Phase transformation of ZrO2 by Si incorporation and catalytic activity for isopropyl alcohol dehydration and dehydrogenation

Min, Hyung; Kim, Young Woo; Kim, Chansong; Ibrahim, I. I.; Han, Jeong Woo; Suh, Young Woong; Jung, Kwang‐Deog; Park, Min Bum; Shin, Chae Ho

doi:10.1016/j.cej.2021.131766

Cited by 21 publications

(15 citation statements)

References 50 publications

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“…As the Si mole fraction increases, the calculated crystallite sizes decrease from 23.7 nm (pure ZrO 2 ) to 7.5 nm (19 mol% Si) ( Table 1 ). These findings are in good agreement with recently published results from Min et al , 24 who reported 20.7 nm (pure ZrO 2 ) and 8.9 nm (20 mol% Si), obtained from the same calcination temperature of 973 K. At a Si mole fraction of 27 mol%, no XRD reflections are found, likely due to even smaller crystallite sizes, as an amorphous, growth-constraining SiO 2 network forms around the ZrO 2 crystallites.…”

Section: Resultssupporting

confidence: 93%

“…20,21 Apart from doping with metal ions, the stabilization of t-ZrO 2 by introduction of Si has been thoroughly investigated. 9,[22][23][24] Commonly, Si is incorporated into ZrO 2 through the dissolution of Si from glass vessels during basic treatment of hydrous ZrO 2 precipitates, oen referred to as "digestion". 25 From these studies, a correlation between the Si content and the specic surface area of the zirconia has been reported, 22,23 though the reproducible dissolution of Si from glass may be problematic.…”

Section: Introductionmentioning

confidence: 99%

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Thermally stable mesoporous tetragonal zirconia through surfactant-controlled synthesis and Si-stabilization

et al. 2022

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Section: Resultssupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Thermally stable mesoporous tetragonal zirconia through surfactant-controlled synthesis and Si-stabilization

et al. 2022

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“…11 Currently, DIPE can be produced through the dehydration of alcohol using a heterogeneous catalyst. In this context, a wide type of catalysts such as iron and alumina, 7 Ni−Cu−Crand Ni−Cu-loaded H-β-zeolite, 9 carbon acid, 12 Pt-promoted CuO/TiO 2 -ZrO 2 , 13 Ru-and Pd-supported N-doped carbon nanotubes, 14 crystalline heteropolyacids, 15 Al 2 O 3 −TiO 2 , 16 SiO 2 −ZrO 2 , 17 Ni-W sulfides, 18 they are economically favorable, abundantly available, and have adequate catalytic active sites, which have catalyzed various reactions. Zeolites are readily preferred over other acid catalysts because of their wide pore size distribution, thermal stability, and selectivity on the desired product.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Turek et al 15 reported that γ-Al 2 O 3 and ZrO 2 catalysts produced 8.6 and 0% toward diisopropyl ether selectivity, respectively, whereas heteropoly acids with various molar ratios produced 24−33.2%, under the temperature reaction of 206.85 °C. Min et al 17 81 reported that high DIPE selectivity up to 100% was achieved using the TiO 2 catalyst at a temperature of 175 °C, but the isopropyl alcohol conversion was only 6%. 81 According to Figure 6, the catalytic activity of zeolite-Ni(H 2 PO 4 ) 2 on isopropyl alcohol dehydration was relatively comparable with other catalysts.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Currently, DIPE can be produced through the dehydration of alcohol using a heterogeneous catalyst. In this context, a wide type of catalysts such as iron and alumina, 7 Ni–Cu–Cr- and Ni–Cu-loaded H-β-zeolite, 9 carbon acid, 12 Pt-promoted CuO/TiO 2 -ZrO 2 , 13 Ru- and Pd-supported N-doped carbon nanotubes, 14 crystalline heteropolyacids, 15 Al 2 O 3 –TiO 2 , 16 SiO 2 –ZrO 2 , 17 Ni-W sulfides, 18 and (WO 3 ) n and (MoO 3 ) n 19 have been extensively employed, which show various catalytic activities. Presently, natural alumina silicate-based catalysts such as zeolites and clays are promisingly auspicious because they are economically favorable, abundantly available, and have adequate catalytic active sites, which have catalyzed various reactions.…”

Section: Introductionmentioning

confidence: 99%

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Enhanced Isopropyl Alcohol Conversion over Acidic Nickel Phosphate-Supported Zeolite Catalysts

et al. 2022

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In this preliminary research, the catalytic activity of isopropyl alcohol conversion to diisopropyl ether through dehydration reaction catalyzed by zeolite-Ni and zeolite-Ni(H2PO4)2 was comparatively described. The natural zeolite was treated with 1% HF and 6 N HCl prior to modifications using the impregnation method. Isopropyl alcohol conversion was examined at a mild temperature of 150 °C for 3.5 h on the reflux system with various catalyst loadings. X-ray diffraction and Fourier transform infrared analysis confirmed the successful impregnation of nickel and nickel phosphate into the zeolite. Scanning electron microscopy analysis revealed a cubic-like structure on zeolite-Ni(H2PO4)2, whereas homogenously distributed nickel species were observed on the zeolite-Ni catalyst. Energy-dispersive X-ray spectroscopy analysis reinforced the accomplishment of zeolite modifications. The N2 physisorption isotherms showed a decline in the surface area and total pore volume of the zeolite because of the blocking of pores. The zeolite-Ni(H2PO4)2 catalyst had higher acidity than unmodified zeolite and zeolite-Ni catalysts, which inherently suggested that the presence of phosphate groups results in higher catalytic activity toward isopropyl alcohol. The highest catalytic activity was attained by 8 mEq/g metal loading zeolite-Ni(H2PO4)2 with isopropyl alcohol conversion of 81.51%, diisopropyl ether yield, and selectivity of 40.77 and 33.16%. The reusability study suggested that the zeolite-Ni(H2PO4)2 catalyst was still active and had sufficient catalytic activity stability toward isopropyl alcohol after the third cycle was reused. This nickel phosphate-based modified zeolite was adequately potential for diisopropyl ether production through isopropyl alcohol dehydration.

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Zirconia Incorporated Aluminum Phosphate Molecular Sieves as Efficient Microporous Nano Catalysts for the Selective Dehydration of Methanol into Dimethyl Ether

2023

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Annually, a growing demand was noted for replacing petroleum fuels with second-generation eco-friendly fuels like dimethyl ether (DME). Methanol dehydration into DME process has been considered as one of the potential pathways for the manufacture of a clean fuel. However, stable, and active catalyst is exceedingly requisite for generation of DME particularly at reasonably low temperature. In the current study, zirconia incorporated AlPO4 tridymite microporous molecular sieve catalysts were fabricated by a hydrothermal method in the presence of triethylamine (TEA) as a structure directing agent. The catalysts were characterized by X-ray diffraction (XRD), energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and N2-sorption assessments. Catalysts’ acidity was estimated by decomposition of isopropanol, pyridine and dimethyl pyridine chemisorption, and pyridine-TPD. Results revealed that catalysts surfaces composed acid sites of Brønsted nature and of weak and medium strengths. Activity results showed that 1 wt% H2SO4 modified zirconia incorporated AlPO4-TRI catalyst calcined at 400 °C presented the best activity with a conversion of 89% and a 100% selectivity into DME at 250 °C. The significant catalytic activity is well-connected to the variation in BET-surface area, acidity, and activation energy of methanol dehydration. The catalysts offered long-term stability for 120 h and could be regenerated with almost the same activity and selectivity. Graphical Abstract

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Phase transformation of ZrO2 by Si incorporation and catalytic activity for isopropyl alcohol dehydration and dehydrogenation

Cited by 21 publications

References 50 publications

Thermally stable mesoporous tetragonal zirconia through surfactant-controlled synthesis and Si-stabilization

Thermally stable mesoporous tetragonal zirconia through surfactant-controlled synthesis and Si-stabilization

Enhanced Isopropyl Alcohol Conversion over Acidic Nickel Phosphate-Supported Zeolite Catalysts

Zirconia Incorporated Aluminum Phosphate Molecular Sieves as Efficient Microporous Nano Catalysts for the Selective Dehydration of Methanol into Dimethyl Ether

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