Engineering Heterogeneous Catalysis with Strong Metal–Support Interactions: Characterization, Theory and Manipulation

Pu, Tiancheng; Zhang, Wenhao; Zhu, Minghui

doi:10.1002/anie.202212278

Cited by 148 publications

(107 citation statements)

References 132 publications

Supporting

Mentioning

103

Contrasting

Unclassified

Order By: Relevance

“…Various strategies have been developed to create defect sites, , metal–oxide interfaces, , grain boundaries, and hierarchical pore structures. , Among them, metal–oxide interfaces are of particular importance since they can induce electronic metal–support interaction (EMSI) by causing charge redistribution at the interface. This can modulate the unoccupied d states of noble metal sites and significantly improve reactant adsorption and activation, thereby enhancing catalytic performance. − …”

Section: Introductionmentioning

confidence: 99%

Tunable Interfacial Electronic Pd–Si Interaction Boosts Catalysis via Accelerating O₂ and H₂O Activation

Dong

et al. 2023

JACS Au

View full text Add to dashboard Cite

Engineering the interfacial structure between noble metals and oxides, particularly on the surface of non-reducible oxides, is a challenging yet promising approach to enhancing the performance of heterogeneous catalysts. The interface site can alter the electronic and d-band structure of the metal sites, facilitating the transition of energy levels between the reacting molecules and promoting the reaction to proceed in a favorable direction. Herein, we created an active Pd–Si interface with tunable electronic metal–support interaction (EMSI) by growing a thin permeable silica layer on a non-reducible oxide ZSM-5 surface (termed Pd@SiO2/ZSM-5). Our experimental results, combined with density functional theory calculations, revealed that the Pd–Si active interface enhanced the charge transfer from deposited Si to Pd, generating an electron-enriched Pd surface, which significantly lowered the activation barriers for O2 and H2O. The resulting reactive oxygen species, including O2 –, O2 2–, and −OH, synergistically facilitated formaldehyde oxidation. Additionally, moderate electronic metal–support interaction can promote the catalytic cycle of Pd0 ⇆ Pd2+, which is favorable for the adsorption and activation of reactants. This study provides a promising strategy for the design of high-performance noble metal catalysts for practical applications.

show abstract

Section: Introductionmentioning

confidence: 99%

Tunable Interfacial Electronic Pd–Si Interaction Boosts Catalysis via Accelerating O₂ and H₂O Activation

Dong

et al. 2023

JACS Au

View full text Add to dashboard Cite

show abstract

“…A nonnegligible portion of the signals are contributed by the bulk counterparts of the supported nanoparticles. Low-energy ion scattering (LEIS), particularly high sensitivity-low energy ion scattering (HS-LEIS), enables a more precise analysis of the elemental composition of the outmost atomic layers, yet assessing the corresponding electronic characteristics remains challenging.…”

Section: Characterization and Identification Of Smsimentioning

confidence: 99%

“…Nishihata et al discovered that Pd in LaFe 0.57 Co 0.38 Pd 0.05 O 3 reversibly moves into (as lattice cations) and out of (as supported particles) the perovskite substrates at oxidative and reductive atmospheres, respectively . The driving force behind this is minimization of surface energies involving enthalpy changes, while recent studies have indicated that the entropy aspect also plays a significant role. The emergence of high-entropy materials directs a fundamentally distinct route to manipulating the dispersion of the supported active species.…”

Section: New Architectures For Smsimentioning

confidence: 99%

Nonclassical Strong Metal–Support Interactions for Enhanced Catalysis

Sun

Yang

Dai

2023

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

Figure 1. (a) Schematic summarizing the characterization techniques for identifying the occurrence of SMSI. (b) In situ DRIFT spectra monitoring evolution of the adsorbed CO species on the Ru nanoparticles with partial TiO x encapsulation under H 2 flow at 160 °C. The inset shows the emergence of CH 4 species with the characteristic frequency at 3015 cm −1 upon introducing H 2 . Reproduced with permission from ref 26. Copyright 2020 Springer Nature. (c) In situ XRD result of the Pt-TiO 2 catalyst treated with H 2 at 200 and 600 °C, respectively, as well as the corresponding Pawley fitting result for the Pt unit cell after H 2 reduction at different temperatures. The diffraction shift toward higher angles and lattice contraction of the Pt unit cell indicates the alloying pathway along with the suboxide overlayer formation. Reproduced with permission from ref 27. Copyright 2020 Springer Nature. Annular bright field (ABF) image of the Pd(111) surface interfaced with the TiO x overlayer composed of a bilayer structure with the lattice spacing being ∼2.9 and ∼3.0 Å, respectively. The Pd/TiO x interface is highlighted using the dashed yellow line. Adapted with permission from ref 31.

show abstract

“…For example, supported metal nanoparticles can be dispersed into isolated metal atoms through an electronic or covalent metal−support interaction and then possess high stability and activity. 1,2 Migration of support species onto the surface of metal nanoparticles and formation of ultrathin encapsulation overlayers, known as the strong metal−support interaction, 3,4 can strongly influence catalytic reactions over metal/oxide catalysts. 5,6 For supported oxide catalysts, a strong oxide− support interaction effectively modulates their interfacial atomic and electronic structures and forms interfacial active centers.…”

mentioning

confidence: 99%

“…For supported metal or oxide nanocatalysts, the interfacial interaction between catalyst and support plays an important role in their structures and catalytic performance. For example, supported metal nanoparticles can be dispersed into isolated metal atoms through an electronic or covalent metal–support interaction and then possess high stability and activity. , Migration of support species onto the surface of metal nanoparticles and formation of ultrathin encapsulation overlayers, known as the strong metal–support interaction, , can strongly influence catalytic reactions over metal/oxide catalysts. , For supported oxide catalysts, a strong oxide–support interaction effectively modulates their interfacial atomic and electronic structures and forms interfacial active centers. , Oxide nanolayers grown on metal surfaces are usually metastable but highly active, which has been discussed in terms of the interface confinement effect in the oxide/metal inverse catalysts …”

mentioning

confidence: 99%

Oxide-Metal Interaction Probed by Scanning Tunneling Microscope Manipulation of Cr₂O₇ Clusters on Au(111)

Lin

Luo

et al. 2023

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

Interfacial interaction plays a crucial rule in catalysis over supported catalysts, and the catalyst−support interaction needs to be explored at microscopic scale. Here, we use the scanning tunneling microscope (STM) tip to manipulate Cr 2 O 7 dinuclear clusters on Au(111) and find that the Cr 2 O 7 −Au interaction can be weakened by an electric field in the STM junction, facilitating rotation and translation of the individual clusters at the imaging temperature (78 K). Surface alloying with Cu makes the manipulation of the Cr 2 O 7 clusters hard due to the enhanced Cr 2 O 7 −substrate interaction. Density functional theory calculations reveal that barrier for translation of a Cr 2 O 7 cluster on the surface can be increased by surface alloying, influencing the tip manipulation. Our study demonstrates that the oxide−metal interfacial interaction can be probed by STM tip manipulation of supported oxide clusters, which provides a new method to investigate the interfacial interaction.

show abstract

Engineering Heterogeneous Catalysis with Strong Metal–Support Interactions: Characterization, Theory and Manipulation

Cited by 148 publications

References 132 publications

Tunable Interfacial Electronic Pd–Si Interaction Boosts Catalysis via Accelerating O₂ and H₂O Activation

Tunable Interfacial Electronic Pd–Si Interaction Boosts Catalysis via Accelerating O₂ and H₂O Activation

Nonclassical Strong Metal–Support Interactions for Enhanced Catalysis

Oxide-Metal Interaction Probed by Scanning Tunneling Microscope Manipulation of Cr₂O₇ Clusters on Au(111)

Contact Info

Product

Resources

About

Engineering Heterogeneous Catalysis with Strong Metal–Support Interactions: Characterization, Theory and Manipulation

Cited by 148 publications

References 132 publications

Tunable Interfacial Electronic Pd–Si Interaction Boosts Catalysis via Accelerating O2 and H2O Activation

Tunable Interfacial Electronic Pd–Si Interaction Boosts Catalysis via Accelerating O2 and H2O Activation

Nonclassical Strong Metal–Support Interactions for Enhanced Catalysis

Oxide-Metal Interaction Probed by Scanning Tunneling Microscope Manipulation of Cr2O7 Clusters on Au(111)

Contact Info

Product

Resources

About

Tunable Interfacial Electronic Pd–Si Interaction Boosts Catalysis via Accelerating O₂ and H₂O Activation

Tunable Interfacial Electronic Pd–Si Interaction Boosts Catalysis via Accelerating O₂ and H₂O Activation

Oxide-Metal Interaction Probed by Scanning Tunneling Microscope Manipulation of Cr₂O₇ Clusters on Au(111)