Size effect on the adsorption and dissociation of CO2 on Co nanoclusters

Hua, Yu; Cao, Dapeng; Fisher, Adrian C.; Johnston, Roy L.; Cheng, Daojian

doi:10.1016/j.apsusc.2016.10.192

Cited by 26 publications

(23 citation statements)

References 54 publications

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“…The presence of preadsorbed oxygen was responsible for forming carbonates of different structures [87,93]. On most metal surfaces, CO 2 activation is highly surface orientated, pressure-and particle size-dependent [89,[94][95][96]. Yu et al [96] demonstrated through spin-polarized DFT calculations that adsorption and dissociation of CO 2 was dependent on the Co particle size.…”

Section: Co 2 Activation On Representative Pure Metalsmentioning

confidence: 99%

“…On most metal surfaces, CO 2 activation is highly surface orientated, pressure-and particle size-dependent [89,[94][95][96]. Yu et al [96] demonstrated through spin-polarized DFT calculations that adsorption and dissociation of CO 2 was dependent on the Co particle size. They showed that Co 55 nanoclusters had the highest CO 2 dissociation activity in comparison to Cu-based materials have gained much attention in the CO 2 conversion process due to their wide applicability in the different conversion processes and low cost [12,97].…”

Section: Co 2 Activation On Representative Pure Metalsmentioning

confidence: 99%

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Impacts of the Catalyst Structures on CO2 Activation on Catalyst Surfaces

2021

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Utilizing CO2 as a sustainable carbon source to form valuable products requires activating it by active sites on catalyst surfaces. These active sites are usually in or below the nanometer scale. Some metals and metal oxides can catalyze the CO2 transformation reactions. On metal oxide-based catalysts, CO2 transformations are promoted significantly in the presence of surface oxygen vacancies or surface defect sites. Electrons transferable to the neutral CO2 molecule can be enriched on oxygen vacancies, which can also act as CO2 adsorption sites. CO2 activation is also possible without necessarily transferring electrons by tailoring catalytic sites that promote interactions at an appropriate energy level alignment of the catalyst and CO2 molecule. This review discusses CO2 activation on various catalysts, particularly the impacts of various structural factors, such as oxygen vacancies, on CO2 activation.

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Section: Co 2 Activation On Representative Pure Metalsmentioning

confidence: 99%

Section: Co 2 Activation On Representative Pure Metalsmentioning

confidence: 99%

Impacts of the Catalyst Structures on CO2 Activation on Catalyst Surfaces

2021

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“…The clusters shown an optimal oxygen binding at the low coordinated edge sites in spite of the presence of high coordinated threefold sites. It is also noteworthy that most of the computational studies which reported the monotonic activity increment with nanocluster size toward saturation limit have adapted metallic clusters with periodic increase in number of surface layers as seen for cluster stoichiometries like 38, 55, 147 for cuboctahedron geometry 57,58 . However, global optimization studies have predicted that these cluster sizes can have different minima or nearby lying isomers which breaks the evolutionary structural pattern of these clusters 59 .…”

Section: Unique Size Shape and Composition Dependent Activity Of Nanoclustersmentioning

confidence: 99%

“…It is also noteworthy that most of the computational studies which reported the monotonic activity increment with nanocluster size toward saturation limit have adapted metallic clusters with periodic increase in number of surface layers as seen for cluster stoichiometries like 38, 55, 147 for cuboctahedron geometry. 57,58 However, global optimization studies have predicted that these cluster sizes can have different minima or nearby lying isomers which breaks the evolutionary structural pattern of these clusters. 59 In addition, the competition between Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) Pathways which differ in terms of the order of simultaneous interactions of adsorbates has a strong dependence on cluster size.…”

Section: Size Effectsmentioning

confidence: 99%

Computational strategies to address the catalytic activity of nanoclusters

Nair

Pathak

2020

WIREs Comput Mol Sci

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Metal nanoclusters have been emerged as imperative elements of heterogenous catalysis. Remarkably different properties from the bulk at the atomic level asserts construction of unique principles for understanding nanocluster catalysis. Computational studies abided by delicate theoretical framework are versatile tools for unveiling the structural, energetic, and mechanistic aspects of nanocluster‐based catalysis. Unlike other systems, nanoclusters feature properties derived from the unique surface structure, size dependence, and dynamics insisting fine‐tuning of computational approaches for accurate prediction of catalytic properties. Finding a balance between realistic simulation and computational affordability is of pressing priority. We highlight the urgency of computational models and practices to be updated by learning from the recent developments in this field. Focus is given to less explored factors governing the catalytic potential of nanoclusters. This article is categorized under: Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Density Functional Theory Structure and Mechanism > Reaction Mechanisms and Catalysis

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“…56 These varied outcomes show that the particle size be strategic to control CO 2 adsorption, moreover, there are experimental efforts connected to the optimization of catalytic activities through substrate particle size effects. [173][174][175] The interest to study such effects on the adsorption is not only due to the area per volume ratio and presence of low-coordinated atoms, compared to condensed phases, but also due to thermodynamic, electromagnetic and quantum effects that influence the properties of nanoparticles in the atomistic level. 19,176 The ability to control the type of CO 2 interaction would be valuable, especially for the aforementioned TM that do not stabilize chemisorbed CO 2 easily.…”

Section: Introduction and State Of The Artmentioning

confidence: 99%

>i<Ab Initio>/i< investigation of the adsorption of molecules, involved in carbon dioxide and glycerol utilization, on transition-metal substrates

Mendes¹

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This study was motivated by technologies involving the utilization of glycerol and carbon dioxide to obtain higher value products, which are economically promising and can benefit the environment. Carbon dioxide is a greenhouse gas, abundant in the atmosphere, that could be converted into monomers, fuels and other moieties, while glycerol is a polyol, accumulated as a byproduct in the production of biodiesel, that can be used to obtain other three-carbon alcohols. The aforementioned technologies could be developed by the use of transition-metal substrates as nanoparticles or extended surfaces to design catalysts with great control over properties, such as particle size, morphology and composition, which can be tuned towards optimal catalytic performance. Our study focused on adsorption, a pivotal step of the catalytic process. In this thesis, we present an extensive ab initio investigation, based on density functional theory, of the adsorption of carbon dioxide, glycerol and additional small model molecules on finite-sized and extended TM substrates. Concerning size effects, we found that the adsorption properties for physisorbed and chemisorbed CO 2 depended significantly on the particle size. For CO and H 2 , there was alternation of the most stable adsorption site for the various substrate sizes, which resulted in small size-induced oscillations of properties, while for H 2 O, the adsorption was almost independent of size effects. We also studied the adsorption of CO 2 on Pt-based nanoalloys and found that for systems containing metals with completely filled d-states, alloying with Pt facilitated the charge transfer to CO 2 ; on the other hand, for metals from groups 8, 9 and 10 of the periodic table, alloying with increasing Pt content either caused small effects on the adsorption properties or impaired charge transfer to CO 2 . Moreover, we explored several stable morphologies and chemical orderings and found that CO 2 tends to bend on low-coordinated and heterogeneous adsorption sites. Concerning glycerol and other three-carbon alcohols, we systematically studied the influence of OH groups on the adsorption on model surfaces and found that increasing the number of OH groups increases the adsorption strength, while changing their relative positions leads to similar adsorption strength, but with distinctions of other properties, such as bond stretching for the molecules, such trends were discussed in terms of the reactivities of the alcohols.

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Size effect on the adsorption and dissociation of CO2 on Co nanoclusters

Cited by 26 publications

References 54 publications

Impacts of the Catalyst Structures on CO2 Activation on Catalyst Surfaces

Impacts of the Catalyst Structures on CO2 Activation on Catalyst Surfaces

Computational strategies to address the catalytic activity of nanoclusters

>i<Ab Initio>/i< investigation of the adsorption of molecules, involved in carbon dioxide and glycerol utilization, on transition-metal substrates

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