Mechanisms governing selective hydrogenation of acetylene over γ-Mo<sub>2</sub>N surfaces

Jaf, Zainab N.; Altarawneh, Mohammednoor; Miran, Hussein A.; Jiang, Zhong Tao; Dlugogorski, Bogdan Z.

doi:10.1039/c6cy02110g

Cited by 25 publications

(15 citation statements)

References 46 publications

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“…Based on DFT calculations, Dlugogorski and co-workers also observed stable O atoms adsorbed on the N-vacant Mo sites during NO reduction and H atoms adsorbed strongly on the surface N sites during H 2 dissociation on the Mo 2 N(111) surface. 43 , 60 Experimental studies performed by He et al revealed the transformation of γ-Mo 2 N into a Mo 2 O x N y phase in the presence of NO, and this phase can be reduced back to γ-Mo 2 N by H 2 . 61 Thus, in Table 2 , the removal process of adsorbed oxygen atoms on the Mo 2 N surface by H 2 to form H 2 O is reported.…”

Section: Resultsmentioning

confidence: 99%

Unraveling Unique Surface Chemistry of Transition Metal Nitrides in Controlling Selective C–O Bond Scission Pathways of Glycerol

Lin

Ammal

Denny

et al. 2022

JACS Au

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Controlled C–O bond scission is an important step for upgrading glycerol, a major byproduct from the continuously increasing biodiesel production. Transition metal nitride catalysts have been identified as promising hydrodeoxygenation (HDO) catalysts, but fundamental understanding regarding the active sites of the catalysts and reaction mechanism remains unclear. This work demonstrates a fundamental surface science study of Mo 2 N and Cu/Mo 2 N for the selective HDO reaction of glycerol, using a combination of model surface experiments and first-principles calculations. Temperature-programmed desorption (TPD) experiments showed that clean Mo 2 N cleaved two or three C–O bonds of glycerol to produce allyl alcohol, propanal, and propylene. The addition of Cu to Mo 2 N changed the reaction pathway to one C–O bond scission to produce acetol. High-resolution electron energy loss spectroscopy (HREELS) results identified the surface intermediates, showing a facile C–H bond activation on Mo 2 N. Density functional theory (DFT) calculations revealed that the surface N on Mo 2 N interacted with the H atoms in glycerol and blocked some Mo sites to enable selective C–O bond scission. This work shows that Mo 2 N and Cu/Mo 2 N are active and selective for the controlled C–O bond scission of glycerol and in turn provides insights into the rational catalyst design for selective oxygen removal of relevant biomass-derived oxygenates.

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Section: Resultsmentioning

confidence: 99%

Unraveling Unique Surface Chemistry of Transition Metal Nitrides in Controlling Selective C–O Bond Scission Pathways of Glycerol

Lin

Ammal

Denny

et al. 2022

JACS Au

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“…Altarawneh et al [47], used computational methods to study mechanism of the selective hydrogenation C 2 H 2 over γ-Mo 2 N to C 2 H 4 rather than complete hydrogenation to the corresponding alkane.…”

Section: Transition Metal Nitrides As Catalystmentioning

confidence: 99%

Recent Progress on Transition Metal Nitrides Nanoparticles as Heterogeneous Catalysts

Dongil

2019

Nanomaterials

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This short review aims at providing an overview of the most recent literature regarding transition metal nitrides (TMN) applied in heterogeneous catalysis. These materials have received renewed attention in the last decade due to its potential to substitute noble metals mainly in biomass and energy transformations, the decomposition of ammonia being one of the most studied reactions. The reactions considered in this review are limited to thermal catalysis. However the potential of these materials spreads to other key applications as photo- and electrocatalysis in hydrogen and oxygen evolution reactions. Mono, binary and exceptionally ternary metal nitrides have been synthetized and evaluated as catalysts and, in some cases, promoters are added to the structure in an attempt to improve their catalytic performance. The objective of the latest research is finding new synthesis methods that allow to obtain smaller metal nanoparticles and increase the surface area to improve their activity, selectivity and stability under reaction conditions. After a brief introduction and description of the most employed synthetic methods, the review has been divided in the application of transition metal nitrides in the following reactions: hydrotreatment, oxidation and ammonia synthesis and decomposition.

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“…35 The γ-Mo 2 N that has special crystal and electronic structure was usually used as a support in various catalytic processes but not including the WGS reaction. 12,36−38 Although its surface is partially oxidized during reactions, the γ-Mo 2 N was found to maintain a sustained and stable surface structure, 39,40 which makes it a promising candidate as the substrate for the heterostructure.…”

Section: ■ Introductionmentioning

confidence: 99%

Intrinsically Active Surface in a Pt/γ-Mo₂N Catalyst for the Water–Gas Shift Reaction: Molybdenum Nitride or Molybdenum Oxide?

Zhang

et al. 2020

J. Am. Chem. Soc.

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Apart from active metals, supports also contribute significantly to the catalytic performance of supported metal catalysts. On account of the formed strain and defects, the heterostructured surface of the support may play a crucial role to activate the reactant molecules, while it is usually neglected. In this work, the Pt/γ-Mo2N catalyst was prepared via a facile solution method. This Pt/γ-Mo2N catalyst showed excellent activity and stability for catalyzing the water–gas shift (WGS) reaction. The reaction rates at 240 °C were 16.5 molCO molPt –1s–1 in product-free gas and 5.36 molCO molPt –1 s–1 in full reformate gas, which were almost 20 times that of the catalysts reported. It is found that the molybdenum species in the surface of the Pt/γ-Mo2N catalyst is molybdenum oxide as MoO3. This surface MoO3 is very easily reduced even at room temperature, and it transformed into highly distorted MoO x (2 < x < 3) in the WGS reaction. The MoO x on the catalyst surface greatly enhanced the capability of generating active oxygen vacancies to dissociate H2O molecules, which induced unexpectedly superior catalytic performance. Therefore, the intrinsically active surface in the Pt/γ-Mo2N catalyst for the WGS reaction was molybdenum oxide as MoO x (2 < x < 3).

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Mechanisms governing selective hydrogenation of acetylene over γ-Mo₂N surfaces

Abstract: We demonstrate that the selective hydrogenation of acetylene depends on energy profile of the partial and full hydrogenation routes and the thermodynamic stability of adsorbed C2H2 in comparison to C2H4.

Cited by 25 publications

References 46 publications

Unraveling Unique Surface Chemistry of Transition Metal Nitrides in Controlling Selective C–O Bond Scission Pathways of Glycerol

Unraveling Unique Surface Chemistry of Transition Metal Nitrides in Controlling Selective C–O Bond Scission Pathways of Glycerol

Recent Progress on Transition Metal Nitrides Nanoparticles as Heterogeneous Catalysts

Intrinsically Active Surface in a Pt/γ-Mo₂N Catalyst for the Water–Gas Shift Reaction: Molybdenum Nitride or Molybdenum Oxide?

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Mechanisms governing selective hydrogenation of acetylene over γ-Mo2N surfaces

Abstract: We demonstrate that the selective hydrogenation of acetylene depends on energy profile of the partial and full hydrogenation routes and the thermodynamic stability of adsorbed C2H2 in comparison to C2H4.

Cited by 25 publications

References 46 publications

Unraveling Unique Surface Chemistry of Transition Metal Nitrides in Controlling Selective C–O Bond Scission Pathways of Glycerol

Unraveling Unique Surface Chemistry of Transition Metal Nitrides in Controlling Selective C–O Bond Scission Pathways of Glycerol

Recent Progress on Transition Metal Nitrides Nanoparticles as Heterogeneous Catalysts

Intrinsically Active Surface in a Pt/γ-Mo2N Catalyst for the Water–Gas Shift Reaction: Molybdenum Nitride or Molybdenum Oxide?

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Product

Resources

About

Mechanisms governing selective hydrogenation of acetylene over γ-Mo₂N surfaces

Intrinsically Active Surface in a Pt/γ-Mo₂N Catalyst for the Water–Gas Shift Reaction: Molybdenum Nitride or Molybdenum Oxide?