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    Correlation of urea precipitation temperature with phase formation, morphology, and catalytic activity for CO2 conversion of CeO2
    (2025-08-01)
    Seeharaj, Panpailin
    ;
    Duangtanon, Jenjira
    ;
    Sreemueang, Chanakan
    ;
    Noppharat, Phetchphalin
    ;
    Kulthananat, Tachatad
    This study proposes a simple method for tailoring the morphology and activity of cerium oxide (CeO<inf>2</inf>) catalysts in converting carbon dioxide (CO<inf>2</inf>) and methanol to green organic carbonate, dimethyl carbonate (DMC), to utilize and reduce CO<inf>2</inf> emissions. CeO<inf>2</inf> was prepared by urea precipitation at 85, 105, and 125 °C for 2 h, then calcining at 600 °C for 2 h. The phase structure and morphology of CeO<inf>2</inf> correlated with the urea hydrolysis rate. A low degree of supersaturation at 85 °C led to heterogeneous precipitation of cerium oxycarbonate (Ce<inf>2</inf>O(CO<inf>3</inf>)<inf>2</inf>.H<inf>2</inf>O) and CeO<inf>2</inf> with spherical morphology, while a higher degree of supersaturation at 105 °C and 125 °C resulted in homogeneous precipitation of single-phase Ce<inf>2</inf>O(CO<inf>3</inf>)<inf>2</inf>.H<inf>2</inf>O with spindle and elongated octahedral morphology, respectively. The spindle-shaped CeO<inf>2</inf> prepared at 105 °C with a predominant surface (111) facet showed the highest catalytic activity, with a DMC yield of 18.81 mmol.g<inf>cat</inf><sup>−1</sup>. The enhanced catalytic efficiency of spindle-shaped CeO<inf>2</inf> was due to the high concentration of surface-active defect sites of exposed cerium cations and oxygen vacancies, which optimized the number of acid–base sites in adsorbing and activating CO<inf>2</inf> and methanol to produce DMC.
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    Alkanolamine-Grafted and Copper-Doped Titanium Dioxide Nanosheets-Graphene Composite Heterostructure for CO2 Photoreduction
    (2023-11-13)
    Karawek, Apisit
    ;
    Kitjanukit, Nutkamol
    ;
    Neamsung, Wannisa
    ;
    Kinkaew, Chonlathon
    ;
    Phadungbut, Poomiwat
    CO<inf>2</inf> photoreduction is an intriguing approach to carbon capture, utilization, and storage (CCUS). It relies on an effective photocatalyst to generate photoinduced electrons that incorporate carbon dioxide (CO<inf>2</inf>), yielding fuel products, e.g., methane, methanol, and ethanol. The heterostructure of titanium dioxide nanosheets (TNS) and graphene oxide (GO) is a sandwich-type composite consisting of two 2-dimensional nanostructures (2D-2D). It was demonstrated as an excellent candidate for CO<inf>2</inf> photoreduction due to its outstanding charge separation ability. This research studied the photoactivity of alkanolamine-grafted TNS and alkanolamine-grafted and copper-doped TNS/GO composites. In the first experiment, triethanolamine-grafted TNS (TEA-TNS) exhibited the best ability in CO<inf>2</inf> photoreduction compared to monoethanolamine- and diethanolamine-grafted TNS (MEA-TNS and DEA-TNS) due to the base-catalyzed hydration nature of CO<inf>2</inf>-TEA interactions. In the second experiment, we studied the photoactivity of four composites, including copper-doped TNS/GO (Cu-TNS/GO), TEA-[Cu-TNS/GO] (grafting TEA on Cu-TNS/GO), Cu-[TEA-TNS]/GO (doping Cu on TEA-TNS/GO), and TEA-Cu-TNS/GO (one-step hydrothermal synthesis with the Cu precursor, TEA, and GO). TEA-[Cu-TNS/GO] showed the best photoactivity since TEA was added last to the heterostructures, which benefited in avoiding side chelation reactions between TEA and Cu ions and ensuring TEA exposure to CO<inf>2</inf>