Archive for the ‘Materials’ Category

A cloak of many carbons

Catalysts can be exceedingly useful in the real world, from treating our car’s exhaust fumes to creating fertilisers.  There are many ways to make catalysts and even multiple ways to make the same catalyst.  The path that you choose to a catalyst can have a significant impact on the quality of the end product.

Eloy del Rio and team from the Structure and Chemistry of Nanomaterials group at the University of Cadiz in Spain have investigated ceria-based oxide-supported gold catalysts for carbon monoxide oxidation.  The routine for depositing the metal phase onto the oxide support and the subsequent catalyst activation step can ultimately affect the activity of the catalyst.  Catalysts prepared by deposition-precipitation with urea followed by activation under oxidising conditions result in significantly more activity than those prepared under reducing conditions.

Variation in catalyst activity under oxidising and reducing activation protocols.

This had previously been observed by others, but the reason for the difference was never discussed.  The authors set out to find out why the activity differed.  They used a suite of nano-analytical and nano-structural techniques to probe the catalysts, finding that the catalyst prepared under reducing conditions had a coat of amorphous carbon which severely hampered the catalyst activity.  This could be removed by a re-oxidation treatment that burnt away the carbon layer and produced an active catalyst similar to the one produced under oxidising conditions.

The precipitating agent used in the synthesis can also influence the resulting activities of catalysts prepared via the deposition-precipitation method.  No difference between oxidising and reducing activations is observed when sodium carbonate is used in place of urea.

To read the details, check out the ChemComm article in full:

Dramatic effect of redox pre-treatments on the CO oxidation activity of Au/Ce0.50Tb0.12Zr0.38O2-x catalysts prepared by deposition-precipitation with urea: a nano-analytical and nano-structural study
E. del Rio, M. López-Haro, J.M. Cies, J.J. Delgado, J.J. Calvino, S. Trasobares, G. Blanco, M.A. Cauqui and S. Bernal
Chem. Commun., 2013, 49, Accepted Manuscript
DOI: 10.1039/C3CC42051e

Iain Larmour is a guest web writer for ChemComm.  He has researched a wide variety of topics during his years in the lab including nanostructured surfaces for water repellency and developing nanoparticle systems for bioanalysis by surface enhanced optical spectroscopies.  He currently works in science management with a focus on responses to climate change.  In his spare time he enjoys reading, photography and art.

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It’s getting hot in here…

Stimuli-responsive nanoparticles are the focus of much current research, and what could be better than a nanoparticle that responds to one stimulus?  A nanoparticle which responds to two or three.

Xianmao Lu and his team have coupled plasmonic silver nanoparticles to magnetic iron oxide nanoparticles and wrapped both in a thermoresponsive polymer – poly(n-isopropylacrylamide).

When illuminated by sunlight the silver nanoparticles absorb the light and convert it to heat.  The increase in temperature causes the polymer wrapping to collapse and reduces steric repulsion between the nanoparticle dimers leading to clustering.

Sunlight induced clustering of Magnetic-Plasmonic Heterodimers.

This clustering enhances the magnetic separation of the very small dimers from the solution (the nanoparticles are less than 9 nm each).  When you’ve caught the nanoparticles and are done with them, you can turn the lights off and they will re-disperse.

Don’t worry if you live in a cloudy part of the world, you can use a solar simulator to induce the clustering.  It would probably be easier to turn off than the sun, too.

To read the details, check out this HOT Chem Comm article in full:
Thermoresponsive Nanoparticles + Plasmonic Nanoparticles = Photoresponsive Heterodimers: Facile Synthesis and Sunlight-Induced Reversible Clustering
Hui Han, Jim Yang Lee and Xianmao Lu
Chem. Commun., 2013, 49, Accepted Manuscript
DOI: 10.1039/C3CC42273A

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Photocatalysis in a nanocup

Written by Geoff Nelson, web writer.

Nanocups of anatase TiO2 coated with Au nanoparticles are efficient photocatalysts, as reported in a recent ChemComm article by Chemical Science and Chem Soc Rev Advisory Board member Jinlong Gong and  his group at Tianjin University, China.

This new shape promises to increase reactive surface area by exposing the normally inaccessible surface of hollow spheres.  Compared to TiO2 hollow spheres, TiO2 nanocup particles increase the rate of the photocatalytic degradation of methylene blue in the visible light region by 46%.

This performance and the ease of nanocup synthesis are reasons to promote further research.  Thus, we may expect nanocups made from other metal oxides and inorganic materials to be incorporated into solar, photochemical, and catalytic applications in the future.

In addition, the ability of nanocups to confine small amounts of reactants may find utility in nanofluidic devices.

Gong et al.‘s work has recently been highlighted as part of a C&EN article on novel nanostructures.

Read this ChemComm article in full:

Mesoporous anatase TiO2 nanocups with plasmonic metal decoration for highly active visible-light photocatalysis

Jianwei Lu, Peng Zhang, Ang Li, Fengli Su, Tuo Wang, Yuan Liu and Jinlong Gong
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC42029A

Geoff Nelson is a guest web-writer for ChemComm.  He currently works as a post-doctoral research associate in Dr David Payne’s research group in the Department of Materials at Imperial College, London.  Geoff’s current research concerns the synthesis and characterization of post-transition metal oxides for use in the energy sector.  His other research interests include carbon-based materials, biophysical chemistry, and surface science.

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Metal organic frameworks for moisture-triggered fragrance release

The controlled release of fragrance molecules is of great interest in the development of fragranced products such as deodorants, as the volatility of the fragrance molecules can reduce the action of the product over time.  In this HOT ChemComm article, Jing Li and her group at Rutgers University, New Jersey have joined forces with researchers from Colgate-Palmolive Company to investigate using metal organic frameworks (MOFs) to take up and release fragrances in response to external stimuli.

frangrance release by MOFs

MOFs are a class of porous materials that are receiving a significant amount of research interest.  In particular, their ability to take up and store small molecules makes them an exciting prospect for storing gases, such as hydrogen, for catalysis and for drug delivery.

In this study, researchers examined the ability of some zinc based MOFs containing hydrophobic channels to take up and release the fragrances ethyl butyrate and D-limonene.  They found that the release of these fragrances could be triggered by moisture.

Importantly, both the hydrophilic ethyl butyrate and the hydrophobic D-limonene could be stored and released in this way, whereas leading encapsulation technologies based on modified starch are generally only useful for storing hydrophobic fragrances.  MOFs could therefore well find commercial applications for storing a wide range of fragrances.

Read this ‘HOT’ ChemComm article today!

Encapsulated recyclable porous materials: an effective moisture-triggered fragrance release system
John Vaughn, Haohan Wu, Bisera Efremovska, David H. Olson, Jairajh Mattai, Claudio Oritz, Allen Puchalski, Jing Li and Long Pan
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC41236A

Cally Haynes is a guest web-writer for ChemComm.  She is currently a post doctoral researcher  at the University of Southampton, and her research interests include the supramolecular chemistry of anions.  When not in the laboratory, she likes travelling and watching football.

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Nitrogen-containing graphene-like structures: Theory and experiment combine to reveal active sites

There is significant interest in nitrogen-containing electrocatalysts, driven by the need to find cost-effective and efficient material solutions for replacing platinum in polymer electrolyte membrane fuel cells.  However, the active sites of non-platinum group metal, oxygen reduction reaction electrocatalysts have been contentious for over 50 years.

Fortunately researchers are agreed that Metal(Me)-Nx centres may serve as possible active sites but whether it is Me-N2 or Me-N4 remains unresolved.  X-ray Photoelectron Spectroscopy (XPS) would be the ideal technique to answer this question if it didn’t rely on the use of reference spectra; none exist for the Me-N2 species which makes it less than ideal.

Fitting of DFT calculated curves to experimental results.

Kateryna Artyushkova, Plamen Atanassov and their team have overcome this problem by using density functional theory (DFT) to calculate the binding energy shifts of the species.  Calculating the binding energy shifts, rather than just the binding energies, allows the team to overcome the challenges associated with DFT calculations including; treatment of the core electrons and the poorly screened Coulomb potential near the nucleus.

Once validated, the DFT output can be used as input for XPS curve fitting.  This has revealed rearrangement around Cobalt-Nx centres in an oxidizing atmosphere and supports the understanding of these catalysts as vacancy-and-substitution defects in a graphene-like matrix.

This work demonstrates the synergy between experiment and theory which allows critical information to be extracted that might otherwise remain hidden.

For more, read this ChemComm article in full:

Density functional theory calculations of XPS binding energy shift for nitrogen-containing graphene-like structures
K. Artyushkova, B. Kiefer, B. Halevi, A. Knop-Gericke, R. Schlogl and P. Atanassov
Chem. Commun., 2013, 49, 2539-2541
DOI: 10.1039/C3CC40324F

Iain Larmour is a guest web-writer for ChemComm.  He has researched a wide variety of topics during his years in the lab including nanostructured surfaces for water repellency and developing nanoparticle systems for bioanalysis by surface enhanced optical spectroscopies.  He currently works in science management with a focus on responses to climate change.  In his spare time he enjoys reading and photography.

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Porous organic polymers filter toxins from the air

In a search for the next generation of filtration materials, for use in devices such as gas masks, a group of US scientists has synthesised a series of porous organic polymers (POPs) bearing metal-catecholate groups. By changing the molecular building blocks the researchers were able to tailor the materials to hydrogen bond to, and consequently remove, different toxins, such as ammonia.

POPs are very similar in nature to metal-organic frameworks (MOFs) but do not suffer from such instability, particularly towards water, making them ideal for use as filters in real-word environments.

Read this ‘HOT’ Communication now:

Removal of airborne toxic chemicals by porous organic polymers containing metal–catecholates
Mitchell H. Weston , Gregory W. Peterson , Matthew A. Browe , Paulette Jones , Omar K. Farha , Joseph T. Hupp and SonBinh T. Nguyen
Chem. Commun., 2013,49, 2995-2997

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Ready to order? Yes, I’ll have the extra cold superconducting penne, please…

Written by guest web-writer Kevin Murnaghan.

In this highly original work, researchers from the Complex Functional Materials Group at the University of Bristol and the Superconductivity and Magnetism Group at the University of Warwick have used off-the-shelf, supermarket pasta as a sacrificial template for the production of a variety of superconducting wires, tubes and spirals.  They have even made a superconducting ‘jolly roger’ skull and crossbones.

Here’s how: The pasta was pre-washed to remove impurities and then rehydrated in a solution containing a mixture of nitrates of yttrium, barium and copper. A slight excess of barium nitrate was used to make sure the desired superconducting material YBa2Cu2O7-x phase (Y123) was attained. Via a calcination process the superconducting pasta shapes were produced, removing the organic material of the sacrificial template and neatly retaining the macroscopic shape of the template.

C3CC38271K_graphical abstract

‘Chemical black pepper and parmesan’ were provided by the use of silver nitrate in the process, which boosts electrical and structural properties. Without using this salt, structures formed are brittle, but with it, compressive strength of the shapes doubled in strength from 0.76 to 1.56 MPa.  This helped counteract the effect of porosity formed from the outgassing of the sacrificial pasta during the calcination process.

Interestingly, the pasta had its own influence on the properties of the material.  Starch-mediated reduction of Ag(I) to Ag(0) is the reason for the dark colour of the materials formed, and trace transition metals in the foodstuff were found to have an effect on electrical and superconducting properties.

Critical temperatures, Tc and current densities, Jc, in early samples were found to be low, relative to typical Y123 type superconductors when silver was not included in the synthesis, and were markedly improved when it was.  Further improvements to the superconductivity of the spaghetti-based replicas were achieved via sintering and annealing.  This work represents a highly cost-effective route to a range of superconducting materials with macroscopic architectures, compared with current state of the art processes such as CVD or PLD.  Future work will focus, in part, on further densification of the product, and purity of the sacrificial template.  Further fascinating information is provided in the electronic supplementary information.  Buon appetito!

C3CC38271K_coverRead this ChemComm cover article today:

Designed 3D architectures of high-temperature superconductors

David C. Green, Martin R. Lees and Simon R. Hall
Chem. Commun., 2013,49, 2974-2976
DOI: 10.1039/C3CC38271K

Kevin Murnaghan is a guest web-writer for Chemical Communications. He is currently a Research Chemist in the Adhesive Technologies Business Sector of Henkel AG & Co. KGaA, based in Düsseldorf, Germany. His research interests focus primarily on enabling chemistries and technologies for next generation adhesives and surface treatments. Any views expressed here are his personal ones and not those of Henkel AG & Co. KGaA.

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11th International Conference on Materials Chemistry (MC11)– Registration now open!

We are delighted to announce that registration for the 11th International Conference on Materials Chemistry (MC11) is now open.

Why take part in this conference?

In the 20th year of this international Materials Chemistry conference series, this meeting will bring together researchers from across this exciting field to discuss four key areas of application of materials chemistry:

  • Energy Materials – including all aspects of Materials Chemistry related to energy generation, conversion and storage.
  • Environmental Materials – the design, synthesis and applications of materials that facilitate processes to provide a sustainable environment.
  • Biomaterials – materials for tissue engineering and healthcare, green biomaterials and advanced synthesis methods of biomaterials.
  • Electronic, Magnetic and Optical Materials – encompassing inorganic, organic, hybrid and nano materials, soft matter and interfaces.

Registering early guarantees you an early bird discount of £50 – so register now!  And you can showcase your own work by presenting a poster.

MC11 will appeal to academic and industrial scientists working on the chemistry, physics and materials science of functional materials.  Come and hear the best in the field and take advantage of many opportunities for discussion with other researchers in materials chemistry.

For more information visit: http://rsc.li/mc11

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Penny Brothers joins ChemComm as Associate Editor

ChemComm warmly welcomes Professor Penny Brothers (University of Auckland, New Zealand) as a new Associate Editor. 

Penny Brothers is now accepting submissions to ChemComm in the areas of porphyrin chemistry, the main group elements and organometallic chemistry.  Her current research interests also include the chemistry of new sustainable materials and inorganic medicinal chemistry. 

Submit your next top-notch, high-impact Communication to Penny Brother’s Editorial Office.

Biography

Penny Brothers was born and grew up in Auckland, New Zealand, and completed her BSc and MSc(Hons) degrees in chemistry at the University of Auckland.  In 1979 she was awarded a Fulbright Fellowship and set off for Stanford University to begin a PhD in chemistry under the supervision of Professor Jim Collman.  Her PhD thesis, and much of her subsequent research work, has centered around the chemistry of porphyrin complexes.Professor Penny Brothers

In 1986 she returned to Auckland and spent two years working as a postdoctoral fellow with Professor Warren Roper in the Department of Chemistry, focussing on organometallic chemistry.  In 1988 she took up her current academic position at the University of Auckland.

She has been a visiting scientist at Los Alamos National Laboratory (2003, 2005, 2006) and a visiting professor at the University of California at Davis (1993), the University of Heidelberg (2003) and the University of Burgundy (2004, 2006).  She has been awarded a Fulbright Senior Scholar Award for 2007.

Her current research brings together her interests in porphyrin chemistry, the main group elements and organometallic chemistry.  She investigates how the porphyrin ligand can be used to modify the chemistry of elements such as boron and bismuth, and as a ligand in complexes containing unusual chemical bonds between transition metal and main group elements.  She has a number of research collaborations in NZ and internationally.

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Liquid crystal relaxation controlled by dopant kinetics

Liquid crystals are an area of intense interest due to their potential use in smart materials such as displays. Cholesteric liquid crystals are of particular interest due to their helical nature and their ability to selectively reflect light over a narrow range of wavelengths. This range can be modified by the inclusion of photo-responsive dopants.  

Dopants include overcrowded alkenes which undergo a stable to unstable (cistrans) transition upon irradiation with UV light. This results in an unwinding and eventual inversion of the cholesteric helix. This is accompanied by a red-shift of the reflection band which then returns close to the original position. However, the handedness of the helix has changed, and therefore the polarization of the light has also changed.  

Helix inversion of a cholesteric liquid crystal.

An important parameter with all liquid crystals is their relaxation step which needs to be suitable for the envisioned application. Nathalie Katsonis and her team have studied cholesteric liquid crystals doped with overcrowded alkenes in an effort to find a general paradigm correlating relaxation kinetics with the rate of helix inversion.  

In their recent Communication, Katsonis’ group shows that the helix relaxation kinetics are fully determined by the kinetics of the light-sensitive dopants. The relaxation of the dopants from unstable to stable is unperturbed by the liquid crystalline environment.  

On the other hand, the presence of the dopants can dramatically accelerate helix inversion. Therefore the inversion can be time-programmed by judicious choice of the dopant. This opens up the great potential of fine tuning cholesteric liquid crystals for smart materials with sophisticated functions.  

For more, read this ‘HOT’ Chem Comm article in full:  

Time-programmed helix inversion in phototunable liquid crystals  

Sarah J. Aßhoff, Supitchaya Iamsaard, Alessandro Bosco, Jeroen J. L. M. Cornelissen, Ben L. Feringa and Nathalie Katsonis
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C2CC37161H
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