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Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0003-0007-0394
2014 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 16, no 18, 8367-8375 p.Article in journal (Refereed) Published
Abstract [en]

The single atom alloy of extended surfaces is known to provide remarkably enhanced catalytic performance toward heterogeneous hydrogenation. Here we demonstrate from first principles calculations that this approach can be extended to nanostructures, such as bimetallic nanoparticles. The catalytic properties of the single-Pd-doped Cu-55 nanoparticles have been systemically examined for H-2 dissociation as well as H atom adsorption and diffusion, following the concept of single atom alloy. It is found that doping a single Pd atom at the edge site of the Cu-55 shell can considerably reduce the activation energy of H-2 dissociation, while the single Pd atom doped at the top site or in the inner layers is much less effective. The H atom adsorption on Cu-55 is slightly stronger than that on the Cu(111) surface; however, a larger nanoparticle that contains 147 atoms could effectively recover the weak binding of the H atoms. We have also investigated the H atom diffusion on the 55-atom nanoparticle and found that spillover of the produced H atoms could be a feasible process due to the low diffusion barriers. Our results have demonstrated that facile H-2 dissociation and weak H atom adsorption could be combined at the nanoscale. Moreover, the effects of doping one more Pd atom on the H-2 dissociation and H atom adsorption have also been investigated. We have found that both the doping Pd atoms in the most stable configuration could independently exhibit their catalytic activity, behaving as two single-atom-alloy catalysts.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2014. Vol. 16, no 18, 8367-8375 p.
Keyword [en]
Density-Functional-Theory, Oxygen Reduction Activity, Total-Energy Calculations, Core-Shell Nanoparticles, Finding Saddle-Points, Near-Surface Alloys, Wave Basis-Set, H-2 Dissociation, Cu(111) Surface, Metal-Clusters
National Category
Other Chemistry Topics Other Physics Topics
URN: urn:nbn:se:kth:diva-145619DOI: 10.1039/c4cp00399cISI: 000334602900020ScopusID: 2-s2.0-84898449548OAI: diva2:719130
Swedish Research Council

QC 20140523

Available from: 2014-05-23 Created: 2014-05-23 Last updated: 2015-02-11Bibliographically approved
In thesis
1. First-Principles Modeling of Selected Heterogeneous Reactions Catalyzed by Noble-Metal Nanoparticles
Open this publication in new window or tab >>First-Principles Modeling of Selected Heterogeneous Reactions Catalyzed by Noble-Metal Nanoparticles
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Heterogeneous catalysis is an important branch in catalysis, in which the catalyst and reactants are in different physical phases. In this thesis, we have carried out extensive first-principles calculations to explore the selected heterogeneous reactions catalyzed by the noble-metal nanoparticles. The major results of the thesis fall into two categories: (1) the discovery of the scaling relations for predicting the catalytic activity of nanoparticles; (2) the computational characterization of the catalytic activity and mechanism for specific catalytic reactions. For the first category, we have made efforts to develop the scaling relations for binary noble-metal nanoparticles. The obtained results show that the scaling relation not only holds at the nanoscale, but can also be unified with those obtained for the extended surfaces. Our findings shed new light for the efficient screening of nanoparticles with superior catalytic properties. The second part of the thesis summarizes our studies on different catalytic systems. One of the focuses is to study the catalytic properties of the single Pd-doped Cu55 nanoparticle toward H2 dissociation and propane dehydrogenation. The possible reaction mechanisms and effects of the single and multiple Pd doping on the catalytic activity have been extensively examined. Our calculations reveal that single-Pd-doped Cu55 cluster bears good balance between the maximum use of the noble metal and the high activity, and it may serve as a promising single-atom catalyst. We have also systematically studied the reduction process of graphene fluoride catalyzed by the Pt-coated metallic tip under different atmospheres, aiming to provide a feasible strategy for scanning probe lithography to fabricate electronic circuits at the nanoscale on graphene fluoride. It is found that the tip-induced reduction of graphene fluoride with assistance of pure hydrogen atmosphere is facile despite the release of hazard hydride fluoride. The ethylene molecule is predicted to be an excellent acceptor for fluoride abstraction from graphene fluoride, but the corresponding defluorination cycle can not be recycled. Our calculations have finally revealed that under the mixture hydrogen and ethylene atmosphere, the Pt-coated tip can effectively and sequentially reduce graphene fluoride with the release of relatively harmless reduction product, fluoroethane. The proposed cyclic reduction strategy is energetically highly favorable and is ready to be employed in experiments. Our theoretical studies provide yet another convincing example to demonstrate the power of the density functional theory for studying the nano-catalysis. It should also been mentioned that the present calculations are restricted to relatively small-sized clusters due to the limited computational resources. It is highly desirable to further study complicated interfacial systems and to provide a full picture of heterogeneous catalysis with the aid of ab initio molecular dynamics simulations in the future.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. x, 59 p.
TRITA-BIO-Report, ISSN 1654-2312 ; 2015:6
National Category
Natural Sciences Natural Sciences
urn:nbn:se:kth:diva-159883 (URN)978-91-7595-454-7 (ISBN)
Public defence
2015-03-06, FA32, Roslagstullsbacken 21, AlbaNova, KTH, Stockholm, 14:30 (English)

QC 20150211

Available from: 2015-02-11 Created: 2015-02-10 Last updated: 2015-02-11Bibliographically approved

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