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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
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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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Sustainable Liquid-Phase Selective Hydrogenation of CO2 to C1–C3 Alcohols over Mg-, Zn-, and Pt-Modified Copper Phyllosilicate Catalysts: Insight Reaction Pathways
(2026-07-27)
Poson, Suttiporn
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Teerawatananond, Thapong
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Shoosri, Tanyarat
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Miyake, Takanori
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Panpranot, Joongjai
The sustainable conversion of carbon dioxide (CO<inf>2</inf>)into value-added chemicals remains a major challenge, particularly for the selective formation of C<inf>1</inf>–C<inf>3</inf> alcohols. Herein, bimetallic copper phyllosilicate catalysts (1%X-20%CuPS, X = Zn, Mg, Pt) were developed and systematically evaluated for the liquid-phase hydrogenation of CO<inf>2</inf> to alcohols compared with monometallic 20%CuPS as a benchmark. Among these catalysts, 1%Mg-20%CuPS exhibited the highest activity, excellent stability, and good reusability, highlighting the beneficial role of earth-abundant metal promotion. The enhanced performance is attributed to increased surface basicity and stronger CO<inf>2</inf> adsorption, which facilitated the formation and stabilization of formate intermediates. Concurrently, in situ reduction of Cu+/Cu0 sites promotes efficient H<inf>2</inf> dissociation and subsequent hydrogenation steps. A high surface Mg/Si ratio further stabilizes CO-derived intermediates and promotes CO-mediated C–C coupling, favoring C<inf>2</inf><inf>+</inf> alcohol formation. Zn incorporation induced similar but less pronounced effects, whereas Pt altered the reaction network, leading to increased byproduct formation and lower alcohol selectivity. After 24 h, the total alcohol selectivity followed the order 1%Mg-20%CuPS (98%) > 1%Zn-20%CuPS (88%) > 1%Pt-20%CuPS (73%) > 20%CuPS (67%). Overall, second metal modification effectively tunes catalyst properties and reaction pathways, with Mg emerging as a sustainable and industrially viable promoter for CO<inf>2</inf> valorization to C<inf>1</inf>–C<inf>3</inf> alcohols.
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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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Bimetallic copper- and nickel-rich Cu-Ni phyllosilicate catalysts for the liquid phase selective hydrogenation of furfural to furfuryl alcohol
(2024-12-02)
Shoosri, Tanyarat
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Chotiwilaiwan, Pisacha
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Rattanapornchaiwat, Tanisorn
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Teerawatananond, Thapong
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Miyake, Takanori
Bimetallic Cu-Ni phyllosilicates (Cu-NiPS) with various Ni/Cu ratios (5 : 15, 10 : 10, 15 : 5 wt%) were synthesized using ammonia evaporation hydrothermal method to obtain copper-rich or nickel-rich Cu-Ni alloys. These catalysts were evaluated for the selective hydrogenation of furfural (FF) to furfuryl alcohol (FA) in the liquid phase under relatively mild conditions (100 °C, 20 bar H<inf>2</inf>). The bimetallic Cu-NiPS catalysts exhibited excellent dispersion of the Ni-Cu alloy with average particle sizes ranging from 3.8 to 4.8 nm and demonstrated significantly enhanced catalytic performance over the monometallic nickel phyllosilicate (20% NiPS). The copper-rich Ni-Cu alloy (15% Cu-5% NiPS) exhibited the highest FF conversion efficiency (88%) and FA selectivity (90%). This superior performance is attributed to its smallest particle size, higher proportion of Cu0 and the synergistic interactions between Ni and Cu. This synergy effectively stabilizes the carbonyl group while promoting efficient H<inf>2</inf> dissociation and FA desorption, thereby facilitating the hydrogenation of FF to FA. Furthermore, the catalyst exhibited excellent recyclability and maintained high conversion efficiency and selectivity over multiple cycles.
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Elucidation of the Catalytic Pathway for the Direct Conversion of Furfuryl Alcohol into γ-Valerolactone over Al2O3-SiO2 Catalysts
(2023-12-12)
Chuangpusri, Pichaya
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Jantasee, Sasiradee
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Weerachawanasak, Patcharaporn
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Tolek, Weerachon
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Ngamcharussrivichai, Chawalit
The one-pot conversion of furfuryl alcohol (FA) into GVL was investigated over the sol-gel-synthesized Al<inf>2</inf>O<inf>3</inf>-SiO<inf>2</inf> (AlSi) catalysts with various Al<inf>2</inf>O<inf>3</inf> loadings (0.2-10 wt %) and commercial zeolites including MFI-1, H-ZSM5, H-beta, and HY-15 in a batch reactor under mild reaction conditions (130 °C, 1 bar N<inf>2</inf>, and 15-120 min). The reaction pathways depend largely on the acid properties of the catalysts, especially the types of Bronsted (B) and Lewis (L) acid sites. A tandem alcoholysis/hydrogenation/cyclization sequence is dominant on the AlSi catalysts (Al ≥ 4%) and all the zeolites except MFI-1, resulting in complete conversion of FA and GVL with an yield 64-75% with IPL as the major side-product, regardless of the differences in their B/L ratios 0.06-1.35. In the absence of B acid sites (i.e., 0.2% AlSi and MFI-1 catalysts), FA could be straightforwardly converted into GVL on the weak Lewis acid sites from the isolated silanol groups using 2-propanol as a hydrogen source. The AlSi catalysts are promising tunable catalysts for FA conversion with good recyclability.
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One-Pot Conversion of Furfural to γ-Valerolactone over Co- and Pt-Doped ZSM-5 Catalysts
(2023-03-01)
Tolek, Weerachon
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Auppahad, Warucha
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Weerachawanasak, Patcharaporn
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Mekasuwandumrong, Okorn
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Praserthdam, Piyasan
γ-Valerolactone (GVL) is one of the useful biomass compounds produced via different reaction pathways from hemicellulose. In this study, Co- and Pt-doped/ZSM-5 catalysts with different Co loadings (0–10 wt.%) and Pt loadings (0.5–2 wt.%) were prepared by impregnation method and employed in a one-pot conversion of furfural to GVL. The yield of GVL increased with increasing reaction temperature from 100 to 140 °C. At the reaction temperature of 120 °C, higher amounts of secondary products such as AL and IPL can be converted to GVL, especially on the Co- and Pt-modified ZSM-5 catalysts. Compared to the non-modified H-ZSM-5 (GVL yield 35.4%), Co- and Pt-doped ZSM-5 catalysts exhibited much higher yield of GVL with the 1%Pt/ZSM-5 catalyst showing the highest yield of GVL at 85.4% at 120 °C and 1 bar N<inf>2</inf> without the use of liquid acid or external H<inf>2</inf> supply. The catalyst performances were correlated to the physicochemical properties of the catalysts such as the amount and type of acid sites. The NH<inf>3</inf>-TPD and in situ FTIR spectra of pyridine adsorption results revealed that Co- and Pt-loaded on ZSM-5 enhanced Lewis and weak acid sites, which are beneficial for the reaction. The results present a simple strategy to obtain high GVL yield under relatively mild conditions.
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Liquid-Phase Selective Hydrogenation of Furfural to Furfuryl Alcohol over Ferromagnetic Element (Fe, Co, Ni, Nd)-Promoted Pt Catalysts Supported on Activated Carbon
(2022-04-01)
Saknaphawuth, Sureeporn
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Weerachawanasak, Patcharaporn
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Chuenchom, Laemthong
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Praserthdam, Piyasan
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Panpranot, Joongjai
Ferromagnetic element (x = Fe, Co, Ni, and Nd)-promoted Pt/AC catalysts were prepared by co-impregnation method or physical mixing and tested in the liquid-phase hydrogenation of furfural to furfuryl alcohol (FA) under mild conditions (50◦C and 20 bar H<inf>2</inf> ) using water and methanol as the solvent. Among the various catalysts studied, the 0.15FePt/AC exhibited complete conversion of furfural with an FA selectivity of 74% after only 1 h of reaction time in water. The promotional effect of the bimetallic catalysts became less pronounced when methanol was used as the solvent and a 2-furaldehyde dimethyl acetal solvent product was formed. The superior catalyst performances were correlated with the higher Pt dispersion, the presence of low coordination Pt sites, and the strong Pt–Fe interaction as characterized by X-ray diffraction, H<inf>2</inf> temperature-programmed reduction (H<inf>2</inf>-TPR), N<inf>2</inf> physisorption, and infrared spectroscopy of the adsorbed CO (CO-IR). However, to simply use a magnet for catalyst separation, 0.5 wt% Fe was the minimum Fe loading on the Pt/AC. The 0.5FePt/AC still exhibited good magnetic properties after the third consecutive runs.
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Determining the role of oxygen vacancies in palmitone selectivity and coke formation over acid metal oxide catalysts for the ketonization of methyl palmitate
(2021-11-25)
Guntida, Adisak
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Rattanachartnarong, Thanwarat
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Jongsomjit, Bunjerd
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Sooknoi, Tawan
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Weerachawanasak, Patcharaporn
In the present study, TiO<inf>2</inf>, CeO<inf>2</inf>, MnO<inf>2</inf>, and ZrO<inf>2</inf> catalysts were used to investigate the catalytic performance in methyl palmitate ketonization. The reaction was accelerated by weak Lewis acid, while the oxygen vacancies promoted the palmitone selectivity. The use of various characterization techniques revealed that oxygen vacancies played an important role for trapping the hydrogen atom and inhibited its spillover. This caused the suppression of the Lewis acid transformation to new Bronsted acid. Thus, the cracking of palmitone over the new Bronsted acid was diminished, leading to the decrement of selectivity to undesired products. However, when the hydrogen atom was trapped in the oxygen vacancies, the coke deposition was dominant. This phenomenon arose because hydrogen could not suppress the deep dehydrogenation, resulting in the transformation of aliphatic coke to aromatic coke. The role of oxygen vacancies was determined, and it had the positive effect on the palmitone selectivity, whereas it raised the coke formation.
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Development of bimetallic Ni-Cu/SiO2 catalysts for liquid phase selective hydrogenation of furfural to furfuryl alcohol
(2021-01-15)
Weerachawanasak, Patcharaporn
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Krawmanee, Pacharaporn
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Inkamhaeng, Weerachat
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Cadete Santos Aires, Francisco J.
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Sooknoi, Tawan
Bimetallic Ni-Cu/SiO<inf>2</inf> catalysts with different Cu loading (2–5 wt%) were developed for liquid phase selective hydrogenation of furfural to furfuryl alcohol. Among these, bimetallic 2%Ni-X%Cu/SiO<inf>2</inf> (X = 2, 5) catalysts exhibited better catalytic performances than monometallic 2%Ni/SiO<inf>2</inf> and 2%Cu/SiO<inf>2</inf>. Moreover, the bimetallic 2%Ni-5%Cu/SiO<inf>2</inf> catalyst showed the best catalytic performance with 94% of furfural conversion and 64% of furfuryl alcohol selectivity. The synergetic effect of NiCu alloy particles that are present on bimetallic Ni-Cu/SiO<inf>2</inf> catalysts change the adsorption configuration of furfural on the catalyst surface resulting in high catalytic performance in liquid phase selective hydrogenation of furfural to furfuryl alcohol.
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Flame spray-synthesized Pt-Co/TiO2 catalysts for the selective hydrogenation of furfural to furfuryl alcohol
(2021-01-15)
Tolek, Weerachon
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Khruechao, Kitima
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Pongthawornsakun, Boontida
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Mekasuwandumrong, Okorn
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Cadete Santos Aires, Francisco José
Flame spray-synthesized Pt/TiO<inf>2</inf> and PtCo/TiO<inf>2</inf> catalysts with 0.7 wt% Pt and 0–0.4 wt% Co were studied in the hydrogenation of furfural to furfuryl alcohol (FA) at 50 °C and 2 MPa H<inf>2</inf>. Particle formation under high temperature flame facilitated high Pt dispersion and formation of Pt-TiO<inf>x</inf> interface sites, which were beneficial for furfural conversion to FA. Modifying with Co accelerated rutile phase TiO<inf>2</inf> formation, which strongly diminished hydrogenation activity on the (FSP)-PtCo/TiO<inf>2</inf>. On the other hand, (I)-PtCo/TiO<inf>2</inf> prepared by conventional impregnation, anatase phase TiO<inf>2</inf> was preserved (> 85%) and both furfural conversion and FA selectivity increased upon increasing Co loading.

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