Author Archive

Hot Article: Highly transparent mixed electron and proton conducting polymer membranes

Highly transparent mixed electron and proton conducting polymer membranesUS researchers have made a transparent membrane that is highly electron and proton conductive.

Transparent materials with both ionic and electrical conductivity and mixed conducting properties are used in devices which require a membrane with both electrical and protonic conductivity but minimal light absorption– such as some water splitting solar cells. Blending conjugated polymers is one approach to achieve electrical and ionic conductivity; however, polymer membranes formed from blending two polymers often suffer from poor mechanical properties and polymer phase separation.

In this hot paper Paula T. Hammond and co-workers at Massachusetts Institute of Technology, USA, demonstrate that they can tune the ionic conductivity, the electrical, optical, and mechanical properties of PEDOT:sPPO by changing the composition ratio and by DMSO treatment. The polymer thin films become more transparent, smoother, softer, and exhibit higher proton conductivity as the sPPO ratio in PEDOT:sPPO is increased. After DMSO treatment, the polymer electrical conductivity dramatically increased without jeopardizing the protonic conductivity.

Highly transparent mixed electron and proton conducting polymer membranes: Junying Liu, Nicole R. Davis, David S. Liu and Paula T. Hammond, J. Mater. Chem., 2012, DOI: 10.1039/C2JM32296J (Advance Article)

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This week’s hot papers – Read for free until 2nd August

Electrothermally driven structural colour based on liquid crystal elastomers Electrothermally driven structural colour based on liquid crystal elastomers
Photonic crystal structures offer tremendous potential for use in a range of applications such as optical transistors and waveguides, data storage media, and chemical sensors. Liquid crystals are good candidates to form tunable photonic crystals because they can show optical anisotropy and their refractive index can be changed by an external electric field or temperature change; however, in most cases, liquid crystals are not used as inverse opaline materials directly, but instead, infiltrated into the voids of the inverse opaline films– which limits their suitability for some applications. In this hot paper a new type of electrothermally driven photonic crystal based on liquid crystal elastomers is reported, and its optical properties driven by voltage are described. The authors say this is the first example where a pure liquid crystal elastomer is introduced into photonic crystals as an inverse opaline structure material. (J. Mater. Chem., 2012, 22, 11943-11949)

Origin of long-range orientational pore ordering in anodic films on aluminium Origin of long-range orientational pore ordering in anodic films on aluminium
Porous anodic aluminium oxide has long been used for colouring and to prevent corrosion. It’s now also finding uses in hi-tech nanostructured devices such as gas sensors, nanocapacitors and microcantilevers. In this hot paper Kirill S. Napolskii and co-workers at Lomonosov Moscow State University show that the long range in-plane orientational pore ordering originates from the anisotropy of oxidation rates of the substrate during the anodization process. This finding offers a new approach for tailoring and controlling the in-plane orientational pore ordering by crystallographic manipulation with the Al substrate. (J. Mater. Chem., 2012, 22, 11922-11926)

A chiral co-crystalline form of poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) A chiral co-crystalline form of poly(2,6-dimethyl-1,4-phenylene)oxide (PPO)
The crystalline structure of an industrially relevant specialty polymer, poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) is resolved for the first time in this hot paper. The structure is a co-crystalline structure of the polymer with a chiral guest molecule (α-pinene), exhibiting a 2/1 monomer-unit–guest molar ratio. The authors say the most striking feature of this co-crystalline structure is its chirality. (J. Mater. Chem., 2012, 22, 11672-11680)

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Challenges in Nanoscience (ISACS9), 31 August – 3 September 2012, China

Don’t miss your chance to be part of the 9th conference in the International Symposia on Advancing the Chemical Sciences (ISACS) series – Challenges in Nanoscience (ISACS9).

Deadlines are fast approaching, so be sure to showcase your work by submitting a poster and take advantage of the reduced early bird registration rate before Friday 6 July 2012.

For further details on this significant event, please visit the dedicated webpage.

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Three Hot Reviews – Read them for free for 4 weeks

Highlight
Recent advances in high mobility donor–acceptor semiconducting polymers
Laure Biniek, Bob C. Schroeder, Christian B. Nielsen and Iain McCulloch, J. Mater. Chem., 2012, DOI: 10.1039/C2JM31943H (Advance Article)

Recent advances in high mobility donor–acceptor semiconducting polymers

Click here to see all three reviews

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A trio of hot papers

Electrochemical sensing by surface-immobilized poly(ferrocenylsilane) graftsElectrochemical sensing by surface-immobilized poly(ferrocenylsilane) grafts
Xiaofeng Sui ,  Xueling Feng ,  Jing Song ,  Mark A. Hempenius and G. Julius Vancso
J. Mater. Chem., 2012,22, 11261-11267

Poly(ferrocenylsilane) based materials have useful redox characteristics that make them suitable for the electrochemical detection of biological analytes; however, only a few accounts of covalently surface-tethered poly(ferrocenylsilane) films have been reported in the literature. In this hot paper chemically modified electrodes, decorated with covalently tethered poly(ferrocenylsilane) chains are fabricated. Led by G. Julius Vancso the team employed a “grafting to” approach for the covalent attachment of PFS chains to an electrode surface using amine alkylation reactions. Using this technique the team fabricated an ascorbic acid electrochemical sensor which showed high sensitivity and a stable response.

Incorporation of fused tetrathiafulvalene units in a DPP–terthiophene copolymer for air stable solution processable organic field effect transistors Incorporation of fused tetrathiafulvalene units in a DPP–terthiophene copolymer for air stable solution processable organic field effect transistors
Diego Cortizo-Lacalle ,  Sasikumar Arumugam ,  Saadeldin E. T. Elmasly ,  Alexander L. Kanibolotsky ,  Neil J. Findlay ,  Anto Regis Inigo and Peter J. Skabara
J. Mater. Chem., 2012, 22, 11310-11315

In this hot paper a team led by Anto Regis Inigo & Peter J. Skabara report the synthesis and properties of a new polymer p(DPP-TTF) featuring a fused thieno-TTF unit that has been copolymerised with a dithieno-DPP derivative. Bottom gate/bottom contact field effect transistors were fabricated from films of p(DPP-TTF). The transistors showed excellent air-stability which the team attribute to the incorporation of the TTF unit into the polymer.

Frozen polymerization for aligned porous structures with enhanced mechanical stability, conductivity, and as stationary phase for HPLCFrozen polymerization for aligned porous structures with enhanced mechanical stability, conductivity, and as stationary phase for HPLC
Michael Barrow ,  Ali Eltmimi ,  Adham Ahmed ,  Peter Myers and Haifei Zhang
J. Mater. Chem., 2012,22, 11615-11620

Ice templating is a simple and versatile route to prepare a wide range of porous materials. In general, a solution or colloidal suspension is frozen prior to the removal of ice crystals by freeze drying– which leaves a porous structures; however, the structures produced are often fragile and mechanically weak. In this hot paper a directional freezing and frozen polymerization method is developed to prepare crosslinked aligned porous polymers with improved mechanical stability. In the process monomer solutions are directionally frozen in liquid nitrogen to orientate the growth of solvent crystals after which the frozen samples are polymerized by UV irradiation. Removal of the solvent under vacuum produces the aligned porous structure. The team behind the research say the mechanical stability is improved by two orders of magnitude compared to similar materials produced using a freeze-dried process. The team also showed the resulting materials can be modified with graphene and a conducting polymer.

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Author Profile: Andrew Grimsdale

Andrew GrimsdaleAndrew Grimsdale was born in Waiouru, New Zealand in 1963 and received his Ph.D. from the University of Auckland, in 1990 under the supervision of Prof. R. C. Cambie. After postdoctoral research into materials for optoelectronic applications with Prof. Andrew Pelter at University of Wales, Swansea, and Prof. Andrew Holmes at the University of Cambridge, he was project leader in charge of research into conjugated polymers in the group of Prof. Klaus Müllen at Mainz from 1999-2005. After working again with Prof. Holmes at University of Melbourne, he joined the faculty of Nanyang Technological University in November 2006, as an Assistant Professor in the School of Materials Science and Engineering. His current research interests are the synthesis of materials for optoelectronic applications and on the formation of functional nanomaterials by self-assembly. He is the author of over 100 publications (>6800 citations, h-index 35) including some major reviews on the synthesis and applications of conjugated polymers and organic nanomaterials.

1. Which research projects are you working on at the moment?
I am working on a number of projects related to energy storage and conversion, which is a major focus of research here in Singapore, as it is a country currently almost totally dependent upon imported energy supplies. I am involved in one industry funded project on developing new materials for organic solar cells. I am collaborating with two projects on batteries including new types of batteries and new materials for existing types. I am also part of a big project on trying to understand the working principles of and optimise the design of light-harvesting systems, which has obvious implications for organic photovoltaic devices and also to related areas such as solar fuels. In relation to these projects I am not just interested in making classical polymers and oligomers but also in investigating the use of self-assembly to make functional materials including nanocomposite materials. Finally I am part of a project on developing new anti-fouling coatings for ships – it is amazing how much fuel can be saved by preventing things like barnacles from growing on the sides of ships, and it is fascinating to think that an understanding of how mollusc proteins bind to surfaces could be useful for fighting global warming.

Read the full interview

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Kitchen sponge used as platform for energy device

Scientists in Saudi Arabia have used a kitchen sponge as an electrode platform for supercapacitor devices. The MnO2–carbon nanotube–sponge supercapacitor electrode demonstrates reasonably good electrochemical performance in both aqueous and organic electrolytes, they say.

Compared to aqueous electrolytes, the energy density of supercapacitors in 1M Et4NBF4 tripled and the value was improved six-fold when using 1M LiClO4 as the electrolyte. The team behind the research also said that the cycling performance in organic electrolytes was inferior to aqueous electrolytes, but the devices in organic electrolytes retained a significant energy density advantage even after 10,000 cycles. (Read the article for free until the 5th July)

High energy density supercapacitors using macroporous kitchen sponges: Wei Chen, Rakhi Raghavanbaby and Husam N Alshareef, J. Mater. Chem., 2012, DOI: 10.1039/C2JM32030D

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This Week’s Hot Papers: aggregation-induced emission, photonic anti-counterfeiting and Pickering emulsions

Graphical abstract: Synthesis and self-assembly of tetraphenylethene and biphenyl based AIE-active triazoles

Synthesis and self-assembly of tetraphenylethene and biphenyl based AIE-active triazoles:
Wang Zhang Yuan,  Faisal Mahtab,  Yongyang Gong,  Zhen-Qiang Yu,  Ping Lu,  Youhong Tang,  Jacky W. Y. Lam,  Caizhen Zhu and Ben Zhong Tang, J. Mater. Chem., 2012, 22, 10472-10479.

Aggregation-caused quenching effects are often encountered when luminophores are condensed and aggregated. This hot paper reports a new family of luminophors which can be easily fabricated into high efficiency fluorescent helical nanofibers that show aggregation-induced emission. The biphenyl and TPE-containing luminogens are practically nonluminescent in solution, but become highly fluorescent when aggregated as nanosuspensions, solid powders, or thin films.

Photonic anti-counterfeiting using structural colors derived from magnetic-responsive photonic crystals with double photonic bandgap heterostructures

Photonic anti-counterfeiting using structural colors derived from magnetic-responsive photonic crystals with double photonic bandgap heterostructures:
Haibo Hu ,  Qian-Wang Chen ,  Jian Tang ,  Xian-Yi Hu and Xu-Hui Zhou, J. Mater. Chem., 2012, 22, 11048-11053.

A simple and low-cost method to fabricate photonic crystals with double photonic band-gap hetero-structures is reported by Chinese scientists. These photonic crystals could be suitable for use in anti-counterfeiting measures as they are more difficult to imitate than chemical dyes and pigments. Using a magnetic-induced self-assembly technique the team were able to create a range of structural colours.

Preparation of Pickering emulsions and colloidosomes using either a glycerol-functionalised silica sol or core–shell polymer/silica nanocomposite particlesPreparation of Pickering emulsions and colloidosomes using either a glycerol-functionalised silica sol or core–shell polymer/silica nanocomposite particles:
Lee A. Fielding and Steven P. Armes, J. Mater. Chem., 2012, 22, 11235-11244.

Microcapsules with shells constructed from colloidal particles have been widely reported; however, there are few reports on the formation of stable colloidosomes using solely nano-sized silica or polymer/silica nanocomposite particles using cross-linking chemistry. In this hot paper a glycerol-functionalised colloidal silica sol and core–shell polymer/silica nanocomposite particles are used to prepare oil-in-water Pickering emulsions.

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Author Profile: Ram Seshadri

Ram SeshadriSeshadri is a professor of Materials and a Professor in the Department of Chemistry and Biochemistry at the University of California, Santa Barbara (UCSB). He received his BS degree in chemistry from St. Stephens College, Delhi, in 1989, and his PhD degree in solid state chemistry from the Indian Institute of Science, Bangalore, in 1995. After some years as a postdoctoral fellow in Caen, France, and Mainz, Germany, he started a faculty career as an assistant professor in Bangalore in 1999, before moving to UCSB in 2002. Seshadri’s research program addresses structure-composition-property relations in functional inorganic materials, focusing currently on magnetic and correlated materials, catalysts, and phosphors.

1.      Which research projects are you working on at the moment?
This is an exciting time in our research. We continue to look at magnetic properties of oxides, and have added intermetallics to the list of materials. We also have an active and continuing program in phosphors for solid state lighting, and materials for heterogeneous catalysis. Newer avenues include thermoelectrics and batteries.

2.      What motivated you to focus on functional solid state materials?
Love at first sight. I started researching the chemistry and physics of solids — specifically carrying our redox titrations of high-temperature copper oxide superconductors — under the guidance of Professor C. N. R. Rao FRS, whilst an undergraduate, and I continue to be both fascinated and ignorant in the area. I will quit researching solids when I understand them, which is likely never!

3.      What are the hot topics in materials chemistry at the moment?
Materials for processes related to energy conversion and energy efficiency.

4.      What current problem would you like to see science provide a solution to?
I would love to see an understanding of high-temperature superconductors.

5.      What do you find to be the most rewarding aspect of your career?
Working with smart students at a great institution (UC Santa Barbara).

6.      What’s the secret to being a successful scientist?
I wish I knew. I do know how to be a happy scientist – work on things you don’t understand, but wish to.

7.      Which scientist past or present do you most admire?
Helen Megaw (1907-2002). Everything I do traces back to her in some way. An unsung hero of materials science.

8.      If you weren’t a scientist, what would you be?
I am a third-generation scientist. To even think of alternate careers is tantamount to apostasy.

If you’re interested to learn more about research in the Seshadri lab you can read a selection of papers below or check out their research pages on the group website.

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A trio of hot papers: Sequestering oil from emulsions, reducing graphene oxide & simulating Li ion batteries

Sequestration of edible oil from emulsions using new single and double layered microcapsules from plant spores Sequestration of edible oil from emulsions using new single and double layered microcapsules from plant spores

Microcapsules developed from modified plant spores can sequester efficiently edible oils from oil-in-water emulsions. The microcapsules contain either a single layered shell or double layered shell and are modified by converting their surface hydroxyl groups (alcohols, phenols carboxylic acids) into salts (Na+ and K+), acetates and methyl ethers. (J. Mater. Chem., 2012, 22, 9767-9773)

Chemical reduction of an aqueous suspension of graphene oxide by nascent hydrogenChemical reduction of an aqueous suspension of graphene oxide by nascent hydrogen

South Korean scientists have shown that nascent hydrogen can effectively reduce graphene oxide. Using a combination of X-ray photoelectron spectroscopy and thermogravimetric analysis they demonstrate that most of the labile oxygen functional groups were removed during nascent hydrogen reduction. Compared to other reducing agents the use of low cost, non-toxic metals for nascent hydrogen reduction is a promising method for bulk preparation of high quality reduced graphene oxide. (J. Mater. Chem., 2012, 22, 10530-10536)

Structural requirements for fast lithium ion migration in Li10GeP2S12 Structural requirements for fast lithium ion migration in Li10GeP2S12

Developing high performance electrolytes that combine fast lithium ion conductivity with electrochemical stability and safety is one of the challenges facing scientists creating the next generation of batteries. In this hot article atomistic molecular dynamics simulations shed new light on the dynamic lithium distribution, structural stability and ion transport mechanism in the ultrafast ion conductor Li10GeP2S12. (J. Mater. Chem., 2012, 22, 7687-7691)

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