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Synergistic NiCo-BTC Catalysts for the Catalytic Transfer Hydrogenation of Furfural to γ-Valerolactone: Insights from Monometallic Cu-, Ni-, and Co-BTC Comparison
(2026-10-01)
Thansirisunthorn, Sudarat
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Teerawatananond, Thapong
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Shoosri, Tanyarat
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Rungtaweevoranit, Bunyarat
;
Miyake, Takanori
A series of monometallic Cu-BTC, Ni-BTC, and Co-BTC catalysts was successfully synthesized via the solvothermal method to evaluate their performance in the catalytic transfer hydrogenation of furfural (FF) to γ-valerolactone (GVL). The Co-BTC and Ni-BTC catalysts exhibited higher FF conversion, selectivity, and GVL yield than Cu-BTC due to favorable redox properties of Co2+ and Ni2+ and stronger acidity that enhance substrate activation and key ring-opening and lactonization steps. To further enhance performance, bimetallic NiCo-BTC catalysts with different Ni/Co mole ratios (0.25, 0.50, 0.75, 1.00) were developed. All bimetallic NiCo-BTC catalysts outperformed the monometallic counterparts, with 0.50NiCo-BTC achieving complete FF conversion and the highest GVL selectivity and yield of 89% at 200 °C after 24 h. TEM, XPS, XANES, and NH<inf>3</inf>-TPD analyses indicated that the enhanced catalytic activity and selectivity arise from synergistic Ni-Co interactions and increased surface acidity. Time-resolved product analysis confirmed a sequential pathway with furfuryl alcohol (FA) as a key intermediate. Moreover, the 0.50NiCo-BTC catalyst exhibited good reusability over three cycles with minimal activity loss, demonstrating structural stability under reaction conditions. These results highlighted the importance of metal synergy and acid site tuning in designing highly efficient metal organic framework catalysts for biomass upgrading via catalytic transfer hydrogenation.
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Role of Copper Species in Copper Phyllosilicate Catalysts for the Catalytic Transfer Hydrogenation of Furfural to γ-Valerolactone
(2025-02-17)
Shoosri, Tanyarat
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Thongratkaew, Sutarat
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Rungtaweevoranit, Bunyarat
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Kraithong, Wasawat
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Faungnawakij, Kajornsak
Copper phyllosilicate (CuPS) catalysts were synthesized and evaluated for the catalytic transfer hydrogenation of furfural to γ-valerolactone (GVL). Various copper loadings (10–30 wt.%) were studied to elucidate the impact of copper species on catalytic performance. Notably, a high dispersion of copper (%D<inf>Cu</inf> ≈ 70%) and a substantial BET surface area (620 m2/g) were achieved, even at the maximum copper loading of 30 wt.%. TR-XANEs and XPS analyses identified the two geometric structures of Cu2⁺ on the CuPS catalysts; square planar and octahedral alongside Cu⁺/Cu⁰ species were formed upon reduction at temperatures exceeding 200 °C. The reduced 30% CuPS-R catalyst, enriched in metallic Cu⁰, achieved complete conversion of furfural, but exhibited low GVL selectivity (22%). Conversely, the as-synthesized 30% CuPS, predominantly composed of Cu2⁺, showed a lower furfural conversion (14%) but higher selectivity for GVL (37%). The physical mixing of 30% CuPS-R and 30% CuPS in a 50:50 ratio yielded the best catalytic performance, resulting in 100% furfural conversion and 86% GVL selectivity. The findings suggest that metallic Cu⁰ is essential for initiating the conversion of furfural, while Cu2⁺ plays a critical role in GVL formation. An optimal Lewis/Brønsted acidity (L/B) ratio of 5.7 is proposed for the mixed catalysts. The proposed reaction mechanism underscores the complex interplay between different copper species and acid sites, emphasizing the need for optimizing both metal and acid functionalities in catalyst design.
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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
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Boonyoung, Pawan
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Pansakdanon, Chaianun
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Suttisintong, Khomson
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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>K2 values are 121.7 and 56.0 kJ mol K−1 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
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Eiad-ua, Apiluck
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Kraithong, Wasawat
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Viriya-empikul, Nawin
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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.
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Production of γ-valerolactone from methyl levulinate via catalytic transfer hydrogenation on nickel-copper oxide catalyst
(2016-01-01)
Tanwongwal, Worapak
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Kuboon, Sanchai
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Kraithong, Wasawat
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Eiad-Ua, Apiluck
γ-Valerolactone (GVL) is successfully produced via catalytic transfer hydrogenation from methyl levulinate on nickel copper oxide catalysts with the comparable result to that of Raney-nickel. This catalyst is prepared at lower temperature (lower than 1000ºC) and pretreatment is not required before its use. Among different calcination temperature, Ni-Cu-O which synthesis at 700ºC shows the best catalytic performance with 100% methyl levulinate conversion and more than 95% GVL yield and characterization result was shows this calcination temperature was affect catalyst to highest crystallization and surface area. The study of atomic ratio effect indicates that nickel-copper oxide which had nickel oxide more than copper oxide is better for this reaction.

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