Mechanism of strong metal-support interaction in Ni/TiO2

Chung, Yip Wah; Xiong, Guoxing; Kao, Chia Chieh

doi:10.1016/0021-9517(84)90126-x

Cited by 126 publications

(17 citation statements)

References 16 publications

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“…The conditions for copper chromite activation were taken from literature protocols [41], and the conditions for Ni/TiO 2 were established experimentally, since lowering the reduction temperature to 300 °C gave an approximately three-fold more active catalyst, but did not significantly affect selectivity. The decrease in activity is entirely consistent with the well-known strong metal support interaction (SMSI) effect [42], whereby TiO 2 diffuses onto the metal surfaces (including nickel specifically [43]) as a result of reduction at 500 °C or above, in this case reducing access to the nickel. During furfural hydrogenation, the hydrogen flow rate was increased to 70 mL min −1 and distilled furfural was supplied at a rate of 0.0138 mL min −1 using a syringe pump (World Precision Instruments, molar H 2 :furfural ratio 19:1).…”

Section: Vapor-phase Furfural Hydrogenationsupporting

confidence: 74%

Nickel-Catalysed Vapour-Phase Hydrogenation of Furfural, Insights into Reactivity and Deactivation

MacIntosh

Beaumont

2020

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Furfural is a key bioderived platform molecule, and its hydrogenation affords access to a number of important chemical intermediates that can act as "drop-in" replacements to those derived from crude oil or novel alternatives with desirable properties. Here, the vapour phase hydrogenation of furfural to furfuryl alcohol at 180 °C over standard impregnated nickel catalysts is reported and contrasted with the same reaction over copper chromite. Whilst the selectivity to furfuryl alcohol of the unmodified nickel catalysts is much lower than for copper chromite as expected, the activity of the nickel catalysts in the vapour phase is significantly higher, and the deactivation profile remarkably similar. In the case of the supported nickel catalysts, possible contribution to the deactivation by acidic sites on the catalyst support is discounted based on the similarity of deactivation kinetics on Ni/SiO 2 with those seen for less acidic Ni/TiO 2 and Ni/CeO 2. Powder X-ray diffraction is used to exclude sintering as a primary deactivation pathway. Significant coking of the catalyst (~ 30 wt% over 16 h) is observed using temperature programmed oxidation. This, in combination with the solvent extraction analysis and infrared spectroscopy of the coked catalysts points to deactivation by polymeric condensation products of (reactant or) products and hydrocarbon like coke. These findings pave the way for targeted modification of nickel catalysts to use for this important biofeedstock-to-chemicals transformation.

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Section: Vapor-phase Furfural Hydrogenationsupporting

confidence: 74%

Nickel-Catalysed Vapour-Phase Hydrogenation of Furfural, Insights into Reactivity and Deactivation

MacIntosh

Beaumont

2020

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“…Strong similarities were found in the kinetic data for the close-packed (111) and for the more open (100) crystal plane of Ni, indicating that the methanation reaction is structure insensitive [10,11]. Subsequent studies for Ni/TiO 2 (100) catalysts indicate that the formation of bonds between the admetal and oxide support can enhance the methanation activity of Ni [12,13]. It is worthwhile to investigate if the same phenomenon occurs in Ni/CeO 2 (111) catalysts.…”

Section: Introductionmentioning

confidence: 84%

“…Since CO methanation is a secondary reaction competing with the WGS on Ni/CeO 2 (111) catalysts, we decided to study it in more detail using mixtures of CO/H 2 as reactants [10,11]. The CO methanation activity of Ni-based catalysts is well established [2,[10][11][12][13]. The top panel in Fig.…”

Section: C1smentioning

confidence: 99%

Water–Gas Shift and CO Methanation Reactions over Ni–CeO2(111) Catalysts

et al. 2011

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X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO2(111) surfaces. Upon adsorption on CeO2(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500–800 K) leads to partial reduction of the ceria substrate with the formation of Ni2+ species that exists as NiO and/or Ce1−xNixO2−y. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO2(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce+3 cations, CO dissociates on the surface at 300 K forming NiCx compounds that may be involved in the formation of CH4 at higher temperatures. At medium and large Ni coverages (>0.3 ML), the Ni/CeO2(111) surfaces are able to catalyze the production of methane from CO and H2, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (<0.3 ML), the Ni/CeO2(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water–gas shift reaction

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“…SMSI greatly affects chemisorption and catalytic properties in reactions involving species such as hydrogen and carbon monoxide (Chung et al, 1984;Raupp andDumesic, 1985b, 1986;Tanaka and White, 1983). For example, when titania is used as a support for platinum (as well as other metals such as palla-Correspondence concerning this paper should be addressed to S .…”

Section: Introductionmentioning

confidence: 99%

Oxygen transfer between metals and oxygen‐ion conducting supports

Metcalfe

Sundaresan

1988

AIChE Journal

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The charge-transfer reactions in the three-phase interfacial region, between a platinum catalyst, an yttria-stabilized zirconia (YSZ) support, and the gas phase, were studied electrochemically during carbon monoxide oxidation. From electrochemical and reaction-rate measurements, it appeared that oxygen was being removed from the support by carbon monoxide adsorbed on the platinum, while being suppfied to the support by atomic oxygen adsorbed on either the platinum or the YSZ.Highly disperse Pt /YSZ catalyst outperformed a Pt /A1,03 catalyst, the rate difference being explained in terms of interfacial reactions. Even in the presence of species such as water and sulfur dioxide, catalysts with YSZ supports outperformed those with alumina supports.

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Mechanism of strong metal-support interaction in Ni/TiO2

Cited by 126 publications

References 16 publications

Nickel-Catalysed Vapour-Phase Hydrogenation of Furfural, Insights into Reactivity and Deactivation

Nickel-Catalysed Vapour-Phase Hydrogenation of Furfural, Insights into Reactivity and Deactivation

Water–Gas Shift and CO Methanation Reactions over Ni–CeO2(111) Catalysts

Oxygen transfer between metals and oxygen‐ion conducting supports

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