VOLUME 55 NUMBER 3 JULY 2011 Platinum Metals Review www.platinummetalsreview.com E-ISSN 1471-0676 © Copyright 2011 Johnson Matthey Plc http://www.platinummetalsreview.com/ Platinum Metals Review is published by Johnson Matthey Plc, refi ner and fabricator of the precious metals and sole marketing agent for the six platinum group metals produced by Anglo American Platinum, South Africa. All rights are reserved. Material from this publication may be reproduced for personal use only but may not be offered for re-sale or incorporated into, reproduced on, or stored in any website, electronic retrieval system, or in any other publication, whether in hard copy or electronic form, without the prior written permission of Johnson Matthey. Any such copy shall retain all copyrights and other proprietary notices, and any disclaimer contained thereon, and must acknowledge Platinum Metals Review and Johnson Matthey as the source. No warranties, representations or undertakings of any kind are made in relation to any of the content of this publication including the accuracy, quality or fi tness for any purpose by any person or organisation. E-ISSN 1471-0676 • Platinum Metals Rev., 2011, 55, (3), 152• Platinum Metals Review A quarterly journal of research on the platinum group metals and of developments in their application in industry http://www.platinummetalsreview.com/ JULY 2011 VOL. 55 NO. 3 Contents The PGM 2011 Industrial Commercialization Competition 153 A guest editorial by Michael Joseph Carbon Nanotubes as Supports for Palladium and Bimetallic Catalysts 154 for Use in Hydrogenation Reactions By R. S. Oosthuizen and V. O. Nyamori 6th International Conference on Environmental Catalysis 170 A conference review by Noelia Cortes Felix 9th International Frumkin Symposium 175 A conference review by Alexey Danilov “Heterogenized Homogeneous Catalysts for Fine Chemicals 180 Production: Materials and Processes” A book review by Raghunath V. Chaudhari Phase Diagram of the Rhenium-Rhodium System: State of the Art 186 By Kirill V. Yusenko “Ruthenium Oxidation Complexes: Their Uses as 193 Homogenous Organic Catalysts” A book review by Peter Maitlis The Early Life of Smithson Tennant FRS (1761–1815) 196 By David G. Lewis “Platinum 2011” 201 Publications in Brief 203 Abstracts 206 Patents 209 Final Analysis: Is Gold a Catalyst in Cross-Coupling Reactions 212 in the Absence of Palladium? By Madeleine Livendahl, Pablo Espinet and Antonio M. Echavarren Editorial Team: Jonathan Butler (Publications Manager); Sara Coles (Assistant Editor); Ming Chung (Editorial Assistant); Keith White (Principal Information Scientist) Platinum Metals Review, Johnson Matthey Plc, Orchard Road, Royston, Hertfordshire SG8 5HE, UK Email: [email protected] 152 © 2011 Johnson Matthey doi:10.1595/147106711X587273 •Platinum Metals Rev., 2011, 55, (3), 153• Guest Editorial The PGM 2011 Industrial Commercialization Competition Anglo American Platinum, the world’s largest The unique qualities of pgms make them a vital primary platinum miner, is a proud partner component in many technological inventions and of the 2011 SA Innovation Summit. This aims a part of our everyday lives – in applications as to provide opportunities for innovators and diverse as transport, industrial processes, electronic inventors to communicate their ideas, including device manufacture and medicine. Their catalytic new applications for the platinum group metals properties make them a signifi cant contributor to (pgms) mined by Anglo improving the environment by American Platinum. Access to providing cleaner, more effi cient these opportunities is promoted energy. Research and development through the PGM Industrial into the applications of the pgms Commercialization Competition. has brought signifi cant technical South Africa is home to 77% of the world’s and commercial success in all of these areas. platinum reserves, and Anglo American Platinum Together with their ability to be recycled, pgm use accounts for about 42% of newly mined production is also increasingly sustainable. globally, with its operations primarily based in Innovation and economic growth are integrally South Africa. Benefi ciation of South Africa’s mineral linked. This competition should help promote wealth before export has huge potential for major innovative, commercially viable technology that fi nancial growth with many opportunities for job will add value to the pgm economic chain. creation in the country. South Africa’s strengths include technical and production expertise as MICHAEL JOSEPH well as comprehensive research and development Anglo American Platinum, South Africa activities. Anglo American Platinum launched the PGM Email: [email protected] Development Fund in 2009 with the specifi c objective of providing capital for future pgm More Information market development and benefi ciation. The Fund To download an entry form, visit the PGM seeks to invest primarily in early stage or start-up Development Fund website: activities with commercial viability. The Industrial www.pgmdevelopmentfund.co.za Commercialization Competition for the best new For more information on the Innovation Summit, application for pgms or an improvement on a visit: www.innovationsummit.co.za current commercialised product will be a platform for funding consideration by the PGM Development The Author Fund. Michael Joseph is the Manager: Industrial Development and The competition is open to researchers, Benefi ciation at Anglo American Platinum, and leads the PGM institutions, manufacturers, designers or teams Industrial Commercialization Competition. resident in South Africa and must be submitted by 30th November 2011. 153 © 2011 Johnson Matthey •Platinum Metals Rev., 2011, 55, (3), 154–169• Carbon Nanotubes as Supports for Palladium and Bimetallic Catalysts for Use in Hydrogenation Reactions doi:10.1595/147106711X577274 http://www.platinummetalsreview.com/ By R. S. Oosthuizen‡ and V. O. Nyamori* Carbon nanotubes (CNTs) possess unique properties which make them competitive with conventional catalyst School of Chemistry, University of KwaZulu-Natal, supports. This short review collates fi ndings from many Westville Campus, Private Bag X54001, Durban 4000, research groups on the benefi ts of palladium/carbon South Africa nanotubes in hydrogenation reactions. The effects of ‡ Email: [email protected]; *[email protected] modifi ed CNTs and bimetallic platinum group metal (pgm) catalyst/CNT systems for hydrogenation reactions are also discussed. Introduction The need to optimise industrially important processes and new technologies, and to create a sustainable society and environment, drives the search for better energy sources and better materials. Coupled with this is the need for economic development and competi- tiveness in the global market. Worldwide trends are towards greener chemistry, greener energy and a decrease in our reliance on fossil fuels. Catalysis plays an important role in this and two recent papers have discussed how it has shaped, and will continue to shape, society (1, 2). Progressive research into novel catalytic systems is a part of this endeavour. Palladium is one of the most versatile metal catalysts used in industry. Two of the main reasons for its importance are its ability to catalyse the formation of carbon–carbon bonds and the insensitivity of many Pd catalysts to water or oxygen. Pd is particularly effi - cient as a catalyst in hydrogenation reactions. Metal catalysts reach a much greater potential when sup- ported. This is because metal catalyst particles can be dispersed to a greater degree, and therefore are exposed to a larger number of substrate molecules. Up to 75% of hydrogenation reactions are currently carried out over Pd/C catalysts. A variety of carbon supports for precious metal cata- lysts have, for several decades, been used in heteroge- neous catalysis (3). Emerging carbonaceous supports, such as the newly discovered carbon allotropes and shaped carbon nanomaterials (SCNMs), including CNTs (4), see Figure 1(a), carbon microspheres (5), 154 © 2011 Johnson Matthey doi:10.1595/147106711X577274 •Platinum Metals Rev., 2011, 55, (3)• (a) (b) (c) 40 nm 40 nm 50 nm Fig. 1. TEM image of: (a) Pd/MWCNTs used for heterogeneous hydrogenation of trans- stilbene (76); (b) Pd/microspheres before a hydrogenation reaction (5); (c) Pd/CNFs used for the heterogeneous hydrogenation of cinnamaldehyde (6) (Reproduced by permission of The Royal Society of Chemistry and Elsevier) see Figure 1(b), and carbon nanofi bres (CNFs) (6), This article covers a wide range of literature on Pd/ see Figure 1(c), are gaining more interest. The CNT systems. The examples chosen for this review remarkable properties of CNTs, such as being rela- mainly involve some current studies of Pd/CNT sys- tively light in weight and strong in nature, make them tems for hydrogenation reactions. Specifi cally, exam- worthwhile to investigate as supports for Pd metal ples based on cinnamaldehyde (Figure 2(a)), which catalysts. Although the existence of fi lamentous car- has useful applications such as a fl avouring, fungicide, bon nanomaterials (7) has been known for decades, antimicrobial agent or anticancer agent among others, it is only since the report in 1991 by Iijma (8) that are provided. The reduction of this organic compound many researchers have devoted much time and effort in is interesting because it has more than one functional developing new strategies for the synthesis of SCNMs. group that can be reduced. The useful products that Trends in technological