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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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    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<sup>+</sup>/Cu<sup>0</sup> 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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    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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    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 Co<sup>2+</sup> and Ni<sup>2+</sup> 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.