Numwong, Natthida

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Numwong, Natthida
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natthida.nu@kmitl.ac.th

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    Effect of cobalt complex precursors on reactivity of cationic cobalt catalysts: Cyclohexane dehydrogenation
    (2019-05-10)
    Choojun, Kittisak
    ;
    Worathanaseth, Arucha
    ;
    Kuhatasanadeekul, Satu
    ;
    Kurato, Teeraporn
    ;
    Ketaniruj, Supanut
    Effect of the cobalt precursors, including [Co(bipy)<inf>3</inf>](NO<inf>3</inf>)<inf>2</inf>, [Co(NH<inf>3</inf>)<inf>5</inf>Cl]Cl<inf>2</inf>, [Co(NH<inf>3</inf>)<inf>6</inf>]Cl<inf>3,</inf> and [Co(en)<inf>2</inf>Cl<inf>2</inf>] Cl, on reactivity of the cationic Co/SiO<inf>2</inf> prepared by strong electrostatic adsorption (SEA) was investigated for the dehydrogenation of cyclohexane as a model reaction. According to the charge density of the cobalt complex, highly dispersed Co<sup>2+</sup> species and/or Co<sup>3+</sup> oxide can be obtained on the silica surface. The dehydrogenation activity is in the order of Co/SiO<inf>2</inf> catalysts prepared by [Co(bipy)<inf>3</inf>](NO<inf>3</inf>)<inf>2</inf> > [Co(NH<inf>3</inf>)<inf>5</inf>Cl]Cl<inf>2</inf> > [Co(NH<inf>3</inf>)<inf>6</inf>]Cl<inf>3</inf> > [Co(en)<inf>2</inf>Cl<inf>2</inf>] Cl, correlating to the Co<sup>2+</sup> content of the final catalysts. The cationic cobalt catalysts are more active than the pre-reduced one. Although metallic cobalt is found to be less active, the activity of cationic cobalt catalyst is enhanced under H<inf>2</inf> flow, presumably due to the formation of cobalt hydride intermediate. The inter-conversion of Co<sup>2+</sup>/cobalt hydride intermediate is readily reversible and regulated by presence of hydrogen.
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    Effect of Pd particle size on activity and cis-trans selectivity in partial hydrogenation of soybean oil-derived FAMEs over Pd/SiO2 catalysts
    (2020-06-15)
    Numwong, Natthida
    ;
    Prabnasak, Panisa
    ;
    Prayoonpunratn, Patsakol
    ;
    Triphatthanaphong, Pholawat
    ;
    Thunyaratchatanon, Chachchaya
    Partial hydrogenation of soybean oil-derived fatty acid methyl esters (FAMEs) was performed to improve oxidative stability of biodiesel. The reaction was tested in a semi-batch reactor at 100 °C, 0.4 MPa. The effect of Pd particle size on activity and cis-trans selectivity was investigated over SiO<inf>2</inf>- and MCM-41-supported Pd catalysts, with different Pd loadings (0.5 and 1 wt.%). For Pd/SiO<inf>2</inf> catalysts with relatively large Pd particle sizes (6.1–7.8 nm), the adsorption of polyunsaturated C18:2 and C18:3 FAMEs was promoted on the flat metal surface, providing 2- to 3-fold higher turnover frequency (TOF) compared with Pd/MCM-41 catalysts. In contrast, the Pd/MCM-41 catalysts with relatively small Pd particle sizes (2.7–4.0 nm), showed higher selectivity towards the desired monounsaturated C18:1 FAMEs due to lower affinity of isolated double bond (presented in C18:1) on the Pd surface. In addition, selectivity towards the desired cis-C18:1 FAMEs was found to be highly sensitive to Pd particle size. The 0.5Pd/MCM-41 catalyst with small Pd particle size (2.7 nm), provided high cis-C18:1 selectivity, resulting in a biodiesel with better cold flow property compared with the trans-isomers. With partial hydrogenation over the prepared Pd catalysts, biodiesel with significantly improved oxidative stability (>10 h) could be obtained.
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    Stabilized Pd Nanoparticles Encapsulated in MIL-101(Cr) for Chemoselective Hydrogenation of Polyunsaturated FAMEs
    (2025-11-24)
    Preedawichitkun, Yardthip
    ;
    Numwong, Natthida
    ;
    Chanlek, Narong
    ;
    Chung, Po Wen
    ;
    Kumar, Raju
    Palladium nanoparticles (Pd NPs) were successfully encapsulated within the porous framework of MIL-101(Cr) via a double solvent method to produce highly dispersed and stable catalysts for the chemoselective hydrogenation of polyunsaturated fatty acid methyl esters (FAMEs). Pd loadings ranging from 0.5 to 1.5 wt.% were systematically studied to elucidate the effects of nanoparticle size, dispersion, and hydrogen activation behavior on catalytic performance. The 0.8Pd/MIL-101(Cr) catalyst exhibited the highest turnover frequency (TOF ∼9,700 h<sup>−1</sup>) and superior selectivity (>90%) toward monounsaturated products (C18:1), attributed to optimal Pd dispersion. In contrast, the 0.5Pd/MIL-101(Cr) showed an induction period under low H<inf>2</inf> partial pressure, indicating limitations in hydride accommodation, while the 1.5Pd/MIL-101(Cr) suffered from Pd aggregation, resulting in a reduced intrinsic activity. Product selectivity was primarily governed by overall conversion: C18:1 was favored at low conversions, whereas C18:0 formation increased at higher conversions due to secondary hydrogenation. The catalysts demonstrated excellent stability and recyclability over multiple cycles without detectable Pd leaching or structural degradation. These findings establish MIL-101(Cr) as a robust and tunable platform for dispersing Pd NPs and highlight the potential of Pd/MIL-101(Cr) catalysts for efficient, selective upgrading of bioderived feedstocks under mild reaction conditions.