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Author: search.filters.author.Tanwongwan, WorapakSubject: search.filters.subject.Catalytic transfer hydrogenation

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    Mechanistic investigation of Ni and NiCu for catalytic transfer hydrogenation of methyl levulinate to γ-valerolactone: A combined experimental and DFT study
    (2023-06-25)
    Chitpakdee, Chirawat
    ;
    Boonyoung, Pawan
    ;
    Pansakdanon, Chaianun
    ;
    Suttisintong, Khomson
    ;
    Faungnawakij, Kajornsak
    Recently various supported bimetallic catalysts have been employed as effective catalysts for γ-valerolactone (GVL) production from levulinic acid or its esters. However, previous reports have shown synergetic roles of active metals and supports as important keys for superior catalytic performance. This work combines both experimental and simulation studies to focus solely on the role of bimetallic formation between nickel (Ni) and copper (Cu). The experimental results suggest that both Ni and nickel-copper alloy (NiCu) catalysts are good for hydrogenation of methyl levulinate (ML) to an intermediate species, 4-hydroxypentanoic acid (HPA). However, only NiCu has a better tendency to accelerate the conversion of HPA to GVL via cyclization process. Activation energy from experimental study of cyclization step over Ni is about two times larger than that of NiCu (E<inf>a</inf><sup>K2</sup> values are 121.7 and 56.0 kJ mol K<sup>−1</sup> for Ni and NiCu, respectively) provided strong evidence of superior GVL production over NiCu catalyst. Density Functional Theory (DFT) simulation results reveal solid finding to support the high efficiency of NiCu over Ni catalyst for GVL production. The calculated energy barrier for HPA conversion to GVL over the NiCu is 1.0 eV which is lower than that of the Ni catalyst (1.54 eV). The Ni provided only one concerted pathway to transform from ML to GVL, while NiCu could provide either a concerted or nonconcerted pathway where the latter one requires lower activation energy for GVL production. The combination of these experimental and simulation results leads to a better understanding of bimetallic catalyst design for GVL production via catalytic transfer hydrogenation without any support materials.
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    Simultaneous activation of copper mixed metal oxide catalysts in alcohols for gamma-valerolactone production from methyl levulinate
    (2019-06-05)
    Tanwongwan, Worapak
    ;
    Eiad-ua, Apiluck
    ;
    Kraithong, Wasawat
    ;
    Viriya-empikul, Nawin
    ;
    Suttisintong, Khomson
    Catalytic transfer hydrogenation (CTH)of biomass-derivatives to value-added chemicals using metal-based catalysts is a promising process in biorefinery since it does not require high pressure of expensive and flammable hydrogen gas (H<inf>2</inf>). However, an activation of these catalysts using H<inf>2</inf> treatment prior to the CTH process limits this advantage. Here, copper mixed metal oxides are introduced as simultaneously activated catalysts (SACs)in the presence of alcohol for a production of gamma-valerolactone (GVL)from methyl levulinate (ML)without requirement of additional H<inf>2</inf> gas during both catalyst pretreatment and hydrogenation steps. Different alcohols were selected to function as hydrogen sources for both catalyst activation and ML hydrogenation. All copper mixed metal oxides, especially CuNiO showed significant potential as catalysts for ML conversion to GVL at 200 °C within 3 h. While 2-propanol and 2-butanol exhibited effective roles as hydrogen sources for simultaneous reductions of the catalysts to generate metal active sites and provided hydrogen species for hydrogenation of ML to GVL. Hydrogen temperature programmed reduction (H<inf>2</inf>-TPR), alcohol-assisted simultaneous reaction (ASR), in situ X-ray diffraction (in situ XRD)and X-ray photoelectron spectroscopy (XPS)revealed that the complementary cooperation between secondary alcohols and catalysts is the important key for the high GVL production in this work.