Catalysis Science & Technology Blog

Hot Article: Optimising Alkylation in Desilicated ZSM-5

21 Jan 2012

“To acid wash or not to acid wash, that is the question!”

ZSM-5 is a crystalline zeolite structure used in the petroleum industry as a heterogeneous catalyst for hydrocarbon isomerization reactions. Modification of the microporous structure is being investigated to improve the catalytic potential of the zeolites, alkaline treatment can desilicate the structure and introduce interconnected mesopores. However a consequence of this is the production of extra-framework aluminium and amorphous alumina, which can realuminate on the external surface and affect pore direction.

Acid washing after alkali leaching aims to restore the original framework composition and can enhance the micropore volume, mesoporous surface area, and crystallinity. The effects of these modifications to the ZSM-5 structure undoubtedly affect the catalytic properties as the alkali and acid treatments alter the porosity and composition of the catalyst.

This Hot article by Javier Perez-Ramirez et al. at ETH Zurich aims to de-couple the effects of porosity and composition using the alkylation of toluene (and cyclohexylbenzene) with benzyl alcohol as a model reaction. Alkaline-treated ZSM-5 zeolites are prepared with and without subsequent acid treatment and their catalytic properties determined, the separate effects of porosity and composition are then examined with some very insightful results.

Decoupling porosity and compositional effects on desilicated ZSM-5 zeolites for optimal alkylation performance
Maria Milina, Sharon Mitchell, Zair Domínguez Trinidad, Danny Verboekend and Javier Pérez-Ramírez
Catal. Sci. Technol., 2012, Advance Article
DOI: 10.1039/C2CY00456A

All articles are free to access in Catalysis Science & Technology for the duration of 2012, you can also keep up to date with latest news in catalysis by liking us on facbook, following us on twitter and signing up to our e-alert service.

Other articles which may of interest from the Pérez-Ramírez group include:

Design of hierarchical zeolite catalysts by desilication
Danny Verboekend and Javier Pérez-Ramírez
Catal. Sci. Technol., 2011, 1, 879-890
DOI: 10.1039/C1CY00150G, Minireview

Mesoporous ZSM-22 zeolite obtained by desilication: peculiarities associated with crystal morphology and aluminium distribution
Danny Verboekend, André M. Chabaneix, Karine Thomas, Jean-Pierre Gilson and Javier Pérez-Ramírez
CrystEngComm, 2011, 13, 3408-3416
DOI: 10.1039/C0CE00966K, Paper

Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design
Javier Pérez-Ramírez, Claus H. Christensen, Kresten Egeblad, Christina H. Christensen and Johan C. Groen
Chem. Soc. Rev., 2008, 37, 2530-2542
DOI: 10.1039/B809030K, Critical Review

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Semiconductior supported gold in catalysis

19 Jan 2012

By Ruth Doherty, Deputy Editor.

High-quality semiconductor supported Au particles have been successfully made using a simple seeded growth approach. The two Au catalysts produced have shown enhanced photocatalytic performance in the reduction of 4-nitropheno. Read on in the recent free-to-access Hot Article:

Synthesis of high-quality I–III–VI semiconductor supported Au particles and their catalytic performance
Xiao Wang, Dapeng Liu, Shuyan Song and Hongjie Zhang
Catal. Sci. Technol., 2012, DOI: 10.1039/C2CY00372D

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FineCat 2012 – Symposium on catalysis for fine chemicals

19 Jan 2012

By Matthew Cude, Development Editor.

The first FineCat symposium on catalysis for fine chemicals will be held in Palermo, Italy, on April 18-19, 2012. The deadline for both oral and poster abstracts is 10th March and the symposium will be held in Steri Palace, hall of Palermo’s University Rectorate, one of the most beautiful medieval buildings in Palermo!

The symposium will cover some of the latest developments in catalysis science and technology within one of the symposium themes:
Green catalytic processes
Organo- and biocatalysis
Asymmetric heterogeneous catalysis
Atom Economy and clean technology
Green reaction media
Heterogeneous catalysis under flow conditions

The meeting aims to provide an opportunity for contact between academic and industrial researchers, manufacturers and users of solid catalysts for the efficient and selective production of fine chemicals.

The symposium ties in well with the 2011 themed issue of Catalysis Science & Technology, Heterogeneous catalysis for fine chemicals, and the journal is proud to offer a Catalysis Science & Technology poster prize.

For more details on FineCat2012, including abstract submission, registration and details of plenary lectures from Gadi Rothenberg and Graham Hutchings please visit the FineCat2012 website.

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Hot Perspective: Catalytic Supports

19 Jan 2012

By Matthew Cude, Development Editor.

Heterogeneous and homogeneous catalysis are two very distinct classes of catalysts, while the former is commonly easier to recover and re-use the latter is often more selective. This review by Prati et al. (Universita degli Studi di Milano) covers the recent advances in catalysts on supports, in particular the support of metal nanoparticles and their catalytic properties.

The accessibility of the particle surface plays an important role in activity with a high surface area giving a higher reaction rate, however it has also been shown that incarceration of particles inside support cavities can be beneficial with respect to resisting leaching and coarsening.

For full details of this topical review and its findings you can download this Hot Perspective now as all articles in Catalysis Science & Technology are free to access for the duration of 2012.

Material science for the support design: a powerful challenge for catalysis
Alberto Villa, Marco Schiavoni and Laura Prati
Catal. Sci. Technol., 2012, Advance Article
DOI: 10.1039/C2CY00355D

Other interesting articles on nano-scale catalysis can also be found here.

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On Water Hydroformylation

19 Jan 2012

By Ruth Doherty, Deputy Editor.

Dieter Vogt and co-workers have shown that using water as co-solvent in rhodium-catalysed aldehyde hydrogenation under hydroformylation conditions enhances both rate and selectivity towards primary alcohols. Find out more about this cheap and cheerful advance in their recent Hot Article:

“On-water” rhodium-catalysed hydroformylation for the production of linear alcohols
Olivier Diebolt, Christian Müller and Dieter Vogt
Catal. Sci. Technol., 2012, DOI: 10.1039/C2CY00450J

Also of interest – further recent research from the Vogt group:

Recent advances in the recycling of homogeneous catalysts using membrane separation
Michèle Janssen, Christian Müller and Dieter Vogt
Green Chem., 2011, 13, 2247-2257
DOI: 10.1039/C1GC15264E, Critical Review
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C–H activation of 2,4,6-triphenylphosphinine: unprecedented formation of cyclometalated [(PC)Ir(III)] and [(PC)Rh(III)] complexes
Leen E. E. Broeckx, Martin Lutz, Dieter Vogt and Christian Müller
Chem. Commun., 2011, 47, 2003-2005
DOI: 10.1039/C0CC04660D, Communication

Molecular weight enlargement—a molecular approach to continuous homogeneous catalysis
Michèle Janssen, Christian Müller and Dieter Vogt
Dalton Trans., 2010, 39, 8403-8411
DOI: 10.1039/C0DT00175A, Perspective
From themed issue Bridging the gap in catalysis via multidisciplinary approaches

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Interview with Piet van Leeuwen

18 Jan 2012

By Ruth Doherty, Deputy Editor.

Piet van Leeuwen talks about how chemistry meets plumbing and ink can be a child’s toy………

Piet van Leeuwen is Editor-in-Chief of Catalysis Science & Technology and a Group Leader at ICIQ in Tarragona, Spain. Piet worked with Shell Amsterdam for twenty six years heading the section for basic research in homogeneous catalysis. He also initiated and led the homogeneous catalysis group at the University of Amsterdam as a Professor of Homogeneous Catalysis from 1989 until 2007. He held a chair of Industrial Homogeneous Catalysis at the Technical University of Eindhoven from 2001 till 2006, where he was also director of the National Research School Combination on Catalysis. Piet has authored 350 refereed articles and reviews, many book chapters, edited several books, and is author of a textbook on homogeneous catalysis. He has been at the ICIQ since 2004.

Why did you choose to work in the area of catalysis?
Originally, I chose to work for Shell. In this environment doing organometallic chemistry and coordination chemistry I learned that in the long term the new fundamental knowledge we were uncovering might be useful in catalysis. This idea appealed to me, and it still does. It is nice to combine exciting chemistry with future applications in sight.
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What projects are you working on at the moment?
We are working on nanoparticles – bringing together homogeneous and heterogeneous catalysis, bimetallic catalysis, and supramolecular catalysis!

You have worked in both industry and academia – how do these areas fit together in the field of catalysis and is the relationship changing?
Catalysis research has always been strongly linked to industry. Many catalysis research themes find their roots in industry and until two decades ago most inventions of new catalytic reactions stemmed from industrial research laboratories. There are no industrial research labs left that do long term research and this has shifted to universities aided by all sort of financial schemes. In the last two decades we have witnessed an enormous growth of catalysis within the realm of organic synthesis, which has enriched the life of catalysis scientists enormously. Many leading experts are pursuing vigorously applications of their systems and industry indeed has installed a large number of these. I am not writing a plea for “applied research”; curiosity driven research and serendipity remain indispensable ingredients for future inventions.

What role do you see for catalysis in our future?
Catalysis is here to stay! I don´t believe in mature sciences. Before we have completed our wish-list for today’s conversions a whole range of new feedstocks will be available requiring new clean, sustainable conversions. Many multistep syntheses can be improved with the aid of clever catalytic steps. A stronger integration of catalysis research and process engineering, also

for fine chemicals, can bring about important savings.

Welcome to the Catalysis Science & Technology Editorial Board! What excites you most about your new position of co-Editor-in-Chief?
Actually I was a little bit scared in the beginning, as it seemed risky to start a new journal! The RSC team did a fantastic job in starting up the journal. The web has changed the publishers´ way of doing this enormously. The next target, of course, is to get good marks in the polls, but we will get there!

What is your earliest recollection of chemistry and science?
Making ink with tannins and iron salts bought in the pharmacy. I also experimented with soldering!

What achievement are you most proud of?
I am proud of the many people who worked with me who did good things!I have a patent on a non-toxic soldering resin, the first use of dendrimers in catalysis, the bite angle story, mechanistic stories, “the” book, SPOs in catalysis, …..

What advice would you give to a young scientist?
Take a year’s sabbatical after your PhD defence as later you won’t have time for this! I took only half a year and it was easy to convince my two youngest children to take a year off after their Master.

What is your favourite place to be?
There are many exotic places where we can stay only for a short time. I am happy sitting on my terrace with a book and a drink, or another terrace eating tapas with friends! (This sounds more like Spain than the Netherlands!).

What would you do if you weren’t a scientist?
First I wanted to be a cook like my father, who started working in a kitchen as a teenager. Later when leaving primary school I made an appointment with the local plumber to start with him in September. My father was furious and told the plumber and me “no way”! I still would like to do both but being an organometallic chemist sounds like a good compromise!

Piet's cover of issue 3, 2011 Catal. Sci. & Technol.

More info on Piet’s own research can be found in some of his recent research articles:

SPOs as new ligands in Rh(III) catalyzed enantioselective transfer hydrogenation
Pascal M. Castro, Henrik Gulyás, Jordi Benet-Buchholz, Carles Bo, Zoraida Freixa and Piet W. N. M. van Leeuwen
Catal. Sci. Technol., 2011, 1, 401-407 DOI: 10.1039/C0CY00022A, Paper

Zn(II) Robson macrocycles as templates for chelating diphosphines
Sergio Ponsico, Henrik Gulyas, Marta Martínez-Belmonte, Eduardo C. Escudero-Adán, Zoraida Freixa and Piet W. N. M. van Leeuwen
Dalton Trans., 2011, 40, 10686-10697 DOI: 10.1039/C1DT10905G, Paper

An approach to bimetallic catalysts by ligand design
Josep M. López-Valbuena, Eduardo C. Escudero-Adan, Jordi Benet-Buchholz, Zoraida Freixa and Piet W. N. M. van Leeuwen
Dalton Trans., 2010, 39, 8560-8574 DOI: 10.1039/C0DT00011F, Paper

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Advances in catalysis at the nano-scale

16 Jan 2012

By Matthew Cude, Development Editor.

The ability to visualise and manipulate materials at the nano-scale has changed the way we think about all topics in science, including catalysis. There has been substantial research into the production, application and mechanisms of nano-catalysts given the industrial, economic and environmental benefits they can bring. A few interesting reviews from Catalysis Science & Technology which highlight such developments are listed below and are free to access for the duration of 2012.

Studying Fischer–Tropsch catalysts using transmission electron microscopy and model systems of nanoparticles on planar supports
P. C. Thüne, C. J. Weststrate, P. Moodley, A. M. Saib, J. van de Loosdrecht, J. T. Miller and J. W. Niemantsverdriet
Catal. Sci. Technol., 2011, 1, 689-697
DOI: 10.1039/C1CY00056J

Superparamagnetic nanoparticles for asymmetric catalysis—a perfect match
Kalluri V. S. Ranganath and Frank Glorius
Catal. Sci. Technol., 2011, 1, 13-22
DOI: 10.1039/C0CY00069H

Unique catalytic features of Ag nanoclusters for selective NOx reduction and green chemical reactions
Kenichi Shimizu, Kyoichi Sawabe and Atsushi Satsuma
Catal. Sci. Technol., 2011, 1, 331-341
DOI: 10.1039/C0CY00077A

Nanokinetics for nanocatalysis
Dmitry Yu. Murzin
Catal. Sci. Technol., 2011, 1, 380-384
DOI: 10.1039/C0CY00084A

Mimicking nature’s strategies for the design of nanocatalysts
Rohit Bhandari, Ryan Coppage and Marc R. Knecht
Catal. Sci. Technol., 2012, Advance Article
DOI: 10.1039/C1CY00350J

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HOT Article: “self-dosing” catalysts

10 Jan 2012

By Helen Lunn, Publishing Editor.

Compared to homogeneous catalysts, heterogeneous catalysts used in hydrosilylation reactions are quite rare. In this HOT article, the catalytic activity and recyclability of PtO₂ is examined for the hydrosilylation of n-octene with heptamethyltrisiloxane.

Compared to the usual homogeneous catalysts PtO₂ dissolves only to a small degree after reaction with silane. The un-reacted solid catalyst is then easily separated from the reaction mixture by simple decantation or filtration and so can be used for subsequent runs. The observation of an induction period in every cycle indicates that the active species is formed in situ before the reaction can take place and new material has to dissolve for each run.

The active species is formed by reduction of PtO₂ with the silane and is soluble in the reaction mixture. The solubility behavior together with the high activity allows a ‘‘self-dosing’’ of the catalyst—leading to little waste of precious metal in contrast to other ‘‘homogeneous’’ (i.e. better soluble) Pt-based catalysts making it potentially useful for industrial applications.

N-Heterocycles via zeolite catalysts

04 Jan 2012

By Matthew Cude, Development Editor.

N-Heterocycles are important in agrochemicals, pharmaceuticals, as solvents and reagents. The compounds are widely distributed in nature and the synthesis of specific N-heterocycles is a topic of great interest. This thorough review by V. V. Krishna Mohan Kandepi and Nama Narender examines the application of zeolite molecular sieves to produce a wide range of N-heterocyclic compounds. The authors discuss syntheses from pyridine to bis(indolyl)phenylmethane, an anti-oxidant useful in cancer prevention.

The advantages to using these shape selective acid catalysts include thermal stability, re-usability and they are environmentally friendly. To find out more access this Perspective for free in Catalysis Science & Technology, where all are articles are free to access for the duration of 2012.

Synthesis of N-heterocyclic compounds over zeolite molecular sieve catalysts: an approach towards green chemistry
V. V. Krishna Mohan Kandepi and Nama Narender
Catal. Sci. Technol., 2012, Advance Article
DOI: 10.1039/C2CY00162D, Perspective

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Catalysis Science & Technology Blog

Hot Article: Optimising Alkylation in Desilicated ZSM-5

Semiconductior supported gold in catalysis

FineCat 2012 – Symposium on catalysis for fine chemicals

Hot Perspective: Catalytic Supports

On Water Hydroformylation

Interview with Piet van Leeuwen

Advances in catalysis at the nano-scale

Top ten most accessed articles in November

HOT Article: “self-dosing” catalysts

N-Heterocycles via zeolite catalysts

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