TOUCAN: TOwards an Understanding of CAtalysis on Nanoalloys

Lead Research Organisation: King's College London
Department Name: Physics

Abstract

Nanoparticles differ in many ways from their "bulk" or "liquid" structures. Nanoparticles of transition metals have been widely used for accelerating important chemical reactions, thanks to their high surface to volume ratios and increasing surface energy when the cluster size decreases to a few tens of nanometers. Of particular interest are bi- and multi-metallic nanoparticles (the so-called "nanoalloys") due to the richness of structures and mixing patterns that they can exhibit and the control of chemical and physical properties that this affords.

Computational tools play a central role in designing and tailoring of nanomaterials, allowing us to find the "magic" nanoparticles for target applications, since the computing power will recreate and investigate in-silico the experimental conditions in order to suggest optimal candidates to industrial partners. A fundamental use of first-principles simulations in nanoalloy science focuses on the chemical reactions that they induce. It has been experimentally shown that heteroepitaxial grown strained over-layers can present chemical properties different than those of the unstrained surface of the same elements. This fact has been confirmed by first-principles calculations. However, at the nanoscale, due to their peculiar surface and bulk geometries, as well as various chemical orderings, even the characterization of chemisorption sites on nanoalloys is not an easy task.

In this proposed research programme, binary nanoalloys will be investigated for their potential catalytic properties. This project will focus mainly on Pt- alloys (i.e. PtAg and PtAu), Ni-alloys (i.e. AgNi, NiPt), Pd-alloys (i.e. PdAg, and PdPt), Co-alloys (i.e. AgCo and CoPt) and Fe-alloys (i.e. FePt and FeCo). Specific chemical reactions with a strong influence in the field of sustainable energy will be considered, such as CO2-capture, biomass processes - e.g. involving dissociation of CO and CH4, and NH3 dissociation for hydrogen production.

Two conditions must be fulfilled for a spontaneous chemical transformation to occur in the laboratory: (1) the final state must have a lower free energy than the initial state, and (2) there must be at least one pathway that allows the transformation to take place within a reasonable time. In simple chemical reactions, the transformation pathway (the reaction coordinate) is often well understood, which makes it possible to compute reaction rates and predict how external influences (such as catalysts) will affect these rates. However, there are many transformations, including
structural relaxation and nucleation in solids, where the trajectory can follow complex paths that correspond to cooperative or sequential motion of many degrees of freedom. From the point of view of computer simulation, such pathways correspond to rare events, because the waiting time required for the process of interest to occur is very large compared to the time taken for the event itself. To understand and control such complex transformations at the microscopic level, we need to characterise the underlying, high-dimensional potential energy landscape and sample the rare events directly. Based on this knowledge, we aim to predict the relevant transformation pathways and rates and, more ambitiously, to understand how we can influence these rates.

The project is comprised of four inter-linked projects which are aligned with the aims and objectives set out above:

P1. Construction of the Nanoalloy Database

P2. Determination of Thermal Stabilities of Nanoalloy Isomers

P3. Chemisorption Maps

P4. Reaction Rates for Molecular Dissociation on Nanoalloys

Publications

10 25 50

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Baletto F (2015) Doped golden fullerene cages. in Physical chemistry chemical physics : PCCP

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Davis JB (2015) The Effect of Dispersion Correction on the Adsorption of CO on Metallic Nanoparticles. in The journal of physical chemistry. A

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Gould AL (2016) Controlling Structural Transitions in AuAg Nanoparticles through Precise Compositional Design. in The journal of physical chemistry letters

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Pavan L (2015) Metallic nanoparticles meet metadynamics. in The Journal of chemical physics

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Rossi K (2017) Melting of large Pt@MgO(1 0 0) icosahedra. in Journal of physics. Condensed matter : an Institute of Physics journal

 
Description We have providing new insights on the effect of support and alloy on the catalytic activity of Pt-based nanoparticles.We are developing a model to rational design nanocatalysts.
Exploitation Route Eventually they could be used to fabricate better nanocatalyts and exploited in fuel cells applications.
Sectors Energy,Transport

 
Description Stimulating the internal discussion and promoting new international collaborations. A new paper in collaborations with Wales' group (Cambridge) has been published and another between my group, Csanyi (Cambridge) and Bartok (Reading) has been submitted. Further I have published a outreach paper with Johnston: "Catalysts bit by bit", on http://researchfeatures.com/2017/11/01/designing-catalysts-bit-by-bit, which has potential to be used by a wider audience. Several activities at London schools.
First Year Of Impact 2017
Sector Education
Impact Types Societal

 
Description CCP5 - Summer Internship
Amount £4,000 (GBP)
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Academic/University
Country United Kingdom
Start 07/2017 
End 09/2017
 
Description CECAM Travel grant 2015
Amount € 350 (EUR)
Organisation European Centre of Atomic and Molecular Computation (CECAM) 
Sector Academic/University
Country Switzerland
Start 06/2015 
End 06/2015
 
Description COST-Action MP0903: TAMC activity
Amount £800 (GBP)
Organisation European Commission 
Sector Public
Country European Union (EU)
Start 08/2013 
End 09/2013
 
Description Postdoctoral visit/exchange
Amount R$ 50,000 (BRL)
Organisation Government of Brazil 
Department Science without Borders
Sector Public
Country Brazil
Start 06/2016 
End 06/2017
 
Description Psi-K conference funding
Amount € 5,000 (EUR)
Organisation European Science Foundation (ESF) 
Sector Charity/Non Profit
Country European Union (EU)
Start 12/2016 
End 12/2016
 
Description Royal Society equipment
Amount £13,882 (GBP)
Organisation The Royal Society 
Sector Academic/University
Country United Kingdom
Start 09/2012 
End 12/2013
 
Description Workshop support
Amount £400 (GBP)
Organisation Overleaf 
Sector Private
Country United Kingdom
Start 09/2016 
End 02/2017
 
Description Workshop support
Amount £1,000 (GBP)
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Academic/University
Country United Kingdom
Start 10/2016 
End 02/2017
 
Description Workshop support
Amount £250 (GBP)
Organisation Royal Society of Chemistry 
Sector Learned Society
Country United Kingdom
Start 10/2016 
End 02/2017
 
Title developping of an empirical force field for oxide surfaces 
Description A new force field has been derived for the simulation of supported platinum clusters on the pristine MgO surface 
Type Of Material Computer model/algorithm 
Provided To Others? No  
Impact Scientific publication a deeper understanding on the building up of Pt-based nanocatalysts 
 
Description FAPESP collaboration 
Organisation University of Sao Paulo
Country Brazil 
Sector Academic/University 
PI Contribution Providing Pt nanoparticles for ethanol catalysis
Collaborator Contribution Ethanol catalysis on surfaces
Impact A paper is in preparation. Dr Vagner Rigo will come as senior post doc from June 2016 May 2017 supported by a Science without Border fellowship. Thanks to this collaborations, our groups will take part to the KCL/USP week to be held on 11-13 May 2016.
Start Year 2012
 
Title LoDiS-MD: low dimensional systems molecular dynamics 
Description LoDiS-MD: low dimensional systems molecular dynamics is a softaware tool wirtten in Fotran90 designed specifically to the study of metallic nanoparticles. There is long varierty of tools such as ionic minimization one-by-one growth nucleation thermal stability metadynamics It is now coming with a post-processing tool for the geometrical analysis of metallic nanoparticles 
Type Of Technology Software 
Year Produced 2015 
Impact Elucidating how the geometrical shape may influence the physicochemical properties of nano-objects (shape-property relationship) has acquired more and more importance in the design of devices for target applications. We plan to put the code open-sources in two-three years once more potential and how to describe external enviroments will be implemented (our top priority). This will allow small compnies and academics to create a complete database for objects at the nanoscale not only with their peculiar structures but including their thermal stability and hints for investigating their physico-chemical properties. 
 
Description 2nd Meeting of the American Initiative on Metal Clusters and Nanoalloys, San Antonio, Texas, USA 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr. Lauro Oliver Paz-Borbon gave an invited talk on "Embracing the substrate for studying the catalytic properties of Pt-Ni nanoalloys" at a USA meeting on nano clusters. This community is quite well-known and gave him the possibility to become in contact with Dr. Gregory Guisbiers and together they are organising a symposium at the next MRS-conference in Cancun.
Year(s) Of Engagement Activity 2016
 
Description CCP9 Young Researchers' event (25-26 March 2016) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Pico-talk (1 slide - 60 s) + Poster by Dr. Gian Giacomo Asara
We advise our colleagues about the research presented in our poster.
We focused on O2 adsorption on core-shell PtNi supported nanoparticles highlighting the effect of shape, alloying, interaction with an oxide support and chemical composition at the interface.
Year(s) Of Engagement Activity 2016
 
Description CECAM Meeting 2015-Toulose 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact I gave an invited talk on "Modelling metal-based nanoparticles: toward realistic environments". Further discussion gave me the possibility to reach the interest of Johnson Matthey.
Year(s) Of Engagement Activity 2015
 
Description COST Action Final Meeting: AuCu and AgAu nanocages 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact My presentation stimulated a discussion afterwards

Scientific network boosted
Year(s) Of Engagement Activity 2014
 
Description ECOSS-2015: Barcelona 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Invited talk at the ECOSS 2015 on ""Modelling Nanocatalysts", several questions after my talks and potential new collaboration across Europe.
Year(s) Of Engagement Activity 2015
 
Description ENGE: International Conference on Electronic Materials and Nanotechnology for Green Environment, Jeju, South Korea 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr. Lauro Oliver Paz-Borbon gave an invited talk on "O2 adsorption trends on small supported Pt-Ni clusters: Towards an efficient nanocatalyst design", presenting our common results obtained during his time as PDRA at KCL. The audience was listening carefully and asked several questions.
Year(s) Of Engagement Activity 2016
 
Description ICTP-College on Multiscale Computational Modeling of Materials for Energy Applications 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact I did three presentations at this International School host by the Unesco-ICTP.
One presentation was a long invited talk (a keynote) on my recent research.
Then we did a half-day school on the software we are developing and maintaining in my research group. My PhD, Mr Kevin Rossi, attended and helped during this activity.
Further I made a presentation on being an outreach activity to support female academic staff, and in particular on "Being an Academic Mum"
Year(s) Of Engagement Activity 2016
URL http://indico.ictp.it/event/7656/
 
Description International Symposium on 'Semiconductor Clusters and Nanoparticles: Geometric, Electronic, and Optical Properties', Berlin 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact An invited talk to an Int. Symposium linked to a DFG program (German platform grant). This allowed me to show my results to a wide a new community.
Year(s) Of Engagement Activity 2017
 
Description International Workshop on Nanoalloys 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact A quite select group of people working on nano alloys across Europe (following the previous COST-Action network we had). One day presentation, I was invited to give a talk, and the second day dedicated to established a new network. A Faraday discussion meeting is likely to happen in 2018 and I have been offered my support to organise it.
Year(s) Of Engagement Activity 2016
 
Description Invited Lecture at the CATSENSE Summer School, Leuven, Sept 2017 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact It was a privilege to be invited to give a talk to such a high qualified group of students and post-doc actively involved in different aspects of catalysis, as they are part of a EU collaboration. Several questions afterwards.
Year(s) Of Engagement Activity 2017
 
Description Invited Talk at the Faraday Joint Interest Group, Warwick 2017 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Invited talk at the first join Faraday Discussion meeting organised by the Royal Society of Chemistry. A good discussion afterwards.
Year(s) Of Engagement Activity 2017
 
Description Invited talk at Cost-Action, Graz, Austria, Feb 2018 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Delivered a talk to an International community -which gather various EU group under the umbrella of COST-Action CM-1405 MOLIM. Several questions and discussion afterwards.
Year(s) Of Engagement Activity 2018
URL https://www.staff.tugraz.at/andreas.hauser/molim2018/
 
Description Invited talk at the International Symposium Semiconductor Clusters and Nanoparticles, Berlin 2017 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Invited talk to a quite heterogeneous audience working on nanoscale systems. Several questions afterwards and new contacts were made during the event.
Year(s) Of Engagement Activity 2017
 
Description Launch of the EPSRC-Tier2 MMM-Hub 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Postgraduate students
Results and Impact A significant audience for the launch event of the new Tier2 HPC facility which serve London academic groups working on computational material science. The talk was well received by the audience.
Year(s) Of Engagement Activity 2017
 
Description Pacific Chem 2015: Hawaii 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Invited talk on "Supported metallic and bimetallic nanocatalysts". Several new contacts. An invitation to present my work at the Palmer's group in Birmingham.
Year(s) Of Engagement Activity 2015
 
Description Psi-K 2015: San Sebastian (several contributions) 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact A. Poster Presentation on "Understanding the catalytic activity of large polyhedral nanoparticles from first-principles", presenter Dr GianGiacomo Asara
We introduced to other colleagues from all around the world our roadmap that allows to extrapolate results obtained using small in-silico models to experimental sizes.

B. Poster Presentation on "Thermodynamics of CuPt via DFT fitted potential" by Mr. K. Rossi
C. Poster Presentation on "Topological effects on the magentization of platinum nanoclusters"
Year(s) Of Engagement Activity 2015
 
Description RSC solsurf 2016: London 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Other audiences
Results and Impact Poster presentation on "On solid-solid transitions in nanoalloys, towards stable and functional architectures" by Mr. Kevin Rossi
Year(s) Of Engagement Activity 2016
 
Description School Visit (St Eugene) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact 30 pupils attended a "Meet a scientist" event at their school. They made several questions during and after the presentation. The school put the event on their newsletter and we hope to invite a short cohort of students to visit the Physics department at KCL.
Year(s) Of Engagement Activity 2017
 
Description School Visit (St Mary) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact 30 pupils (Year 5) attended a "Meet a scientist" presentation I made at their school. Several questions and discussions during and after the presentation. The school reported a strong interest in science subjects.
Year(s) Of Engagement Activity 2018
 
Description Seminar at DIPC and UPV, San Sebastian, Spain "Unravelling morphologies and chemical ordering at the nanoscale" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact Seminar at DIPC, San Sebastian on "Unravelling morphologies and chemical ordering at the nanoscale" June 2014
My talk stimulates the discussion on how we can model the shape-property relationship.

Networking
Year(s) Of Engagement Activity 2014
 
Description THIS: Theory of Hetero-Interfaces and Surfaces. Yonsei University, Winter School 2016, Seúl, South Korea 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr. Lauro Oliver Paz-Borbon gave an invited talk on "Physics and Chemistry of nanoclusters" showing our common results on Pt onto MgO and the adsorption of O2 onto Pt and PtNi MgO-supported. The audience was mixed, PhD and PDRA students and they have asked different questions.
Year(s) Of Engagement Activity 2016
 
Description TOUCAN Meeting 2015: London 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Other audiences
Results and Impact Annual TOUCAN MEETING, working group related to the EPSRC Critical Mass EP/J010812/1
Year(s) Of Engagement Activity 2015
 
Description TYC 10B'Day (two contributions) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact TYC 10th anniversary, london
A. "Get in Touch and Keep in Contact": interface effect on the ORR activity for supported PtNi nanoparticles by Dr GianGiacomo Asara
B. Poster presentation on "Nanothermodynamics: molecular dynamics vs nested sampling" by Mr. Kevin Rossi
Year(s) Of Engagement Activity 2016
 
Description TYC-Energy workshop and Toucan conference 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact I was the main organiser of the 4th TYC-Energy workshop held at King's College London.

On top of the full organisation, I made a presentation on numerical methods for the design of nano catalysts.
Year(s) Of Engagement Activity 2016
URL http://www.thomasyoungcentre.org/events/energy-materials-workshop
 
Description Understanding the catalytic activity of polyhedral nanoparticles from first principles 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact An invited talk given by Dr. Asara at the FisMat2015, the international conference organised by the Italian Physics Society.
Year(s) Of Engagement Activity 2015
 
Description Understanding the catalytic activity of polyhedral nanoparticles from first principles 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact A talk presentation by Dr. Asara at the Psi-K conference held in San Sebastian Sept. 2015. Psi-K is the largest conference on numerical modelling.
Year(s) Of Engagement Activity 2015