Journal of Materials Chemistrywww.rsc.org/materials

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IN THIS ISSUE

ISSN 0959-9428 CODEN JMACEP 20(20) 3997–4232 (2010)

CoverSee K.-C. Huang et al.,pp. 4067–4073.Multi-wall carbon nanotubeshybridizing with platinumnanoparticles provide a superiorcatalytic ability as the counterelectrode in dye-sensitized solarcells.Image reproduced by permissionof Kuo-Chuan Ho fromJ. Mater. Chem., 2010, 20, 4067.

This journal is ª The Royal Society

of Chemistry 2010

Inside coverSee A. J. Gmitter et al.,pp. 4149–4161.Depiction of a BiF3 / mixedconducting matrixnanocomposite before (left) andafter (right) conversion to a Bi/LiFsub nanocomposite duringdischarge in a lithium battery.Artwork credit: Amy Amatucci,Graphic Designer.Image reproduced by permissionof Andrew J. Gmitter fromJ. Mater. Chem., 2010, 20, 4149.

J. Mater. Ch

HIGHLIGHT

4009

Porous Si anode materials for lithium rechargeablebatteries

Jaephil Cho*

When porous particles contain ordered pores, these pores act asa buffer layer for volume changes, demonstrating another meansof controlling the volume expansion/contraction. These porousparticles demonstrate that the degree of the volume change canbe effectively reduced to utilize its application in anode materials.

FEATURE ARTICLE

4015

Perovskite oxide nanotubes: synthesis, structural

characterization, properties and applications

Xinhua Zhu,* Zhiguo Liu and Naiben Ming

A Sawyer–Tower circuit is used to measure the P–E hysteresisloops of PZT nanotube arrays @100 kHz with applied voltagesbetween 4 and 10 V.

em., 2010, 20, 3999–4008 | 3999

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Journal of Materials Chemistry (print: ISSN 0959-9428; electronic: ISSN 1364-5501) is published 48 times a year by the Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge, UK CB4 0WF. All orders, with cheques made payable to the Royal Society of Chemistry, should be sent to RSC Distribution Services, c/o Portland Customer Services, Commerce Way, Colchester, Essex, UK CO2 8HP. Tel +44 (0)1206 226050; E-mail sales@rscdistribution.org

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Journal of Materials Chemistrywww.rsc.org/materialsJournal of Materials Chemistry is a weekly, international journal that publishes high impact original research that demonstrates novelty and advance, either in the chemistry used to produce materials or in the properties and applications of the materials produced. Coverage of the field is broad and includes the design and synthesis of materials, their characterization, modelling, properties and applications.

EDITORIAL BOARD

ChairGeorge Malliaras, Provence, France

Associate editors for North America

Vincent Rotello, Massachusetts, USARam Seshadri, Santa Barbara, USA

Associate editor for JapanTomiki Ikeda, Tokyo Institute of

Technology, Japan

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Royal Society of Chemistry: Registered Charity No. 207890.

20TH ANNIVERSARY ARTICLE

4031

Chemical routes to chalcogenide materials as thin films or

particles with critical dimensions with the order of

nanometres

Mohammad Afzaal, Mohammad Azad Malikand Paul O’Brien*

Single-source precursors to inorganic materials as thin films andnanocrystals are illustrated and discussed.

This journal is ª The Royal Society of Chemistry 2010

COMMUNICATIONS

4041

A novel architectured negative electrode based on titania

nanotube and iron oxide nanowire composites for Li-ion

microbatteries

Gregorio F. Ortiz, Ilie Hanzu, Pedro Lavela, Jos�e L. Tirado,Philippe Knauth and Thierry Djenizian*

A nanocomposite material based on iron oxide nanowires andtitania nanotubes is grown by electrochemical techniques. Theperformance of this novel nano-architectured electrode may beinteresting for potential applications as anodes for 3D Li-ionmicrobatteries.

4047

Hybrid organic-inorganic light emitting diodes: effect of the

metal oxide

H. J. Bolink,* H. Brine, E. Coronado and M. Sessolo

Efficient hybrid organic-inorganic light emitting diodes(HyLEDs) were obtained using HfO2 and MgO; the currentdensity and the efficacy are directly related to the bandgap of themetal oxide.

4050

Visible-light C–heteroatom bond cleavage and

detoxification of chemical warfare agents using

titania-supported gold nanoparticles as photocatalyst

Sxtefan Neatxu, Bogdan Cojocaru, Vasile I. Parvulescu,*

Vasile Sxomoghi, Mercedes Alvaroand Hermenegildo Garcia*

Gold nanoparticles supported on titania are able to effect thedetoxification of soman and VX nerve agents and mustard gasvesicant agent upon visible light illumination.

J. Mater. Chem., 2010, 20, 3999–4008 | 4001

www.MACRO2010.orgRegistered Charity Number 207890

MACRO2010 43rd IUPAC World Polymer Congress Polymer Science in the Service of Society

11 - 16 July 2010SECC, Glasgow, UK

‘Macro2010’ is the latest in the series of the biennial meetings of the IUPAC Polymer Division. With a history spanning several decades, this is the largest international multi-symposium conference dedicated to all aspects of polymer science and engineering.

Themes

Delivering New Polymers for Service in Society: Advances in Polymer Chemistry

Molecular to Macroscopic Behaviour of Polymers

Sustainability: Renewable Resources and Environmentally-Friendly Polymers

Polymers in Support of Life

Functional Polymers for Electronics, Energy and Analysis

Polymer Science in Everyday Life

Advances in Colloidal and Nanosize Polymer Materials

Young Polymer Scientists: Contributions, Nurturing and Networking

A more detailed list of topics and invited speakers are published on our regularly updated website www.MACRO2010.org.

Confirmed Plenary Speakers

Professor Jean M J Fréchet University of California, Berkeley, USA

Professor Sir Richard Friend, FRSUniversity of Cambridge, UK

Professor Ming JiangFudan University, China

Professor Laura KiesslingUniversity of Wisconsin-Madison, USA

Professor Kiyohito KoyamaYamagata University, Japan

Professor Ludwik LeiblerESPCI CNRS, Paris, France

Register Now!

Take advantage of available discounts by registering early. Book your place at www.MACRO2010.org

Sponsorship and Exhibition

Promote your organisation at the congress – contact us at macro2010@rsc.org for more details

PAPERS

4055

Phase-separation and mixing in thin films of co-deposited

rod-like conjugated molecules

J€orn-Oliver Vogel, Ingo Salzmann, Steffen Duhm,Martin Oehzelt, J€urgen P. Rabe and Norbert Koch*

The co-deposition of rod-like conjugated molecules withsimilarly sized conjugated cores leads to an intimate mixing ofthe two components, whereas dissimilarly sized conjugated coreslead to phase separation.

This journal is ª The Royal Society of Chemistry 2010

4067

A high performance dye-sensitized solar cell with a novel

nanocomposite film of PtNP/MWCNT on the counter

electrode

Kuan-Chieh Huang, Ying-Chiao Wang, Rui-Xuan Dong,Wei-Cheng Tsai, Keng-Wei Tsai, Chun-Chieh Wang,You-Han Chen, R. Vittal, Jiang-Jen Lin*

and Kuo-Chuan Ho*

A DSSC based on a novel semi-transparent PtNP/MWCNTcounter electrode, fabricated using a synthesized poly(oxyethylene)-segmented imide (POEM), exhibited a high cell efficiency of 8%.

4074

Nonlinear optical activity in dipolar organic–lanthanide

complexes

Ga-Lai Law, Ka-Leung Wong, Kok-Kin Lau, Sze-to Lap,Peter A. Tanner,* Fonchu Kuo and Wing-Tak Wong*

The crystal structures, linear and nonlinear optical properties ofa series of fifteen dipolar polymeric lanthanide complexes oftrans-cinnamic acid, [Ln(C9H7O2)3]n, are presented. The SHGparameters show maximum values near the center of thelanthanide series.

4080

A facile approach towards optically isotropic, colorless, and

thermoplastic polyimidothioethers with high refractive

index

Hung-Ju Yen and Guey-Sheng Liou*

A series of novel optically isotropic, transparent, andthermoplastic polyimidothioethers (PITEs) with high refractiveindex were prepared via Michael polyaddition fromcommercially available bismaleimides and dithiols. These PITEsnot only have a useful thermal processing window but alsoexhibit a high refractive index and ultra-low birefringence.

J. Mater. Chem., 2010, 20, 3999–4008 | 4003

PAPERS

4085

4094

4004 | J. Mater. Chem., 2010, 20, 3999–4008

Chiral-mesoporous-polypyrrole nanoparticles: Its chiral

recognition abilities and use in enantioselective separation

Pradip Paik, Aharon Gedanken* and Yitzhak Mastai*

Chiral-mesoporous-polypyrrole (CMPPy) nanoparticles weresynthesized by templating chiral block copolymers, whichshowed selective chiral recognition abilities and preferablyadsorbed the molecules templated with similar chirality, and areuseful for chiral separation.

Fabrication of multi-pitched photonic structure in

cholesteric liquid crystals based on a polymer template withhelical structure

Jinbao Guo, Hao Wu, Fengjin Chen, Lipei Zhang, Wanli He,Huai Yang and Jie Wei*

A novel method for fabricating a single-layer Ch-LC film withmulti-pitched photonic structure by utilizing a polymer templateand various types of Ch-LC for photonic materials applicationswas demonstrated.

4103

4116

In situ neutron diffraction study of the high-temperature

redox chemistry of Ln3�xSr1+xCrNiO8�d (Ln ¼ La, Nd)

under hydrogen

Florent Tonus, Mona Bahout,* Peter D. Battle,*

Thomas Hansen, Paul F. Henry and Thierry Roisnel

The composition and structure of the potential fuel-cellelectrodes Ln3�xSr1+xCrNiO8�d (Ln ¼ La, Nd) have beenstudied under H2 at up to 700 �C by in situ neutron powderdiffraction.

High efficiency amine functionalization of cycloolefin

polymer surfaces for biodiagnostics

Ram P. Gandhiraman,* Cedric Volcke, Vladimir Gubala,Colin Doyle, Lourdes Basabe-Desmonts, Christian Dotzler,Michael F. Toney, Marcello Iacono, Robert I. Nooney,Stephen Daniels, Bryony James and David E. Williams

Amine functional coatings have been deposited on cycloolefinicpolymer biosensor platform by plasma enhanced chemicalvapour deposition. The ability of the coating to covalently bindthe biological molecules with reduced non-specific binding andlowered limit of detection has been demonstrated.

This journal is ª The Royal Society of Chemistry 2010

PAPERS

4128

Controllable growth of highly N-doped carbon nanotubes

from imidazole: a structural, spectroscopic and field

emission study

Kaushik Ghosh, Mukul Kumar,* Takahiro Maruyamaand Yoshinori Ando

A record high N-doping level of 25.7 at% has been achieved inCNx nanotubes grown by thermal CVD (850 �C) of imidazole(a dual precursor of carbon and nitrogen).

This journal is ª The Royal Society of Chemistry 2010

4135

Facile synthesis of a new class of aggregation-induced

emission materials derived from triphenylethylene

Bingjia Xu, Zhenguo Chi,* Zhiyong Yang, Jingbo Chen,Shaozhi Deng, Haiyin Li, Xiaofang Li, Yi Zhang,Ningsheng Xu and Jiarui Xu*

Triphenylethylene derivatives with propeller-like cores werefacilely synthesized as a new class of aggregation-inducedemission materials.

4142

The structure of metallo-supramolecular polyelectrolytes in

solution and on surfaces

Guntram Schwarz,* Torsten K. Sievers, Yves Bodenthin,Iris Hasslauer, Thomas Geue, Joachim Koetzand Dirk G. Kurth*

Conductivity, rheology, AFM and neutron scatteringmeasurements prove that metal-ion induced self-assembly ofditopic ligands in solution results in the formation of linearrigid-rod like macro-assemblies.

4149

Formation, dynamics, and implication of solid electrolyte

interphase in high voltage reversible conversion fluoride

nanocomposites

Andrew J. Gmitter,* Fadwa Badway, Sylvie Rangan,Robert A. Bartynski, Anna Halajko, Nathalie Pereiraand Glenn G. Amatucci

The performance of bismuth-based nanocomposites forrechargeable Li battery cathodes was greatly influenced by thechoice of organic carbonate solvent. Cyclic carbonates werefound to decompose on discharge, negatively impacting cycling.

J. Mater. Chem., 2010, 20, 3999–4008 | 4005

PAPERS

4162

4168

4006 | J. Mater. Chem., 2010, 20, 3999–4008

High performance separation of aerosol sprayed

mesoporous TiO2 sub-microspheres from aggregates viadensity gradient centrifugation

Yichi Zhang, Yifeng Shi, Ya-Hsuan Liou, April M. Sawvel,Xiaohong Sun, Yue Cai, Patricia A. Holdenand Galen D. Stucky*

Post-aerosol synthesis separation using sucrose density gradientcentrifugation is developed as a facile and effective way to isolatemesoporous TiO2 nanospheres with a narrow size distribution.

4176

Real-time monitoring of the evolution of magnetism during

precipitation of superparamagnetic nanoparticles forbioscience applications

Valter Str€om,* Richard T. Olsson and K. V. Rao

Real-time magnetic measurement during nanosized magnetiteco-precipitation gives insight on the impact of high (rapidmixing, RM) vs. low (slow mixing, SM) mixing rates.

High pressure synthesis of superconducting nitrides in the

MoN–NbN system

Edward Bailey and Paul F. McMillan*

Superconducting Mo–Nb nitrides were synthesised at high-P,T.Niobium solution in hexagonal phases leaves Tc unaltered, butmolybdenum in cubic phases lowers Tc. This solvus is closed byhigh temperature.

4183

New directions in carbonitride research: synthesis of resin-

like dense-packed C3N4 using a hydrogen-free precursor

Carsten Ludwig Schmidt and Martin Jansen*

An amorphous ‘‘C3N4’’ has been prepared by decomposingpoly(cyanogen isocyanate) (C2N2O)x. Gaseous CO2 is the onlyby-product. The C–N network, containing the triazine core asthe main constituting building block, is stable up to 500 �C.(C3N4)x is classified as a polymeric non-graphitizing, glassy‘‘heterocarbon’’. A striking analogy to paracyanogen (CN)x

exists. Preliminary high-pressure crystallisation experiments arepresented.

This journal is ª The Royal Society of Chemistry 2010

PAPERS

4193

A strategy for the design of photochromic naphthopyrans

with large optical density at photosteady state and fast

fading speed at ambient temperature in the dark

Kunpeng Guo and Yi Chen*

A photochromic naphthopyran system in which both opticaldensity and fading speed of steady state are significantlyenhanced at ambient temperature has been described.

This journal is ª The Royal Society of Chemistry 2010

4198

Enhanced bulk catalyst dissolution for self-healing

materials

Timothy C. Mauldin and Michael R. Kessler*

A model was developed to aid in the selection of healingmonomers that can rapidly dissolve catalysts in self-healingmaterials.

4207

Rare earth scandate thin films by atomic layer deposition:

effect of the rare earth cation size

Pia Myllym€aki,* Martin Roeckerath, Joao Marcelo Lopes,J€urgen Schubert, Kenichiro Mizohata, Matti Putkonenand Lauri Niinist€o

Depending on the RE3+ cation radius, the REScO3 thin filmsgrown at 300 �C by atomic layer deposition crystallize uponannealing either as an orthorhombic perovskite phase or asa solid solution of the cubic C-type oxides.

4213

Surface and sub-surface reactions during low temperature

aluminium oxide atomic layer deposition on fiber-forming

polymers

Joseph C. Spagnola, Bo Gong, Sara A. Arvidson,Jesse S. Jur, Saad A. Khan and Gregory N. Parsons*

In situ IR transmission and quartz crystal microbalance analysesof aluminium oxide ALD, combined with cross-sectional TEMof coated fibers, show that specific reaction pathways onpolypropylene, polyvinyl alcohol, and polyamide-6 dependstrongly on polymer structure and deposition temperature.

J. Mater. Chem., 2010, 20, 3999–4008 | 4007

PAPERS

4223

AUTHOR INDEX

4008 | J. Mater. Chem., 2010, 20, 3999–4008

Highly ordered mesoporous carbon nanofiber arrays from

a crab shell biological template and its application in

supercapacitors and fuel cells

Hai-Jing Liu, Xiao-Ming Wang, Wang-Jun Cui,Yu-Qian Dou, Dong-Yuan Zhao and Yong-Yao Xia*

Highly ordered mesoporous carbon nanofiber arrays wereprepared by combining surfactant-templating self-assembly oforganic resols with a natural crab shell hard-templating process,and the unique structure gives rise to promising electrochemistryperformance in supercapacitors and fuel cells.

Afzaal, Mohammad, 4031 Ghosh, Kaushik, 4128

Alvaro, Mercedes, 4050Amatucci, Glenn G., 4149Ando, Yoshinori, 4128Arvidson, Sara A., 4213Badway, Fadwa, 4149Bahout, Mona, 4103Bailey, Edward, 4176Bartynski, Robert A., 4149Basabe-Desmonts, Lourdes, 4116Battle, Peter D., 4103Bodenthin, Yves, 4142Bolink, H. J., 4047Brine, H., 4047Cai, Yue, 4162Chen, Fengjin, 4094Chen, Jingbo, 4135Chen, Yi, 4193Chen, You-Han, 4067Chi, Zhenguo, 4135Cho, Jaephil, 4009Cojocaru, Bogdan, 4050Coronado, E., 4047Cui, Wang-Jun, 4223Daniels, Stephen, 4116Deng, Shaozhi, 4135Djenizian, Thierry, 4041Dong, Rui-Xuan, 4067Dotzler, Christian, 4116Dou, Yu-Qian, 4223Doyle, Colin, 4116Duhm, Steffen, 4055Gandhiraman, Ram P., 4116Garcia, Hermenegildo, 4050Gedanken, Aharon, 4085Geue, Thomas, 4142

Gmitter, Andrew J., 4149Gong, Bo, 4213Gubala, Vladimir, 4116Guo, Jinbao, 4094Guo, Kunpeng, 4193Halajko, Anna, 4149Hansen, Thomas, 4103Hanzu, Ilie, 4041Hasslauer, Iris, 4142He, Wanli, 4094Henry, Paul F., 4103Ho, Kuo-Chuan, 4067Holden, Patricia A., 4162Huang, Kuan-Chieh, 4067Iacono, Marcello, 4116James, Bryony, 4116Jansen, Martin, 4183Jur, Jesse S., 4213Kessler, Michael R., 4198Khan, Saad A., 4213Knauth, Philippe, 4041Koch, Norbert, 4055Koetz, Joachim, 4142Kumar, Mukul, 4128Kuo, Fonchu, 4074Kurth, Dirk G., 4142Lap, Sze-to, 4074Lau, Kok-Kin, 4074Lavela, Pedro, 4041Law, Ga-Lai, 4074Li, Haiyin, 4135Li, Xiaofang, 4135Lin, Jiang-Jen, 4067Liou, Guey-Sheng, 4080Liou, Ya-Hsuan, 4162

Liu, Hai-Jing, 4223Liu, Zhiguo, 4015Lopes, Joao Marcelo, 4207Malik, Mohammad Azad, 4031Maruyama, Takahiro, 4128Mastai, Yitzhak, 4085Mauldin, Timothy C., 4198McMillan, Paul F., 4176Ming, Naiben, 4015Mizohata, Kenichiro, 4207Myllym€aki, Pia, 4207Neatxu, Sxtefan, 4050Niinist€o, Lauri, 4207Nooney, Robert I., 4116O’Brien, Paul, 4031Oehzelt, Martin, 4055Olsson, Richard T., 4168Ortiz, Gregorio F., 4041Paik, Pradip, 4085Parsons, Gregory N., 4213Parvulescu, Vasile I., 4050Pereira, Nathalie, 4149Putkonen, Matti, 4207Rabe, J€urgen P., 4055Rangan, Sylvie, 4149Rao, K. V., 4168Roeckerath, Martin, 4207Roisnel, Thierry, 4103Salzmann, Ingo, 4055Sawvel, April M., 4162Schmidt, Carsten Ludwig, 4183Schubert, J€urgen, 4207Schwarz, Guntram, 4142Sessolo, M., 4047Shi, Yifeng, 4162Sievers, Torsten K., 4142

This journal is ª The

Sxomoghi, Vasile, 4050Spagnola, Joseph C., 4213Str€om, Valter, 4168Stucky, Galen D., 4162Sun, Xiaohong, 4162Tanner, Peter A., 4074Tirado, Jos�e L., 4041Toney, Michael F., 4116Tonus, Florent, 4103Tsai, Keng-Wei, 4067Tsai, Wei-Cheng, 4067Vittal, R., 4067Vogel, J€orn-Oliver, 4055Volcke, Cedric, 4116Wang, Chun-Chieh, 4067Wang, Xiao-Ming, 4223Wang, Ying-Chiao, 4067Wei, Jie, 4094Williams, David E., 4116Wong, Ka-Leung, 4074Wong, Wing-Tak, 4074Wu, Hao, 4094Xia, Yong-Yao, 4223Xu, Bingjia, 4135Xu, Jiarui, 4135Xu, Ningsheng, 4135Yang, Huai, 4094Yang, Zhiyong, 4135Yen, Hung-Ju, 4080Zhang, Lipei, 4094Zhang, Yi, 4135Zhang, Yichi, 4162Zhao, Dong-Yuan, 4223Zhu, Xinhua, 4015

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Electronic supplementary information (ESI) is available viathe online article (see http://www.rsc.org/esi for generalinformation about ESI).

Royal Society of Chemistry 2010