 5/22/2026 7:59:59 AM.  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.View Article Onlinecharacteristic ZIF-67 diffraction peaks in MOFOF-1.0 clearlyconrms the successful integration of ZIF-67 onto FNTox, vali-dating the formation of the composite nanostructures. Fig. 2bshows XRD patterns of the Co@HC-0.5, Co@HC-1.0, Co@HC-1.5, and Co@HC-2.0 materials, which obtained from the pris-tine MOFOF-0.5, MOFOF-1.0, MOFOF-1.5 and MOFOF-2.0,respectively. Moreover, Fig. S2 represents the XRD patterns ofthe FDC and Co@ZDC. The XRD patterns in Fig. 2a and S2 areentirely different from those of the parent FNTox, pZIF-67, andMOFOF-1.0 composites (Fig. 2b). This indicates that theintrinsic peaks of the FNTox, pZIF-67, and MOFOF crystals di-sappeared and new peaks were observed concurrently, demon-strating the complete decomposition of FNTox, pZIF-67, andZIF-67 crystalline phases in the MOFOF composites uponthermal and chemical treatment. The XRD patterns of Co@ZDC(Fig. S2), Co@HC-0.5, Co@HC-1.0, Co@HC-1.5, and Co@HC-2.0 (Fig. 2b) materials showed three new peaks at 26.0°, 44.2°,and 51.6°, which are the respective peaks for the 002 plane ofgraphitic carbon phase, 111 and 200 planes of the face-centeredcubic (FCC) Co crystals.47 The particle sizes of Co were esti-mated by using the Scherrer equation that revealed an increasewith increasing the ZIF-67 content into the MOFOF precursors;for instance, the Co@HC-0.5, Co@HC-1.0, Co@HC-1.5, andCo@HC-2.0 materials had particle sizes of 3.3 nm, 5.8 nm,7.3 nm, and 9.6 nm, respectively. The particle size of Co@ZDCwas approximately 20 nm, signicantly larger than that ofCo@HCs. As expected, the Co@HCmaterials obtained from thelowest ZIF-67 content have the smallest Co particles, whichincrease with increasing ZIF-67 content in the precursorMOFOF composite.Fig. S2b and 2c depict the Raman spectra of the FDC,Co@ZDC, Co@HC-0.5, Co@HC-1.0, Co@HC-1.5, and Co@HC-2.0, where all the materials show two characteristic bands at1353 cm−1 and 1587 cm−1, corresponding to the D-band and G-band with respect to the disordered sp3 hybridized C atoms, andsp2 hybridized graphitic C atoms, respectively.48,49 The esti-mated intensity ratio (ID/IG) of the D- and G-bands (as shown inFig. 2c) follows the order: FDC (1.05) < Co@HC-1.0 (1.32) <Co@HC-1.5 (1.37) < Co@HC-2.0 (1.42) < Co@ZDC (1.49). Thistrend indicates that higher ZIF-67 incorporation results ina greater degree of graphitization of the carbon phases. Here,This journal is © The Royal Society of Chemistry 2026the metallic cobalt in ZIF-67 enhances graphitization,50,51thereby increasing the ID/IG ratio with higher ZIF-67 content inthe precursor materials, consistent with the increased intensityof the C (002) peak in the XRD patterns (Fig. 2a).Nitrogen sorption isotherms were recorded to determine thesurface areas, pore volumes, and pore size distributions of thestarting materials FNTox, pZIF-67, and MOFOFs (Fig. S3), andthe resulting materials FDC, Co@ZDC, and Co@HCs aerpyrolysis (Fig. S4 and 3). The isotherms are close to type I forMOFOFs, indicating primarily microporous structures, whileFNTox shows a type IV isotherm, indicating a nearly non-porousstructure. Pore-size distribution analyses using the BJH(Fig. S3b) and DFT (Fig. S3c) methods, summarized in Table 1,indicated bimodal pore architectures in the composites. Theisotherms for FDC, Co@ZDC, and Co@HCs exhibit Type-I/Type-IV mixed-type sorption (Fig. 3a), suggesting the formation ofhierarchical micro- and mesoporous architectures. Largenitrogen adsorption at lower relative pressures (P/P0 < 0.05) isattributed to micropore lling, while gradual nitrogen adsorp-tion at higher pressures with a hysteresis loop is due to capillarycondensation in mesopores.Careful observation reveals that nitrogen adsorption at lowerrelative pressures decreases with increasing the Co2+/C60 ratioin the precursor MOFOFs, suggesting that mesoporosity devel-opment is inuenced by the ZIF-67 content in the MOFOFcomposites during the carbonization. The pore-size distribu-tions from the DFTmethod (Fig. 3b) and the BJHmodel (Fig. 3c)conrm the presence of both micropores and mesopores,indicating the hierarchical pore architecture of Co@HCs.The surface textural parameters summarized in Table 1 showthat the Co2+/C60 ratio in the precursor MOFOFs affects thesurface area and porosity of the samples. The BET surface areasand pore volumes follow the order: FDC > Co@HC-0.5 >Co@HC-1.0 > Co@HC-1.5 > Co@HC-2.0 > Co@ZDC. The high-est surface area in FDC is observed with complete carbonizationof FNTox in the absence of Co2+ or ZIF-67, while Co@ZDC,derived from pZIF-67 with the highest Co content, shows thelowest surface area and pore volume. Additionally, the surfaceareas and pore volumes of Co@HC materials increase as theZIF-67 content in the precursor MOF composites decreases,distributions calculated using the DFT method.J. Mater. Chem. A, 2026, 14, 19423–19431 | 19425http://creativecommons.org/licenses/by/3.0/http://creativecommons.org/licenses/by/3.0/https://doi.org/10.1039/d6ta01685eTable 1 Surface textural properties of FNTox, ZIF-67, MOFOFs and Co@HCsaSample SBET (m2 g−1) Smicro (m2 g−1) Vmicro (cm3 g−1) Vp (cm3 g−1) Dp (nm) Wp (nm)FNTox 36.9 18.0 0.050 0.118 1.63 1.38FDC 530.17 461.2 0.338 2.62ZIF-67 744.7 614.9 0.423 0.535 1.54 0.54Co@ZDC 194.9 136.4 0.267 0.511 1.95 0.57MOFOF-0.5 199.3 44.5 0.094 0.19 1.94 1.94Co@HC-0.5 810.3 711.7 0.687 1.129 1.94 0.29MOFOF-1.0 306.6 279.6 0.281 0.658 1.94 0.45Co@HC-1.0 418.7 367.2 0.380 0.705 1.94 0.29MOFOF-1.5 405.3 331.3 0.321 0.638 1.55 0.45Co@HC-1.5 381.4 347.9 0.390 0.685 1.95 0.29MOFOF-2.0 543.9 469.4 0.408 0.611 1.55 0.51Co@HC-2.0 367.7 266.8 0.323 0.608 1.45 0.25a SBET= BET surface area, Smicro=micropore surface area, Vmicro=micropore volume, Vp= total pore volume, Dp= average pore diameter obtainedfrom the BJH analysis, and Wp = average half pore width obtained from the DFT model.Journal of Materials Chemistry A PaperOpen Access Article. Published on 10 April 2026. Downloaded on 5/22/2026 7:59:59 AM.  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.View Article Onlinehighlighting the inuence of ZIF-67 or Co content on theporosity of Co@HCs. The hierarchical micro-/meso-pore archi-tectures within Co@HC materials are advantageous for prac-tical applications, particularly in heterogeneous catalysis.Fig. 4 illustrates the SEM and TEM analyses of the repre-sentative Co@HC material, specically Co@HC-1.0. The SEMand TEM images indicate that the morphology of MOFOF-1.0remains unchanged aer thermal and chemical treatment.Additionally, dark spots in the TEM image (Fig. 4c) and whitespots in the HAADF image (Fig. 4d) conrm the uniformdistribution of Co nanoparticles within the carbon nano-composite. The interplanar d-spacing values, derived from theintensity proles of the crystal lattice in the HR-TEM image(Fig. 4e), are 0.349 and 0.205 nm. These values closely match thed-spacings obtained from the SAED pattern (Fig. 4f), which are0.346 nm and 0.205 nm, corresponding to the calculated d-spacings of 0.336 and 0.206 nm for the 002 plane of graphiticFig. 4 (a) SEM image, (b) STEM image, (c) TEM image, (d) HAADF image, (the area highlighted regions, and (f) SAED patterns of the Co@HC-1.0 m19426 | J. Mater. Chem. A, 2026, 14, 19423–19431carbon52 and the 111 plane of FCC Co crystals, respectively.47,49These ndings conrm the formation of sp2-hybridizedgraphitic carbon and FCC Co upon the thermal treatment of theMOFOF-1.0 composite, consistent with the XRD analysis (Fig.2b) .Fig. 5 presents the X-ray photoelectron spectroscopy (XPS)analysis of MOFOF-1.0 (a representative MOFOF) and Co@HC-1.0 (a representative Co@HC) samples. The survey spectra(Fig. 5a) show the presence of carbon, oxygen, cobalt, andnitrogen in both materials. The atomic compositions observedare 78.3% C, 1.0% Co, 14.8% O, and 5.9% N for MOFOF-1.0, and80.1% C, 1.5% Co, 16.2% O, and 2.2% N for Co@HC-1.0. Thedeconvoluted C 1s spectrum of MOFOF-1.0 (Fig. 5b) displayspeaks at 284.1 eV (C]C, sp2), 285.6 eV (C–C, sp3/C–OH), and286.4 eV (C–N). For Co@HC-1.0 (Fig. 5b), the C 1s spectrumreveals peaks at 284.3 eV (C–C), 285.6 eV (C–OH), 286.3 eV (C–O/C–N), and 288.7 eV (O–C]O). The O 1s spectra of both samplese) HR-TEM image, lattice fringe and line-scanning intensity profile fromaterial.This journal is © The Royal Society of Chemistry 2026http://creativecommons.org/licenses/by/3.0/http://creativecommons.org/licenses/by/3.0/https://doi.org/10.1039/d6ta01685eFig. 5 (a) XPS observations of MOFOF-1.0 and Co@HC-1.0 materials. (a) XPS survey spectra, and deconvoluted (b) C 1s, (c) O 1s, (d) N 1s, and (e)Co 2p spectra.Paper Journal of Materials Chemistry AOpen Access Article. Published on 10 April 2026. Downloaded on 5/22/2026 7:59:59 AM.  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.View Article Onlineindicate similar C–OH and C–O–C bonding states with slightshis (Fig. 5c). The deconvoluted N 1s spectrum of MOFOF-1.0(Fig. 5d) shows peaks at 400.05 eV (N–H) and 401.0 eV (C–N),while for Co@HC-1.0 (Fig. 5d), the peaks correspond topyridinic N (398.2 eV), pyrrolic N (400.2 eV), and quaternary N(401.4 eV).53 The Co 2p spectrum of MOFOF-1.0 (Fig. 5e) showsa characteristic Co 2p3/2 peak at 781.1 eV accompanied bya satellite peak at 785.4 eV, which is attributed to Co2+ speciescoordinated with nitrogen (Co–N), along with Co 2p1/2 peak at796.2 with a satellite peak at 802.64 eV, consistent with Co2+sites originating from the ZIF-67. In contrast, Co@HC-1.0(Fig. 5e) features peaks at 780.35 eV and 795.95 eV assigned tothe Co 2p3/2 and 2p1/2 levels of metallic Co0, respectively.54Additionally, a peak at 782.4 eV indicates the presence of Co–Nspecies, suggesting partial preservation of metal–nitrogencoordination aer carbonization.In summary, a MOFOF composite with different composi-tions was successfully developed via a simple, room-temperature in situ approach. The resulting MOFOF compos-ites produced hierarchically porous carbon nanocompositeswith well-dispersed Co nanoparticles supported on N-dopedgraphitic carbon. These small, well-distributed metallic Conanoparticles, with Co–N bonding states on N-doped graphiticcarbon supports, offer signicant advantages for various cata-lytic reactions, including heterogeneous catalysis and electro-chemical energy conversion.Fig. 6 (a) Effect of time and (b) plots of the pseudo-first-order kineticsfor the reduction of 4-NP over the FDC, Co@HC-0.5, Co@HC-1.0,Co@HC-1.5, Co@HC-2.0, and Co-ZDC catalysts.3.2 Catalytic activities of the Co@HCsThe synthesized nanostructured hybrid carbons (Co@HCs)were utilized in the heterogeneous catalytic reduction ofnitroarenes, addressing both environmental and chemicalconcerns. This reduction process is signicant in organicsynthesis due to the high value of the resulting aromatic aminesor amino phenols.55–60Fig. 6 shows the performance of the prepared FDC,Co@ZDC, and Co@HCs materials for catalytic reduction paranitrophenol (4-NP) in the presence of aqueous NaBH4 under UVirradiation. Fig. 6a compares the effect of reaction time on theThis journal is © The Royal Society of Chemistry 2026reduction of 4-NP over the FDC, Co@ZDC, and Co@HC cata-lysts, indicating that Co@HC-1.0 had the highest conversionefficiency, and FDC (without any Co-species) had the lowestconversion efficiency. Fig. 6b represents the pseudo-rst-orderkinetic plots over the tested catalysts, and the estimatedkinetic parameters from the respective plots (Fig. 6b) aresummarized in Table 2. The correlation coefficients (R2) are veryclose to 1, which validates the successful use of the rst-orderkinetic model for the reduction of 4-NP over the studied cata-lysts. The estimated kinetic constants (k) conrm the highestreactivity of the Co@HC-1.0 for the reduction of 4-NP with anorder of Co@HC-1.0 > Co@ZDC > Co@HC-1.5 > Co@HC-2.0 >FDC. The turnover frequency (TOF) values calculated from the2-minutes reaction data, summarized in Table 2, furtherdemonstrate the superior performance of the Co@HC-1.0catalyst. Consequently, Co@HC-1.0 stands out as a highlycompetitive catalyst among reported Co-based catalysts for thereduction of 4-NP, both in terms of the rate constant (k) andTOF, as detailed in the comparative analysis presented in TableS1.Fig. 7 compares the reduction efficiencies of a series ofnitroarenes with different or no substituents using the Co@HC-1.0 catalyst in the presence of NaBH4. The effect of reaction timeon nitroarene reduction (Fig. 7a) and the pseudo-rst-orderkinetic plots (Fig. 7b) for the tested nitroarene reduction overJ. Mater. Chem. A, 2026, 14, 19423–19431 | 19427http://creativecommons.org/licenses/by/3.0/http://creativecommons.org/licenses/by/3.0/https://doi.org/10.1039/d6ta01685eTable 2 Pseudo-first-order rate constants and correlation coefficients of the reduction of nitroarene over Co@HC catalysts at roomtemperatureMaterials Co-content (atom%)aNitroarenesubstrateRate constantK (min−1) Relative kb R2 TOF (h−1)FDC 0 4-NP 6.4 × 10−2 1 0.998 —Co@HC-0.5 1.2 4-NP 1.63 × 10−1 2.5 0.998 231Co@HC-1.0 1.5 4-NP 9.25 × 10−1 14.5 (1.3b) 0.982 486Co@HC-1.5 2.3 4-NP 4.16 × 10−1 6.5 0.998 285Co@HC-2.0 3.1 4-NP 3.09 × 10−1 4.8 0.965 142Co@ZDC 12.8 4-NP 7.24 × 10−1 11.3 0.997 55Co@HC-1.0 1.5 4Cl-NB 3.5 × 10−1 — 0.998 —Co@HC-1.0 1.5 2-NP 3.5 × 10−1 — 0.998 —Co@HC-1.0 1.5 NB 1.02 × 10−1 — 0.990 —Co@HC-1.0 1.5 4Me-NM 8.3 × 10−1 — 0.995 —a Co-content was analyzed by EDS analysis. b Relative k was estimated by considering the k of FDC as 1; relative Co@ZDC.Fig. 7 (a) Effect of time and (b) plots of the pseudo-first-order kineticsfor the reduction of different nitroarenes (i.e., 4Cl-NB, 2-NP, 4-NP, NBand 4M-NB) over the Co@HC-1.0 catalyst.Journal of Materials Chemistry A PaperOpen Access Article. Published on 10 April 2026. Downloaded on 5/22/2026 7:59:59 AM.  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.View Article Onlinethe Co@HC-1.0 show different reactivity in terms of theirconversion and kinetics (Table 2). The Co@HC-1.0 catalyst was,as expected, found to be very effective for the reduction ofnitroarenes with different substituents, with reactivity varyingamong them.The metal–N–carbon heterojunction in carbon materials,especially those with an enriched graphitic phase and dopedwith Co and N, can signicantly enhance charge transfer,making them useful for various catalytic oxidation and reduc-tion reactions.51–63 Co and N-doped graphitic carbons withhierarchical porosity not only facilitate the adsorption of reac-tants but also ensure efficient mass transfer of reactants andintermediates/products. Additionally, doping with heteroatomsof different electronegativities (higher and lower) oenproduces a synergistic effect among the doped heteroatoms,driven by the unique electronic structure of these nanohybridmaterials.64,65 Therefore, the activity of the Co@HCs in nitro-arene reduction reactions is likely governed by the Co–N coor-dination sites, Co nanoparticles, hierarchical porosity, N-doping, enriched graphitic carbon, and the synergistic effectbetween Co and N heteroatom.66,67Both the Co–N coordination sites and Co nanoparticles, asevidenced by XPS, play a critical role in facilitating electrontransfer from the reducing agent (here, BH4−; the hydrogendonor) to the nitro group of nitroarenes. These sites act ascatalytic centers, while graphitic carbon enhances electrical19428 | J. Mater. Chem. A, 2026, 14, 19423–19431conductivity and electron mobility, and hierarchical porosity,and N-doping enhances mass transport, adsorption, andstability. Similar synergistic effects of Co–N–C systems havebeen widely reported in catalytic hydrogenation and electro-chemical reactions.59,60 The Co@HC-1.0 catalyst showed thehighest catalytic activity for 4-NP reduction, despite havinglower Co content (the main active sites) than Co@ZDC,Co@HC-1.5, and Co@HC-2.0, but slightly higher than Co@HC-0.5. Additionally, Co@HC-1.0 has higher surface area and porevolumes than Co@ZDC, Co@HC-1.5, and Co@HC-2.0, butlower than Co@HC-0.5. A detailed comparison of Tables 1 and 2reveals that Co@HC-1.0 achieves an optimal balance betweenCo content (1.5 at%), moderate particle size (∼5.8 nm), andhierarchical porosity (SBET = 418.7 m2 g−1). In contrast,Co@HC-0.5, despite a higher surface area, contains insufficientCo active sites, whereas Co@HC-1.5 and Co@HC-2.0 exhibitlarger Co particles and reduced surface areas, leading to lowercatalytic efficiency. This demonstrates that catalytic perfor-mance is governed by a delicate interplay between active sitedensity, nanoparticle size, and pore accessibility. These resultsindicate that both the optimal Co content with controlledparticle size and distribution and the porosity of the Co@HCsare essential for achieving high conversion, kinetic rate, andTOF values for 4-NP reduction, rather than a single parameter.The observed reactivity order for the reduction of differentnitroarenes (as illustrated in Scheme 1) is: nitrobenzene (NB) >para-nitrophenol (4-NP) > ortho-nitrophenol (2-NP) > para-methyl nitrobenzene (4Me-NB) > para-chloro nitrobenzene (4Cl-NB). NB is the easiest to reduce because it lacks substituentsthat affect the nitro group. 4-NP, despite having an electron-donating group, is still relatively easy to reduce due to the –OH group in the para position. The ortho –OH group in 2-nitrophenol introduces steric hindrance, making it harder toreduce. The methyl group in 4-methyl-nitrobenzene, being anelectron-donating group, makes the nitro group less susceptibleto reduction. Lastly, the chloro group in 4-chloro-nitrobenzene,due to its strong electron-withdrawing inductive effect, makesthe nitro group the most electron-decient and hardest toreduce.This journal is © The Royal Society of Chemistry 2026http://creativecommons.org/licenses/by/3.0/http://creativecommons.org/licenses/by/3.0/https://doi.org/10.1039/d6ta01685eScheme 1 Tested nitroarene substrates and their correspondingarylamine products obtained after reduction in aqueousmedium usingCo@HC-1.0 as the catalyst and NaBH4 as the reducing agent. Thecorresponding UV-Vis absorption maxima (lmax) of the nitroaromaticsubstrates and their reduced products in aqueous solution are alsopresented.Paper Journal of Materials Chemistry AOpen Access Article. Published on 10 April 2026. Downloaded on 5/22/2026 7:59:59 AM.  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.View Article Online3.3 Recyclability testFig. 8a illustrates the recyclability of the Co@HC-1.0 catalyst forthe reduction of 4-NP. The results show only a slight decrease inreduction performance aer ve consecutive cycles. The catalystwas magnetically separated and regenerated by washing withethanol and vacuum drying. Fig. 8b compares the N2 adsorp-tion–desorption isotherms of the fresh and recycled Co@HC-1.0catalyst. The isotherms of the recycled catalyst (aer four cycles)are very similar to those of the fresh catalyst, even aer severaluses, conrming the sustainability and recyclability of thedeveloped catalyst. The negligible loss in catalytic activity,together with the nearly unchanged isotherms, suggestsminimal Co leaching and excellent structural stability. Nosignicant aggregation or loss of active sites was observed,although future ICP analysis could further quantify Co leaching.Fig. 8 (a) Recyclability test results in terms of conversion of 4-NP overthe Co@HC-1.0 catalyst; (b) nitrogen adsorption–desorptionisotherms of the fresh and recycled Co@HC-1.0 catalyst.This journal is © The Royal Society of Chemistry 2026Overall, Co@HC-1.0 exhibits high catalytic activity, structuralrobustness, and excellent recyclability, making it a promisingcandidate for sustainable heterogeneous catalysis. Therefore,the precise nanoarchitectonics of Co-anchored, N-doped hier-archical carbon nanohybrids with controlled composition,distribution, and porosity effectively meet the requirements fora highly efficient and recyclable catalytic material, particularlyfor the reduction of nitroarenes.4. ConclusionsIn conclusion, we have successfully demonstrated the synthesisof hierarchical porous carbon nanostructures anchored withCo-metals by carbonizing newly developed MOFOF compositeswith well-distributed ZIF-67 on a self-assembled fullerenenanostructure. Unlike conventional ZIF-67-derived systems, theMOFOF approach incorporates fullerene nanotubes asa secondary carbon scaffold, creating a dual-carbon hierarchicalframework that enhances Co dispersion, controls particle size,and strengthens interactions between Co, N-doped carbon, andgraphitic domains, advantages not achievable in single-precursor MOF-derived materials. To the best of our knowl-edge, it is the rst example of using a nanostructured MOFOFcomposite to get Co@HC materials. The Co@HCs possessa well-distribution of atomic level or ultrasmall Co-nanoparticles wrapped in a graphitic carbon layer on a hybridcarbon support with N-doping and hierarchical porosity andshowed superior catalytic performance in the reduction ofnitroarene compounds to the respective aromatic amines. TheCo@HC-1.0 catalyst not only achieves high conversion effi-ciency in terms of kinetics and TOF values, but also superiorreusability, and retains its structural integrity aer multiplecatalytic cycles. These ndings indicate that Co@HC-1.0 isa highly effective and recyclable catalyst, with signicant rele-vance to pharmaceutical synthesis and environmental remedi-ation. Moreover, the hierarchical Co–N–C architecture exhibitsstrong potential for broader applications, including energystorage and electrocatalysis (e.g., ORR and CO2 reduction), dueto its high surface area, good conductivity, and tunable activesites. Overall, the successful nanoarchitecture of Co-anchored,N-doped hierarchical carbon nanohybrids with controlledcomposition and porosity offers a promising strategy fordeveloping advanced catalytic materials.Author contributionsB. N. B. and L. K. S. contributed equally to conceptualizationand methodology. B. N. B., R. N. A., and S. S. contributed to theinvestigation. B. N. B., R. N. A., S. S., and L. K. S. contributed todata curation. B. N. B. and L. K. S. contributed to the prepara-tion of the original dra. L. K. S. and K. A. contributed to thereview and editing. L. K. S. and K. A. contributed to supervisionand project administration. K. A. contributed to fundingacquisition. All authors have read and agreed to the publishedversion of the manuscript.J. Mater. Chem. A, 2026, 14, 19423–19431 | 19429http://creativecommons.org/licenses/by/3.0/http://creativecommons.org/licenses/by/3.0/https://doi.org/10.1039/d6ta01685eJournal of Materials Chemistry A PaperOpen Access Article. Published on 10 April 2026. Downloaded on 5/22/2026 7:59:59 AM.  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.View Article OnlineConflicts of interestThere are no conicts to declare.Data availabilityThe data supporting this article have been included as part ofthe supplementary information (SI). Supplementary informa-tion: additional TEM images; XRD and Raman data, nitrogenadsorption isotherms and the corresponding pore size distri-bution proles. See DOI: https://doi.org/10.1039/d6ta01685e.AcknowledgementsThis study was partially supported by Japan Society for thePromotion of Science KAKENHI Grant no. JP23H05459 andJP25H00898. R. N. A. and S. S. are thankful to the Ministry ofEducation, Culture, Sports, Science and Technology (MEXT) forthe doctoral program scholarship.Notes and references1 A. Pradhan and P. R. Gogate, J. Hazard. Mater., 2010, 173,517–522, DOI: 10.1016/J.JHAZMAT.2009.08.115.2 M. P. Rayaroth, C. T. Aravindakumar, N. S. Shah andG. 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A, 2026, 14, 19423–19431 | 19431https://doi.org/10.1002/smll.202000158https://doi.org/10.1016/J.JECHEM.2020.08.007https://doi.org/10.1039/D3TA07125Ahttps://doi.org/10.1039/D1TA09645Ahttps://doi.org/10.1039/D1TA09645Ahttps://doi.org/10.1039/C6TA09030Chttps://doi.org/10.1039/D2CE00872Fhttps://doi.org/10.1002/anie.201408856https://doi.org/10.1021/acsami.7b13277https://doi.org/10.1039/D1NR07198Jhttps://doi.org/10.1039/D1NR07198Jhttps://doi.org/10.1002/CHEM.202004535https://doi.org/10.1002/adfm.202106924https://doi.org/10.1039/c9ta03613jhttps://doi.org/10.1002/cplu.202400408https://doi.org/10.1016/j.seppur.2023.125425https://doi.org/10.1016/j.seppur.2023.125425https://doi.org/10.1016/j.matchemphys.2025.131530https://doi.org/10.1016/j.jallcom.2022.164645https://doi.org/10.1038/srep30295https://doi.org/10.1038/s41598-022-11820-6https://doi.org/10.1039/d1ma00937khttps://doi.org/10.3389/fchem.2022.1000680https://doi.org/10.3389/fchem.2022.1000680https://doi.org/10.1039/d4su00531ghttps://doi.org/10.1016/j.apcatb.2025.125686https://doi.org/10.1016/j.jcat.2022.08.012https://doi.org/10.1039/D4TA03635Bhttps://doi.org/10.1039/D4TA03635Bhttps://doi.org/10.1016/j.apcata.2023.119373https://doi.org/10.1039/D1EE00166Chttps://doi.org/10.1039/D1EE00166Chttps://doi.org/10.1039/C6TA01054Ghttps://doi.org/10.1021/acscatal.7b03270https://doi.org/10.1002/anie.201209548https://doi.org/10.1002/anie.201209548https://doi.org/10.1021/acs.chemrev.9b00230https://doi.org/10.1016/J.CEJ.2021.129818https://doi.org/10.1039/C7TA02184Dhttp://creativecommons.org/licenses/by/3.0/http://creativecommons.org/licenses/by/3.0/https://doi.org/10.1039/d6ta01685e Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction Metaltnqh_x2013organic framework on fullerene (MOFOF) derived Co-anchored hierarchical carbon nanocomposite for catalytic nitroarene reduction