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    Rational Design of Isolated Tetrahedrally Coordinated Ti(IV) Sites in Zeolite Frameworks for Methyl Oleate Epoxidation
    (2024-10-16)
    Klinyod, Sorasak
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    Yomthong, Krissanapat
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    Iadrat, Ploychanok
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    Kidkhunthod, Pinit
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    The rational design of isolated metals containing zeolites is crucial for the catalytic conversion of biomass-derived compounds. Herein, we explored the insertion behavior of the isomorphic substitution of Ti(IV) in different zeolite frameworks, including ZSM-35 (FER), ZSM-5, and BEA. The different aluminium topological densities of each zeolite framework lead to the creation of different degrees of vacant sites for hosting the tetrahedrally coordinated Ti(IV) active sites. These observations show the precise control of the degree of four-coordinated Ti(IV) sites in a zeolite framework, especially in BEA topology, by tuning the degree of unoccupied sites in the host zeolite structure via dealumination. Interestingly, the more vacancies in the host zeolite structure, the more isolated tetrahedrally coordinated Ti(IV) can be increased, eventually enhancing the catalytic performance in methyl oleate (MO) epoxidation for producing methyl-9,10-epoxystearate (EP). The engineered Ti-β exhibits outstanding performances in bulky MO epoxidation with the amount of produced EP per number of Ti sites up to 17.1±1.8 mol mol<sup>−1</sup>. This observation discloses an alternative strategy for optimizing catalyst efficiency in the rational design of the Ti-embedding zeolite catalyst, endeavoring to reach highly efficient catalytic performance.
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    Effect of synthesized Ag nanoparticles by using the different amounts of polyvinylpyrrolidone for Ag-natural rubber hybrid sheets and their antibacterial properties
    (2017-01-01)
    Prasanseang, Warot
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    Ag-natural rubber (Ag-NR) hybrid sheets were successfully prepared with a very simple and low cost method. In this method, silver nanoparticles (AgNPs) were firstly synthesized by a rapid and green microwave-assisted using polyvinylpyrroridone (PVP) media. The effect of PVP weight ratios towards the size of AgNPs was also investigated. Then, Ag-NR hybrid sheet samples were prepared by latex mixing-casting method using concentrated natural rubber (NR) latex with the synthesized AgNPs colloids. The characteristic absorption, particles sizes and shapes of the obtained AgNPs were examined through UV-vis, TEM and SAED. Also, the prepared Ag-NR sheet samples were characterized using XRD, FT-IR, SEM and EDS techniques. It was found that the particles sizes of all the synthesized AgNPs had spherical-like shape, and the mean sizes were increased from 29.7 to 90.4 nm upon increasing PVP contents. EDS results showed the AgNPs were well-dispersed and impregnated into the rubber matrix. Moreover, the antibacterial properties of the prepared Ag-NR sheets were tested by agar disk-diffusion method with Gram-positive and Gramnegative bacteria as Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli), respectively. The results showed that the hybrid sheets exhibited excellent antibacterial properties against these bacteria, in which the zones of inhibition were also dependent on the synthesized AgNPs by utilizing the different amounts of PVP.
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    TMPMgnBu(L), where L = THF, 2-MeTHF, pyridine and dimethylaminopyridine and TMP = 1,5,9-trimesityldipyrromethene: Reaction with lactide and ε-caprolactone
    (2017-01-01)
    Balasanthiran, Vagulejan
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    Chisholm, Malcolm H.
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    Durr, Christopher B.
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    Jing, Stanley
    The compounds TMPMg<sup>n</sup>Bu(L), where L = THF, 2-MeTHF, pyridine (py) and dimethylaminopyridine (DMAP) and TMP = 1,5,9-trimesityldipyrromethene, have been synthesized and allowed to initiate polymerization with rac-lactide (rac-LA) and ε-caprolactone (ε – CL). Both the rate of rac-LA polymerization and the tacticity were found to be solvent dependent, with CH<inf>2</inf>Cl<inf>2</inf> being faster than THF and yielding heterotactic polylactic acid with P<inf>r</inf> ∼70% and 95%, respectively. For ε-CL, rates of polymerization were in the inverse order with THF being faster than CH<inf>2</inf>Cl<inf>2</inf>. In CH<inf>2</inf>Cl<inf>2</inf> the reactions showed a dependence on the coordinating ligand with rates, 2-MeTHF > THF > py > DMAP in the polymerization of rac-LA and ε-CL. The molecular structure of TMPMg<sup>n</sup>Bu(2-MeTHF) was shown to contain a trigonally distorted tetrahedron of TMPMg(<sup>n</sup>Bu) with a weak axial Mg—-2-MeTHF bond.
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    Design of a rhenium-decorated mesoporous nickel phyllosilicate-derived Ni–Re/MCM-41 catalyst for efficient hydrogenation of levulinic acid to γ-valerolactone
    (2026-04-27)
    Maneewong, Yupawan
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    Lakhani, Pratikkumar
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    Ratchahat, Sakhon
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    Sakdaronnarong, Chularat
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    Limphirat, Wanwisa
    Herein, Ni and NiRe catalysts supported on mesoporous MCM-41 were synthesized through ammonia evaporation (AE) and impregnation (IM) routes to explore structure–activity correlations in the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). The AE-derived nickel phyllosilicate (Ni-PS) framework provided strong interactions through Ni–O–Si linkages, leading to high dispersion and stabilization of Ni species. Incorporation of Re significantly improved reducibility, hydrogen activation, and the balance between acidic and metallic sites, resulting in enhanced catalytic efficiency. The optimized NiRe-PS catalyst exhibited a uniform nanostructure, strong Ni–Re synergy, and the highest metallic Ni fraction, which collectively promoted superior activity and stability. Under mild conditions (140 °C, 10 bar H<inf>2</inf>), NiRe-PS achieved complete LA conversion and ∼96% GVL yield within 4 h, with a turnover frequency of 26.3 h<sup>−1</sup> (160 °C, 10 bar H<inf>2</inf>) and with an apparent rate constant of 0.0059 min<sup>−1</sup>. Mechanistic and isotopic investigations confirmed that both molecular and solvent-derived hydrogen contributed to the hydrogenation pathway. The exceptional activity, recyclability, and structural robustness of NiRe-PS demonstrate the potential of phyllosilicate-based bimetallic systems as efficient, non-noble catalysts for sustainable biomass valorization.
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    TMPZnN(SiMe3)2, [TMPZn(μ-OiPr)]2 and TMPZn[OCMe2C(O)OEt]. Their role in the ring-opening of rac-lactide and ϵ-caprolactone where TMP = 1,5,9-trimesityldipyrromethene
    (2016-06-15)
    Balasanthiran, Vagulejan
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    Chisholm, Malcolm H.
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    Durr, Christopher B.
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    Wambua, Pasco M.
    From the reaction between Zn[N(SiMe<inf>3</inf>)<inf>2</inf>]<inf>2</inf> and TMP-H (1 equiv.) in toluene at room temperature TMPZn[N(SiMe<inf>3</inf>)<inf>2</inf>] was prepared and subsequently reacted with Pr<sup>i</sup>OH (1 equiv.) and HOCMe<inf>2</inf>C(O)OEt (1 equiv.) to give [TMPZn(μ-OPr<sup>i</sup>)]<inf>2</inf> and TMPZn[OCMe<inf>2</inf>C(O)OEt], respectively. The three compounds were each crystallized and characterized by single crystal X-ray diffraction. The compound TMPZn[N(SiMe<inf>3</inf>)<inf>2</inf>] was a three coordinated N<inf>3</inf>Zn compound with an anagostic N(SiMe<inf>3</inf>)<inf>2</inf> ligand where one SiMe<inf>3</inf> was annexed to the Zn<sup>2+</sup> ion. The compound [TMPZn(μ-OPr<sup>i</sup>)]<inf>2</inf> has a molecular C<inf>2</inf> axis and is dimeric in toluene-d<inf>8</inf> solution having a N<inf>2</inf>ZnO<inf>2</inf> core for each Zn<sup>2+</sup> ion. In TMPZn[OCMe<inf>2</inf>C(O)OEt] compound the Zn<inf>2</inf> + ion is four-coordinated. This too is present in solution (IR) and also present in toluene-d<inf>8</inf> and THF where there is evidence of fluxionality with T<inf>c</inf> ∼15 °C and -85 °C, respectively. The compound [TMPZn(μ-OPr<sup>i</sup>)]<inf>2</inf> polymerizes both ϵ-caprolactone (ϵ-CL) and rac-lactide (rac-LA) to give polycaprolactone (PCL) and polylactic acid (PLA), respectively. The rate of the reactions are ϵ-CL > LA and are influenced by the nature of solvent, THF > CD<inf>2</inf>Cl<inf>2</inf>/CH<inf>2</inf>Cl<inf>2</inf>. The nature of PLA derived from rac-LA is heterotactic: P<inf>r</inf> = 0.96 in THF and P<inf>r</inf> = 0.75 in CD<inf>2</inf>Cl<inf>2</inf>/CH<inf>2</inf>Cl<inf>2</inf>. In the copolymerization of rac-LA: ϵ-CL by both [TMPZn(μ-OPr<sup>i</sup>)]<inf>2</inf> and TMPZn[OCMe<inf>2</inf>C(O)OEt] only PLA is produced, PCL is not formed.
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    Deoxygenation of heptanoic acid to hexene over cobalt-based catalysts: A model study for α-olefin production from renewable fatty acid
    (2020-07-25)
    Phichitsurathaworn, Ploynisa
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    Poo-arporn, Yingyot
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    Deoxygenation of heptanoic acid, a model compound, over bimetallic cobalt (Co-Pt, Co-Au, Co-Pd, Co-Ru) supported silica catalysts, was examined for α-olefin production. The catalysts were prepared by conventional impregnation of the metal precursors on silica and characterized by XRF, TEM, H<inf>2</inf>-TPR, acetic acid-TPD, and XANES. Catalytic testing was performed in a fixed-bed flow reactor under atmospheric H<inf>2</inf> pressure. Monometallic cobalt catalysts yielded mainly 1-hexene, but rapid deactivation was observed. Incorporation of 0.5%wt secondary metal, particularly Pt, increases activity and stability under H<inf>2.</inf> A relatively higher olefin/paraffin ratio can be obtained from the reaction over 5%Co+0.5%Pt/SiO<inf>2</inf> when compared to that with higher Pt loading. The co-impregnation method offers Co-Pt catalysts with stability higher than that prepared by the sequential impregnation method. Over cobalt-based catalysts, the deoxygenation is proposed to proceed via reduction of heptanoic acid to heptanal that is an intermediate for decarbonylation to hexene; while other side reactions are suppressed.
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    Synthesis of nanocrystalline cobalt ferrite by the sonochemical method in highly basic aqueous solution
    (2017-01-01)
    Pasupong, Patchara
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    ; ;
    This study reported the preparation of nanocrystalline CoFe2O4 in single step by the sonochemical method in highly basic aqueous solution without requiring of high temperature calcination process. To prepare nanocrystalline CoFe2O4, the mixed solution of the required molar ratio of cobalt nitrate hexahydrate (Co(NO<inf>3</inf>).6H2O) and ferric nitrate nonahydrate (Fe(NO<inf>3</inf>).9H2O) was precipitated in high concentration of sodium hydroxide medium solution (NaOH) under high intensity ultrasonic irradiation (20 kHz, 150 W/cm2). The effect of NaOH concentration (5, 10, 15 and 20 M) on phase formation, microstructure and magnetic property of CoFe2O4 was investigated. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) results showed that the as-prepared powders were single phase CoFe2O4 with cubic spinel structure. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) study showed that nanocrystalline CoFe2O4 had monosized distorted spherical morphology and an agglomeration of the nanocrystalline CoFe2O4 into nanoparticles was observed when increasing the NaOH concentration. The nanocrystalline CoFe2O4 exhibited superparamagnetic property and the saturation magnetization (Ms) obtained from vibrating sample magnetometry (VSM) was found to correlate with the crystallite size and varied from 39-45 emu/g.
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    Investigation of the influences of reaction temperature and time on the chemical reduction of graphene oxide by conventional method using Vitamin C as a reducing agent
    (2017-01-01) ; ;
    Kongtaweelert, Samart
    The aim of this work is to investigate the synthesis of reduced graphene oxide (rGO) aqueous suspension by a conventional heating method using vitamin C as a reducing agent. The influences of reaction temperatures (70, 90 and 100 °C) and heating times (30, 45 and 60 min) on the chemical reduction of graphene oxide (GO) were studied. Then, the obtained rGO samples were characterized by FT-IR, Raman, UV-Vis, XRD and TEM techniques. The FT-IR and Raman results showed that the reduction degree of GO to rGO was increased with the rising of the reaction temperature and time. Moreover, the UV-Vis spectra demonstrated that the absorption band at around 230 nm (π-π*) of pristine GO had shift to the longer wavelength upon the chemical reduction, indicating that GO is reduced to rGO. The optimal condition of the chemical reduction of GO to achievable rGO was the temperature of 90 °C with the 45 min of heating time. This condition yielded the rGO black aqueous suspension with the high quality and stability. Thus, this method of synthesis has an advantage of the rGO dispersion which led to many potential applications.
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    Hydrogen-Free Production of Green Diesel from Deoxygenation of Methyl Palmitate via Cross-Metathesis with Bio-Ethylene Using Supported WO3 Catalyst
    (2025-06-02)
    Solehudin, Mochamad
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    Wengwirat, Kanokwan
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    Promchana, Pratya
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    Poo-arporn, Yingyot
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    Limphirat, Wanwisa
    Traditional green diesel production from used cooking oils faces challenges in H<inf>2</inf> supply and carbon loss as CO<inf>2</inf>. This study presents a novel hydrogen-free deoxygenation process via cross-metathesis between fatty acids/FAMEs and bio-ethylene under atmospheric pressure as an alternative sustainable solution. The carboxyl end group was removed as CO and blue hydrogen, bearing the hydrocarbons as green diesel, sustainable aviation fuel (SAF), and bio-naphtha. Bifunctional WO<inf>3</inf>/SiO<inf>2</inf> was prepared and characterized by XRD, XANES, EXAFS, DR-UV, and Raman. Lewis site (W = O) promotes the formation of ketene intermediate that undergoes cross-metathesis with ethylene over tungsten carbene (WCH<inf>2</inf>) sites, yielding a C16-ene majority with trace amounts of C17-ene. Smaller hydrocarbons (<C15) are obtained as minor components from decarbonylation, hydrogen transfer, and cracking. The increased contact time (27–106 g h/mol) at 460 °C results in increased conversion (30%–87 %), green diesel (12%–57%), SAF (3.5%–12.7%), and bio-naphtha (1.3%–5.3%). Optimal green diesel production of 2.92 h⁻¹ with 73% selectivity can be achieved at 480 °C. SAF and bio-naphtha yields can be tuned by varying temperature from 460 to 500 °C. This provides a sustainable pathway for renewable liquid fuels without an external hydrogen supply.
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    Selective acetylene removal from ethylene-rich feed by cross-metathesis over supported WO3 catalysts
    (2023-01-25)
    Promchana, Pratya
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    Limphirat, Wanwisa
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    Poo-arporn, Yingyot
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    Acetylene in ethylene-rich feed can be removed via acetylene/ethylene cross-metathesis over WO<inf>3</inf>-supported catalysts at 450 °C, yielding 1,3-butadiene with cyclohexene as a minor product. The catalyst must be treated with ethylene at 600 °C to generate a genuinely active site of tungsten (IV) alkylidene species (W=CH<inf>2</inf>). The H<inf>2</inf> treatment decreases surface W[dbnd]O concentration, and hence the activity. Raman spectroscopy shows that active single-site WO<inf>3</inf> species, including mono oxo-WO<inf>3</inf> ((O=)W(O-Si)<inf>3</inf> and (O=)W(O-Si)<inf>4</inf>) and dioxo-WO<inf>3</inf> species (O=)<inf>2</inf>W(O-Si)<inf>2</inf>) were generated in 2%WO<inf>3</inf>/SiO<inf>2</inf>, while the WO<inf>3</inf> cluster and bulk WO<inf>3</inf> exist in 3–5%WO<inf>3</inf>/SiO<inf>2</inf> and 7%WO<inf>3</inf>/SiO<inf>2</inf>, respectively. The 5%WO<inf>3</inf>/NaX and 5%WO<inf>3</inf>/NaY provide lower activity due to coke formation over the acid sites. With high surface area and confined surface silanol of 5%WO<inf>3</inf>/MCM-41% and 5%WO<inf>3</inf>/SBA-15, in situ TR-EXAFS evidences the formation of only O[dbnd]W(O-Si)<inf>3</inf>. This species provides an isolated W=CH<inf>2</inf> site with relatively higher activity and is less prone to coke formation than the WO<inf>3</inf> cluster in 5%WO<inf>3</inf>/SiO<inf>2</inf>.