Helen Lunn, Publishing Editor – Catalysis Science & Technology Blog

Author Archive

Cleaner diesel engines – not just a pipe dream!

11 Apr 2013

Selective catalytic reduction (SCR) to date presents the most promising deNO_x technology for diesel engines. Removal of NO_x from diesel exhaust is problematic due to the wide temperature range (373–923 K) at which diesel engines operate. This is due to inefficient conversion at low temperature (below 423 K) with the commonly used ionic exchanged zeolites or low selectivity to N₂ with supported MnO_x catalysts.

In this HOT article, Tanaka et al. found that the temperature had a significant effect on the photocatalytic reactions in the gas phase over a TiO₂ photocatalyst with a maximum conversion of 84% (at GHSV 100,000 h^-1 and 433 K). The amount of NH₃ at high temperature was found to be key to a high NO conversion. The results provide evidence of the potential practicality of the use of photo-SCR for diesel engines.

Effects of reaction temperature on photocatalytic activity

Read more about these developments in photocatalysis by downloading the article now:

Effects of reaction temperature on the photocatalytic activity of photo-SCR of NO with NH₃ over a TiO₂ photocatalyst
Akira Yamamoto, Yuto Mizuno, Kentaro Teramura, Tetsuya Shishido and Tsunehiro Tanaka
Catal. Sci. Technol., 2013, Advance Article
DOI: 10.1039/C3CY00022B

This article is part of a themed issue on photocatalysis that is due to be published later this year.

You may also be interested in a perspective recently published by the same author on the subject:

A unique photo-activation mechanism by “in situ doping” for photo-assisted selective NO reduction with ammonia over TiO₂ and photooxidation of alcohols over Nb₂O₅
Tetsuya Shishido, Kentaro Teramura and Tsunehiro Tanaka
Catal. Sci. Technol., 2011, 1, 541-551
DOI: 10.1039/C1CY00104C, Perspective

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Metal oxide films as water oxidation catalysts

02 Apr 2013

Since hydrogen represents an alternative energy source to carbon-based fuel, there is a need to be able to split water using water oxidation catalysts (WOC) preferably by renewable energy sources such as sunlight. In this HOT article, the Spiccia group present a facile preparation of NiO_x films for use as WOC. These WOC films, deposited from macrocyclic Ni complexes in alkaline solution, were significantly more catalytically active at higher pH (12.9), therefore widening the range of conditions over which they can be deposited. Enhanced catalytic activity was also observed in visible light, indicating the films are electrochromic.

To learn more about these catalytic metal oxide films download the full paper now:

Anodic deposition of NiO_x water oxidation catalysts from macrocyclic nickel(II) complexes
Archana Singh, Shery L. Y. Chang, Rosalie K. Hocking, Udo Bach and Leone Spiccia
Catal. Sci. Technol., 2013, Advance Article
DOI: 10.1039/C3CY00017F

This article is part of a themed issue on photocatalysis that is due to be published later this year.

You may also be interested in:
Highly active nickel oxide water oxidation catalysts deposited from molecular complexes
Archana Singh, Shery L. Y. Chang, Rosalie K. Hocking, Udo Bach and Leone Spiccia
Energy Environ. Sci., 2013, 6, 579-586
DOI: 10.1039/C2EE23862D

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Alkene hydration breaks the rules

22 Mar 2013

Alkene hydration (the addition of water to a carbon double bond) is an important industrial process for the direct synthesis of alcohols, widely used as chemical intermediates for resins, agricultural chemicals, surfactants, etc. In an extension of their previous work which involved selective aromatic ring hydroxylation by water with a platinum-loaded titanium oxide photocatalyst, the Yoshida Group, applied this photocatalytic system to alkene hydration.

Hydration of alkenes followed the anti-Markovnikov rule

The Pt–TiO₂ photocatalyst efficiently promoted anti-Markovnikov hydration of various alkenes with high selectivity. A possible reaction mechanism is also discussed in detail based on experiment and molecular orbital calculations. The results should prove useful for designing novel photocatalysts for selective organic transformations.

Read more about these developments in photocatalytic research by downloading the full article now:

Anti-Markovnikov hydration of alkenes over platinum-loaded titanium oxide photocatalyst
Hayato Yuzawa, Shoko Yoneyama, Akihito Yamamoto, Masanori Aoki, Kazuko Otake, Hideaki Itoh and Hisao Yoshida
Catal. Sci. Technol., 2013, DOI: 10.1039/C3CY00019B

This article is part of a themed issue on photocatalysis that is due to be published later this year.

Also, check out the previous paper which sparked this research:

Photocatalytic hydroxylation of aromatic ring by using water as an oxidant
Hisao Yoshida, Hayato Yuzawa, Masanori Aoki, Kazuko Otake, Hideaki Itoh and Tadashi Hattori
Chem. Commun., 2008, 4634-4636
DOI: 10.1039/B811555A

And the latest work by this group:

Heterogeneous palladium catalyst hybridised with titanium oxide photocatalyst for direct C–C bond formation between aromatic ring and acetonitrile
Hisao Yoshida, Yuki Fujimura, Hayato Yuzawa, Jun Kumagai and Tomoko Yoshida
Chem. Commun., 2013, Accepted Manuscript
DOI: 10.1039/C3CC41068D

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Catalysts losing their nobility

13 Feb 2013

The emission of volatile organic compounds (VOCs) has has been a HOT topic in recent years due to their notorious implication in ozone layer depletion and the formation of ground level ozone. A specific type of VOC, Polycyclic Aromatic Hydrocarbons (PAHs) are also known to be carcinogenic. Catalytic oxidation has been utilised as one of the most effective ways to remove unwanted contaminants such as these, however, this usually involves expensive noble metals. In a move towards alternative materials such as metal-oxides, highly-active CeO₂ has recently been applied to reactions such as the above, CO oxidation and soot combustion – however, their widespread uptake by industry has been restricted by their poor thermal stability.

High thermal stability of ceria-based mixed oxide catalysts supported on zirconia for toluene combustion

Chen et al. have developed a simple, inexpensive and effective solution to the thermal stability problem, by loading mixed CeO₂-based oxides on ZrO₂. The catalytic combustion of toluene was studied and the ZrO₂ carrier was shown to not only to stabilise the surface active structure of the catalyst but also to improve its efficiency by enhancing O₂ mobility.

Read more about the potential of these catalysts by downloading the full article for FREE at:

High thermal stability of ceria-based mixed oxide catalysts supported on ZrO₂ for toluene combustion
Han-Feng Lu, Ying Zhou, Wen-Feng Han, Hai-Feng Huang and Yin-Fei Chen
Catal. Sci. Technol., 2013, Advance Article
DOI: 10.1039/C3CY20754D

You may also be interested in a related article:

High activity mesoporous copper doped cerium oxide catalysts for the total oxidation of polyaromatic hydrocarbon pollutants
Asunción Aranda, Elvira Aylón, Benjamín Solsona, Ramón Murillo, Ana María Mastral, David R. Sellick, Said Agouram, Tomás García and Stuart H. Taylor
Chem. Commun., 2012, 48, 4704–4706
DOI: 10.1039/C2CC31206A

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Nanoreactors for efficient oxidation

20 Dec 2012

Burri and co-workers describe the synthesis and application of new efficient mesoporous PdO/SBA-15 catalysts in this HOT article.

Oxidation of cyclohexene to cyclohexanone

The catalysts were reported to have a conversion and selectivity near 100% for the oxidation of cyclohexene to cyclohexenone. This high efficiency was attributed to the close contact with the reactive PdO nanoparticles as the reactants pass through the nanopores of the catalysts which thus may be considered as nanoreactors.

You can read more for FREE about these efficient oxidation nanoreactors at:

Highly efficient and expeditious PdO/SBA-15 catalysts for allylic oxidation of cyclohexene to cyclohexenone
Saidulu Ganji, Padma Bukya, Venkateswarlu Vakati, Kamaraju Seetha Rama Rao and David Raju Burri
Catal. Sci. Technol., 2013, Advance Article
DOI: 10.1039/C2CY20627G, Communication

You may also be interested in other catalysis articles by the same author:

A magnetically recoverable γ-Fe₂O₃ nanocatalyst for the synthesis of 2-phenylquinazolines under solvent-free conditions
Narani Anand, Kannapu Hari Prasad Reddy, Tirumalasetty Satyanarayana, Kamaraju Seetha Rama Rao and David Raju Burri
Catal. Sci. Technol., 2012, 2, 570-574
DOI: 10.1039/C1CY00341K, Paper

Highly active Cu/MgO catalysts for selective dehydrogenation of benzyl alcohol into benzaldehyde using neither O₂ nor H₂ acceptor
Ravi Kumar Marella, Chinna Krishna Prasad Neeli, Seetha Rama Rao Kamaraju and David Raju Burri
Catal. Sci. Technol., 2012, 2, 1833-1838
DOI: 10.1039/C2CY20222K, Communication

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Acid functionalized carbon nanotubes provide superior catalyst support

06 Sep 2012

Aerobic oxidation of benzyl alcohol in base-free aqueous solutions using acid-functionalized CNT as catalyst support

In this HOT Article, Yang et al have investigated the use of acid-functionalized carbon nanotubes (CNT) as a catalyst support for benzyl alcohol oxidation in a base-free aqueous solution under mild conditions.

CNT supported Pt-based bimetallic nanoparticles were synthesized by finely alloying Pt with Ru or Sn by microwave assisted polyol reduction (MAPR). The MAPR method was found to produce superior CNT supports compared to conventional methods of impregnation or deposition, yielding homogeneously dispersed particles with narrow size distribution and hence enhanced surface Pt exposure. Characterization results revealed the mechanism of action of Ru and Sn promoters on the catalysts: Ru reacted with the surface of the Pt-hydride species to liberate free Pt active sites whereas Sn enhanced electronic transfer.

Back to first principles for industry

27 Jul 2012

First-principles kinetic modeling in heterogeneous catalysis

This Perspective article by Reuter et al. focuses on the use of theoretical simulation tools based on ab initio calculations in heterogeneous catalysis –which to date have been rarely utilised by industry. The first half of the review covers state-of-the-art first principles-based kinetic modeling to encourage more widespread application in industry, the latter half then identifies the shortfalls of the modeling and attempts to identify areas in which more progress is needed.

For more information please read the full article for FREE at:

First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs
Maarten K. Sabbe, Marie-Françoise Reyniers and Karsten Reuter
Catal. Sci. Technol., 2012, Advance Article
DOI: 10.1039/C2CY20261A

Also of interest may be:

A first-principles theoretical approach to heterogeneous nanocatalysis
Fabio R. Negreiros, Edoardo Aprà, Giovanni Barcaro, Luca Sementa, Stefan Vajda and Alessandro Fortunelli
Nanoscale, 2012, 4, 1208–1219
DOI: 10.1039/C1NR11051A

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Asymmetric synthesis of chiral nonsteroidal anti-inflammatory drugs (NSAIDs)

23 Jul 2012

Advanced asymmetric synthesis of chiral nonsteroidal anti-inflammatory drugs

In this HOT article, Shiina and co-workers extend their previous work to describe a Dynamic Kinetic Resolution (DKR) of 2-arylpropionic acids, which are used widely as drugs. By careful study and optimization of the reaction conditions the DKR protocol was found to be applicable to a wide range of substrates and the preparation of (S)-ibuprofen is given as an example.

Read more for FREE about this exciting new protocol at:

Non-enzymatic dynamic kinetic resolution of racemic α-arylalkanoic acids: an advanced asymmetric synthesis of chiral nonsteroidal anti-inflammatory drugs (NSAIDs)
Isamu Shiina, Keisuke Ono and Kenya Nakata
Catal. Sci. Technol., 2012, Advance Article
DOI: 10.1039/C2CY20329D

Also of interest:

(R)-(+)-N-Methylbenzoguanidine ((R)-NMBG) catalyzed kinetic resolution of racemic secondary benzylic alcohols with free carboxylic acids by asymmetric esterification
Kenya Nakata and Isamu Shiina
Org. Biomol. Chem., 2011, 9, 7092-7096
DOI: 10.1039/C1OB05736G

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In catalysis, size matters

05 Jul 2012

Titania support dried at 120 °C

In this HOT article, Hutchings et al. investigate the effect of heat treatment to vary the metal particle size (2–20 nm) in Au-core–Pd-shell catalysts. They found that an “optimum size” is required for benzyl alcohol oxidation and hydrogen peroxide synthesis. A mild heat treatment (200 °C) also improved catalytic performance in addition to optimising the heat treatment process.

Green ionic liquids for sugar fatty acid ester biosynthesis

27 Apr 2012

sugar fatty acid synthesis In this Perspective, the use of ionic liquids as alternative reaction media to traditional organic solvents for the biosynthesis of sugar fatty acids esters is explored. Sugar fatty acids are extremely important industrially as non-ionic surfactants in a wide range of applications in food, cosmetics and pharmaceuticals.

Catalysis Science & Technology Blog