Single atoms as highly selective active sites in heterogeneous catalysis

Lead Research Organisation: Aston University
Department Name: Sch of Engineering and Applied Science

Abstract

The production of fuels and chemicals from biomass becomes increasingly important due to the diminishing reserves of fossil fuels. The development and sustainability of bio-based industries will be highly dependent on catalytic processes capable of selectively transforming functionalised organic molecules to chemical intermediates and commercial products. In this respect, cellulosic biomass is the most abundant form of biomass and one of the most important renewable energy resources worldwide available. Cellulose derived chemicals like furfural offer very important commercial opportunities as they can be used as starting materials and building blocks to synthesize a variety of products. Therefore, there is a major industrial interest to develop cheap, environmentally friendly low temperature catalysts with stable and prolonged performance.

The described work aims to develop atom efficient catalysts for a class of hydrogenation reactions that lie at the heart of the bio-based energy and fine chemicals industries. Two different classes of materials will be investigated both of which are based on the catalytic properties of small quantities of isolated catalytically active metal centres of gold, palladium and Pt on the surface of oxide supports or on the surface of relatively inexpensive metal nanoparticles. The activation of hydrogen on isolated sites and its spillover on the oxide support will be investigated in order to identify promising systems for low temperature hydrogenations. The reactions of principal focus will be the selective hydrogenation of furfural, cinnamaldehyde and acrolein. A variety of laboratory and synchrotron based techniques will be used to establish a relationship between molecular structure and hydrogenation activity and selectivity on single atom sites. The materials developed in this project offer the benefit of atom efficiency and low cost of production as only small amounts of precious metals are required. More importantly single atom catalysts offer improved selectivity towards specific products due to the homogeneity of the active center on the catalyst surface. Fine dispersions on oxide supports can provide a relatively cheap alternative to traditionally employed heterogeneous hydrogenation catalysts.

Planned Impact

The proposal aims to develop new materials for chemical transformations of interest to the bio-based energy and pharmaceutical industries by delivering new knowledge about selective heterogeneous hydrogenation processes through the development of better, more selective, cheaper and environmentally friendly catalysts. This will be achieved by studying: the formation of single atomic entities on metal nanoparticles and oxide supports; the selective hydrogenation of bio-derived molecules under a variety of conditions; the mechanistic aspects of hydrogen activation and spillover on these materials. In this respect the proposed work has the potential of important social and economic impact to the following sectors:

1. Industry: The principal industrial beneficiaries of this work are catalyst, fine chemicals and bulk chemicals manufacturers. The proposed research work will open the door to collaborative projects between academia and UK companies including precious metal catalyst and process chemicals manufacturers (including companies such as Johnson Matthey, GSK and BP). Companies interested in the proposed work will be approached directly by the PI and through well-established mechanisms in the University of Hull.

2. General Public: Improved heterogeneously catalyzed processes have the potential to impact the UK national economy and the financial market as they enable cheaper and faster large scale production of products through accurate processes with minimum impact to the environment. The project aims to deliver atom efficient green catalysts to synthesize a variety of products useful in diverse market segments. The local communities and schools will be informed about mitigation of environmental damage through efficient process design via the dissemination methods described in the "pathways to impact" document.

3. Academic community: The continuously increasing importance for environmentally friendly and cost effective processes for the production of chemicals has a large impact in catalysis research. The described experiments will be of interest to the UK and international catalysis community. It will also provide new knowledge on materials synthesis, alloy compounds, hydrogen capture and storage and it will be of interest to other sections of the academic community including materials science, physics and chemical engineering. The proposed work will enable the PI to establish a new research group in the area of heterogeneous catalysis and facilitate academic collaborations at the national and international level.

Related Projects

Project Reference Relationship Related To Start End Award Value
EP/M005186/1 24/10/2014 31/08/2015 £80,153
EP/M005186/2 Transfer EP/M005186/1 02/11/2015 31/03/2017 £36,475
 
Description We have discovered how precious metal platinum nanoparticles can be utilized under very mild conditions to convert molecules derived from biomass to commodity chemicals and strategic intermediates.

We have discovered alternative colloidal methods of generating Single atom alloy nanoparticles in a reproducible manner. We have used the new materials for the conversion of platform biomass molecules to useful chemicals

We have performed experimental work under Ultra high vacuum to elucidate the interaction of Pt extended surfaces with biomass platform molecules. Our work enabled in depth understanding on how Pt catalyses the hydrogenation of furfural.
Exploitation Route Scale up of the process and cost minimization of the materials enabling, which is part of this ongoing process can enable the use of these materials in a larger scale.
Sectors Chemicals,Education,Energy,Environment

 
Description 16th International Congress on Catalysis (ICC 16) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Titile: Highly selective supported nanoparticles for the hydrogenation of furfural under mild conditions
Date: 3rd - 8th July 2016
Year(s) Of Engagement Activity 2016
 
Description Abstract submission and poster presentation in the UK Catalysis Conference 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Submission of abstract and poster presentation in the UK catalysis conference 2018. Authors: Martin Taylor, Mohammed Islam, Thomas Bryant, Christopher Parlett, Mark Isaacs, Karen Wilson, Adam Lee, Georgios Kyriakou. TItle: The effect of Cu in PtCu bimetallic particles for the selective transformation of furfural. Dates: 03/01/2018 - 05/01/2018. Loughborough, UK
Year(s) Of Engagement Activity 2018
URL http://events.manchester.ac.uk/event/event:tq-j2j5qpnp-y3etg1/uk-catalysis-conference-2018
 
Description Invited Lecture, Chemical Engineering, University of Patras, Greece 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Invited talk, Department of Chemical Engineering, University of Patras, Greece. Title: Hydrogenation reactions of model alkenes and biomass derived molecules on Pt based catalysts, Pt(111) single crystals and single atom alloy catalysts. Date: 19/10/2017
Year(s) Of Engagement Activity 2017
 
Description Pre- symposium of 16th ICC SAA 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact International Symposium On Single-Atom Catalysis
June 30 - July 2, 2016, Dalian, China
Title: Single atom alloys for selective catalytic hydrogenation reactions
Year(s) Of Engagement Activity 2016
 
Description RSC Applied Catalysis Group and the SCI Fine Chemicals Group 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Title: Optimising Pt Based Heterogeneous Catalysts for the Hydrogenation of Biomass Derived Molecules

Challenges in Catalysis for Pharmaceuticals and Fine Chemicals IV, Burlington House, London

Date: 5th November 2014
Year(s) Of Engagement Activity 2016
 
Description UK Catalysis Conference 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Title of presentation: Ultra-selective hydrogenation of furfural on Pt based dispersed catalysts and extended Pt(111) single surfaces
Date: 4th - 6th January 2017
Year(s) Of Engagement Activity 2017
 
Description UK Catalysis Conference -2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Title: Highly selective supported nanoparticles for the hydrogenation of furfural under mild conditions
Date: 6th - 8th January 2016
Year(s) Of Engagement Activity 2016
 
Description University of Massachusetts (Amherst) 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Invited talk talk followed by discussion on Single atom catalysts at the University of Massachusetts (Amherst) - Department of Chemical Engineering
Date:2 December 2016
Year(s) Of Engagement Activity 2016
 
Description Visit to the University of Ghana 
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 Participation / organisation in workshop at the University of Ghana. Title: Workshop in Heterogeneous Catalysis, Nanomaterials, X-ray Crystallography and NMR. 20-22 May 2017
Year(s) Of Engagement Activity 2017
 
Description Visit to the University of Massachusetts for an Invited Lecture 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Invited lecture in the Department of Chemical Engineering, UMASS, USA. Title: Ultra-selective hydrogenation of furfural on Pt based dispersed catalysts and extended Pt(111) single crystal surfaces.
Year(s) Of Engagement Activity 2016