Resonant Photoemission Observations and DFT Study of s–d Hybridization in Catalytically Active Gold Clusters on Ceria Nanorods

Zhou, Yunyun; Lawrence, Neil J.; Wang, Lu; Kong, Lingmei; Wu, Tai‐Sing; Liu, Jing; Gao, Yi; Brewer, Joseph R.; Lawrence, Vivianna K.; Sabirianov, Renat; Soo, Y. L.; Zeng, Xiao Cheng; Dowben, Peter A.; Mei, Wai Ning; Cheung, Chin Li

doi:10.1002/ange.201301383

Cited by 4 publications

(4 citation statements)

References 27 publications

(20 reference statements)

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“…Its value is only about half that for CO oxidation on the Au 24 /TiO 2 system (∼0.61 eV). 8 The insets in Figure 7a show the computed initial state (IS), transition state (TS), and final state (FS). In a previous study we had addressed a number of reactions on such gold clusters (but not CO oxidation) and consistently found peripheral sites to be those with the highest adsorption energy; this is the case here as well.…”

Section: ■ Resultsmentioning

confidence: 99%

“…For the past two decades, the original findings, regarding Au nanoparticles on a titania (TiO 2 ) support, have been expanded to other oxides, 3−7 in particular, reduceable oxides such as ceria. 8,9 Gold on irreducible, inert substrates continued to prove itself as inert and as catalytically inactive as its bulk form. In the course of the recent broad focus on two-dimensional (2D) materials for catalysis, first indications have emerged that a single layer of MoS 2 offers a platform for stabilizing nanoscale gold particles and facilitates the requisite electronic states for CO adsorption at room temperature, 10 which is not the case for Au nanoparticles on graphene.…”

Section: ■ Introductionmentioning

confidence: 99%

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A Single Layer of MoS₂ Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate

et al. 2019

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We demonstrate the facile deposition of catalytically active stable Au nanoparticles on single-layer MoS 2 , on an inert oxide substrate (SiO 2 ). Unlike a gold surface, adsorption of CO on these gold particles proceeds even at room temperature. Subsequent exposure to oxygen leads to CO 2 formation and desorption along a reaction pathway described, in detail, by density functional theory. The barrier to CO oxidation, along this pathway, is less than 300 meV, corroborating the facile nature of the CO oxidation reactions in this system. X-ray photoelectron spectroscopy directly reveals that the carbon monoxide, adsorbed on Au nanoparticles on single-layer MoS 2 , can be repeatedly titrated off the substrate by exposure to oxygen. Comparison of computational results assuming a defect-laden and pristine MoS 2 substrate suggest that the pristine single-layer material may be superior in supporting this reaction.

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Section: ■ Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

A Single Layer of MoS₂ Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate

et al. 2019

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“…The gold d-band position and its hybridization 21,50 have been determined to be a crucial descriptor of its catalytic activity. Hence, the ability of single-layer MoS 2 to interact sufficiently strongly with gold to affect a major descriptor of its catalytic potential suggests that MoS 2 may have a use wherever a corresponding shift of the Au 5d state is desired.…”

Section: The Journal Of Physical Chemistry Cmentioning

confidence: 99%

Gold Dispersion and Activation on the Basal Plane of Single-Layer MoS₂

Merida

Echeverría

et al. 2017

J. Phys. Chem. C

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Gold islands are typically associated with high binding affinity to adsorbates and catalytic activity. Here we present the growth of dispersed nanoscale gold islands on single layer MoS 2 , prepared on an inert SiO 2 /Si support by chemical vapor deposition (CVD). This study offers a combination of growth process development, optical characterization, photoelectron spectroscopy at sub-micron spatial resolution, and advanced density functional theory modeling for detailed insight into the electronic interaction between gold and single-layer MoS 2. In particular, we find the gold density of states in Au/MoS 2 /SiO 2 /Si to be far less well-defined than Au islands on other 2-dimensional materials such as graphene, for which we also provide data. We attribute this effect to the presence of heterogeneous Au adatom/MoS 2-support interactions within the nanometer-scale gold cluster. Theory predicts that CO will exhibit adsorption energies in excess of 1 eV at the Au cluster edges, where the local density of states is dominated by Au 5d z 2 symmetry.

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“…CO oxidation by gold nanoclusters, similar to results obtained for reducible oxides, such as titania and ceria. [6][7][8][9][10][11][12] Concomitant computational efforts have predicted a number of feasible, lowbarrier reaction pathways on thus supported gold nanoparticles, 3,13 in contrast to the largely catalytically inactive bulk gold, Au on pristine silica or on other 2D materials like graphene. [14][15][16] Here, we address the carbonylation of methanol as the most fundamental C-C coupling step that can lead to higher alcohol formation from a lower alcohol and a component of syngas, as it may be obtained from biomass gasification.…”

Section: Introductionmentioning

confidence: 99%

Towards Higher Alcohol Formation using a single-layer MoS2 activated Au on Silica: Methanol Carbonylation to Acetaldehyde

Almeida¹,

Chagoya²,

Felix³

et al. 2019

Preprint

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We demonstrate that a fused silica substrate can be rendered active for acetaldehyde (CH3CHO) synthesis from a gas mixture of carbon monoxide (CO) and methanol (CH3OH) under mild process conditions (308 kPa and 393 K) by deposition first of a homogenous single-layer MoS2 film and subsequently of a sub-mnonolayer (1 Angstrom) loading of gold. In operando monitoring of the catalyst performance in a flow reactor reveals uncompromised activity even after 2 hours on stream. The carbonylation of methanol to a C2 species represents a crucial step toward the formation of higher alcohols from syngas derived from methane or biomass. Characterization of the film by imaging and spectroscopy reveals that the single-layer MoS2 film disperses the gold loading into nanoscale islands; density functional theory (DFT) calculations identify low-coordinated edge sites on these islands as active centers for the carbon-carbon coupling at barriers significantly below 1 eV.

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Resonant Photoemission Observations and DFT Study of s–d Hybridization in Catalytically Active Gold Clusters on Ceria Nanorods

Cited by 4 publications

References 27 publications

A Single Layer of MoS₂ Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate

A Single Layer of MoS₂ Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate

Gold Dispersion and Activation on the Basal Plane of Single-Layer MoS₂

Towards Higher Alcohol Formation using a single-layer MoS2 activated Au on Silica: Methanol Carbonylation to Acetaldehyde

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Resonant Photoemission Observations and DFT Study of s–d Hybridization in Catalytically Active Gold Clusters on Ceria Nanorods

Cited by 4 publications

References 27 publications

A Single Layer of MoS2 Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate

A Single Layer of MoS2 Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate

Gold Dispersion and Activation on the Basal Plane of Single-Layer MoS2

Towards Higher Alcohol Formation using a single-layer MoS2 activated Au on Silica: Methanol Carbonylation to Acetaldehyde

Contact Info

Product

Resources

About

A Single Layer of MoS₂ Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate

A Single Layer of MoS₂ Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate

Gold Dispersion and Activation on the Basal Plane of Single-Layer MoS₂