The effect of hydrogen adsorption on the electronic structure of gold nanoparticles

Гатин, А. К.; Grishin, M. V.; Dokhlikova, N. V.; Kolchenko, N. N.; Шуб, Б. Р.

doi:10.1134/s0012501616090013

Cited by 8 publications

(6 citation statements)

References 9 publications

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“…In our work, the adsorption of atomic hydrogen is found to stabilize at 0.8 ML coverage with adsorption energy of −0.025 eV H −1 atom. This value is higher than the calculated adsorption energies on flat gold surfaces or perfect crystal NPs, [31][32][33][34] but is fully consistent with experimental works predicting the dissociative chemisorption of H 2 on gold catalyst [10,28,[35][36][37] for temperature in the range of 298-523 K [10] providing by the way, a rational explanation of the observed structural transformations. The predicted strong hydrogen adsorption governing the structural changes is also illustrated by the drastic changes in the Au 5d-band density of states of Au atoms from both the surface and the center in configuration D' compared to bare TOh_Au 201 NP.…”

Section: Resultssupporting

confidence: 89%

“…[5,6,7] For instance, in reactions of hydrogenation, it is widely accepted that surface atoms on small particles are much more active than those on large particles since the fraction of low coordinated sites, i.e., at edges and corners, which are the hydrogen activation sites, increases when size decreases. [8,9,10,11] This concept has been largely adopted for studying the reactivity of Au NPs, especially by theoreticians and surface science researchers. [12] The common practice is to consider Au nanoparticles as perfect model crystals with well-defined symmetry and static surface facets interacting with low coverage of gas molecules.…”

Section: Introductionmentioning

confidence: 99%

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Revealing Size Dependent Structural Transitions in Supported Gold Nanoparticles in Hydrogen at Atmospheric Pressure

Nassereddine

Wang

Loffreda

et al. 2021

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activity of Au NPs with size smaller than 5 nm has been often attributed to sizedependent physical features such as the fraction of surface atoms. [5][6][7] For instance, in reactions of hydrogenation, it is widely accepted that surface atoms on small particles are much more active than those on large particles since the fraction of low coordinated sites, that is, at edges and corners, which are the hydrogen activation sites, increases when size decreases. [8][9][10][11] This concept has been largely adopted for studying the reactivity of Au NPs, especially by theoreticians and surface science researchers. [12] The common practice is to consider Au nanoparticles as perfect model crystals with well-defined symmetry and static surface facets interacting with low coverage of gas molecules. However, the effect of adsorbates, which induces surface changes, is generally neglected in these studies. [13][14][15] This is a serious drawback that may prevent reliable description of the catalyst reactivity that mainly depends on the configuration of the surface. Aside from structural effects, quantum size effects are also frequently invoked to explain the exceptional activity of Au NPs. [16,17] For instance, using Density Functional Theory, Illas et al. have reported that the minimum energy pathway of O 2 dissociation for different Au NPs is chemically similar whichThe enhancement of the catalytic activity of gold nanoparticles with their decreasing size is often attributed to the increasing proportion of low-coordinated surface sites. This correlation is based on the paradigmatic picture of working gold nanoparticles as perfect crystal forms having complete and static outer surface layers whatever their size. This picture is incomplete as catalysts can dynamically change their structure according to the reaction conditions and as such changes can be eventually size-dependent. In this work, using aberration-corrected environmental electron microscopy, size-dependent crystal structure and morphological evolution in gold nanoparticles exposed to hydrogen at atmospheric pressure, with loss of the face-centered cubic crystal structure of gold for particle size below 4 nm, are revealed for the first time. Theoretical calculations highlight the role of mobile gold atoms in the observed symmetry changes and particle reshaping in the critical size regime. An unprecedented stable surface molecular structure of hydrogenated gold decorating a highly distorted core is identified. By combining atomic scale in situ observations and modeling of nanoparticle structure under relevant reaction conditions, this work provides a fundamental understanding of the size-dependent reactivity of gold nanoparticles with a precise picture of their surface at working conditions.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.202104571.

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Section: Resultssupporting

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Revealing Size Dependent Structural Transitions in Supported Gold Nanoparticles in Hydrogen at Atmospheric Pressure

Nassereddine

Wang

Loffreda

et al. 2021

Small

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“…Therefore, during the unstable state, the electron density or the structure of the Au particle has somehow changed, which influenced the adsorption rate of oxygen and the reaction rate on the surface. Note that the experimental conditions that change the structure of the metal NPs have been widely studied 37 – 44 . It was found that hydrogen adsorption could affect the electronic structure of Au NPs and lead to the rearrangement of the electronic subsystem of NPs 37 , 43 , 44 .…”

Section: Resultsmentioning

confidence: 99%

“…Note that the experimental conditions that change the structure of the metal NPs have been widely studied 37 – 44 . It was found that hydrogen adsorption could affect the electronic structure of Au NPs and lead to the rearrangement of the electronic subsystem of NPs 37 , 43 , 44 . The face-centered cubic crystal structure of Au is lost when exposing the gold sample to the hydrogen conditions 38 .…”

Section: Resultsmentioning

confidence: 99%

Insight into the transient inactivation effect on Au/TiO2 catalyst by in-situ DRIFT and UV–vis spectroscopy

et al. 2022

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Au catalysts have drawn broad attention for catalytic CO oxidation. However, a molecular-level understanding of the reaction mechanism on a fast time-resolved scale is still lacking. Herein, we apply in situ DRIFTS and UV-Vis spectroscopy to monitor the rapid dynamic changes during CO oxidation over Au/TiO2. A pronounced transient inactivation effect likely due to a structural change of Au/TiO2 induced by the reactants (CO and O2) is observed at the beginning of the reaction. The transient inactivation effect is affected by the ratio of CO and O2 concentrations. More importantly, during the unstable state, the electronic properties of the Au particles change, as indicated by the shift of the CO stretching vibration. UV-Vis spectroscopy corroborates the structure change of Au/TiO2 surface induced by the reactants, which leads to a weakening of the Au catalyst’s ability to be oxidized (less O2 adsorption), resulting in the transient inactivation effect.

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“…During the 24 h after the exposure to hydrogen, some relaxation processes take place in the nanostructured system, and the form of the VAC curves changes chaotically. This fact may point to the surface migration of chemisorbed H atoms and their transition to the bridge position from the upper and hollow ones [36]. The last two states are similar in energy, while the first one is 0.12 eV more beneficial (see Figure 11).…”

Section: A Quick Glance At the Adsorption Mechanismmentioning

confidence: 95%

Less and Less Noble: Local Adsorption Properties of Supported Au, Ni, and Pt Nanoparticles

et al. 2023

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In this work, we studied the local adsorption properties of gold, nickel, and platinum nanoparticles. A correlation was established between the chemical properties of massive and nanosized particles of these metals. The formation of a stable adsorption complex M-Aads on the nanoparticles’ surface was described. It was shown that the difference in local adsorption properties is caused by specific contributions of nanoparticle charging, the deformation of its atomic lattice near the M–C interface, and the hybridization of the surface s- and p-states. The contribution of each factor to the formation of the M-Aads chemical bond was described in terms of the Newns–Anderson chemisorption model.

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The effect of hydrogen adsorption on the electronic structure of gold nanoparticles

Cited by 8 publications

References 9 publications

Revealing Size Dependent Structural Transitions in Supported Gold Nanoparticles in Hydrogen at Atmospheric Pressure

Revealing Size Dependent Structural Transitions in Supported Gold Nanoparticles in Hydrogen at Atmospheric Pressure

Insight into the transient inactivation effect on Au/TiO2 catalyst by in-situ DRIFT and UV–vis spectroscopy

Less and Less Noble: Local Adsorption Properties of Supported Au, Ni, and Pt Nanoparticles

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