CrystEngComm Blog

High-magnification FESEM image of 3D flower-like ZnO superstructure

This month’s crystal clear features some truly stunning hierarchical structures. 

These flower-like 3D formations have been made by Kezheng Chen et al. at the Lab of Functional and Biomedical Nanomaterials. The generation of these impressive superstructures is intriguing; the team were able to alter the reaction time to change the morphology of the produced crystals. 

The team propose that the crystalline ZnO aggregates, there is then orientated attachment of nanoclusters followed by heterogeneous nucleation and growth of secondary nanosheets. The result is striking. 

The average diameter of the superstructures is around 3µm, comprised of an intersecting network of nanosheets of the order of 15nm. The large porous surface of these zinc oxide flowers lend themselves to applications in catalysis, solar cells and sensors. 

This article was published in Issue 9 of CrystEngComm and can be downloaded for free. If you’re interested in crystal engineering you can also take a look at the previous winners of Crystal Clear. 

Facile synthesis of flower-like 3D ZnO superstructures via solution route
Yongjiang Sun, Li Wang, Xuegang Yu and Kezheng Chen 

Eu-MOF crystals which look suprisingly like chips or French fries

Fish and chips is a classic dish, however this month’s Crystal Clear is noticeably lacking in the crystal fish department. 

These chips (or French fries) are in fact crystals of a metal organic framework (MOF) constructed with Eu³⁺ and 1,3,5-Benzenetricarboxylic acid. The synthesis is performed in a mixture of water and DMF and the crystal size and shape can be manipulated by altering the ratio of the two liquids. 

The team from Qingdao and Changchun in China were looking at the influence additives and reaction conditions have on the MOF crystal morphology, these materials have interesting luminescence properties and potential application in colour displays and sensors. To read the full details of the teams discoveries take a look at Issue 8 of CrystEngComm, where you can also see how they were able to make ‘urchin-like balls’ as well as the pictured chips! l

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Solvothermal synthesis of luminescent Eu(BTC)(H2O)DMF hierarchical architectures
Biao Xu, Hailing Guo, Song Wang, Yuyang Li, Hongjie Zhang and Chenguang Liu

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This month’s crystal clear could almost be an ice cube, it’s certainly large enough!

In fact this is a single crystal of K₃B₆O₁₀Cl synthesised by Shilie Pan et al. and has dimensions of 25 x 11 x 7 mm³. The team based at Xinjiang Technical Institute of Physics & Chemistry have published their findings in Issue 3 of CrystEngComm, detailing the growth of these crystals as well as their optical properties.

Materials which possess non-linear optical (NLO) properties are of great interest given their potential applications in photonics, including optical storage and frequency mixing. Using a top-seeded solution growth method the team synthesised these large crystals and found them to have a high laser damage threshold and a wide transparency range. The K₃B₆O₁₀Cl crystals are potentially promising in high-power UV light generation.

It is important for application that very high quality single crystals are formed; initially the researchers found that spontaneous nucleation and crack formation hindered quality crystal growth, with crystalline grains floating on the solution surface and attaching to the edge of the growing crystal.

To see how the team overcame these problems to produce the beautiful single crystal displayed here you can download their article now, which has been made free to access for 4 weeks.

Growth, thermal and optical properties of a novel nonlinear optical material K₃B₆O₁₀Cl
Hongping Wu, Shilie Pan, Hongwei Yu, Dianzeng Jia, Aiming Chang, Hongyi Li, Fangfang Zhang and Xia Huang
CrystEngComm, 2012, 14, 799-803
DOI: 10.1039/C1CE05886J

This month’s very festive Crystal Clear looks surprisingly like a Christmas tree!
In fact this is a dendritic nickel nanocrystal synthesised by Zhang et al. using a simple electrolytic process in ethylene glycol solution. The microstructures have trunks of around 10 µm with ordered branches approximately 0.5-1.5 µm long and a thickness of 210 nm. The authors found they were able to control the morphology of the structures by adjusting the experimental conditions such as precursor concentration, voltage and the temperature of the reaction.

Designing nano-structures is an area of great interest as the size and shape can significantly affect the properties, in this instance it was found that compared with bulk Ni the Ni dendritic crystals exhibited a decreased saturation magnetism but an enhanced coercivity.

You can find out more about their work by reading the advance article in CrystEngComm which is free to access for 4 weeks.

Electrolytic approach towards the controllable synthesis of symmetric, hierarchical, and highly ordered nickel dendritic crystals
Jian Wang, Liangming Wei, Liying Zhang, Yafei Zhang and Chuanhai Jiang
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C1CE06066J, Paper

This months crystal clear brings us an eerie looking scene that looks more like something out of ‘Doctor Who’ than CrystEngComm.

These remarkable structures are in fact BaZrO₃ nanotubes,  prepared by electrospinning a metal–organic precursor solution and calcining.

Albert Calleja and co-workers detail the synthesis of these nanoparticle chains in their article High temperature transformation of electrospun BaZrO₃ nanotubes into nanoparticle chains, which is free to access for 4 weeks.

Electrospinning is an interesting technique which shows potential in a range of fields from electronics to smart textiles.  By combining this technique with a chemical precursor for their functional oxide (BaZrO₃) and annealing the fibres they made, the team observed the crystalline nanostructure depicted here (which you’ll see more clearly in the full paper). Some of them look remarkably like Nano-Necklaces! 

Make sure you don’t miss a Crystal Clear by liking us on Facebook or following us on Twitter, we’ll also keep you updated on all Crystal Engineering News, from HOT articles to interviews (such as our interview earlier this month with Dan Shechtman)

High temperature transformation of electrospun BaZrO3 nanotubes into nanoparticle chains
Albert Calleja, Xavier Granados, Susagna Ricart, Judith Oró, Jordi Arbiol, Narcís Mestres, Ana Esther Carrillo, Xavier Palmer, Francesc Cano, Jose Antonio Tornero, Teresa Puig and Xavier Obradors
CrystEngComm, 2011, 13, 7224-7230
DOI: 10.1039/C1CE05108C

This month’s Crystal Clear shows a sunflower-like silica nanostructure made by chemical vapour deposition.

The image was created by Zhizhen Ye, Haiping He and colleagues at Zhejiang University from their work in a paper in Issue 19 of CrystEngComm.

Ye and He looked at the formation mechanism to better understand the unusual growth process observed and investigated the photoluminescent properties of the silica.

Read the full article for FREE to find out more…

Self-catalysis induced three-dimensional SiOx nanostructures
Luwei Sun, Haiping He, Chao Liu and Zhizhen Ye
CrystEngComm, 2011, 13, 5807-5812

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This month’s Crystal Clear shows a vanadia star-shaped nanocrystal.

The crystal was made by Sarbajit Banerjee and colleagues at the State University of New York, Buffalo. They were making six-armed nanocrystallites of binary vanadium oxides, and although in this particular image the arms aren’t fully separated, we still thought it was a great looking crystal. They used a new seeded growth strategy that was very successful in making controlled shapes with good monodispersity, and you’ll have to read the full paper to see the complete nanostars!

Vanadium oxides are important in technology, partly because the variety of structures they can form makes them invaluable as host lattices, but also because of their interesting electonic, electrochromic, magnetic and optical properties. Vanadium oxides have consequently been used in batteries, as well as optical applications like laser crystals and switching devices.

This paper was published in Issue 17 of CrystEngComm, and was featured on the front cover, read our earlier blog to find out more.

Read the full article for free to find our more and to see the fully formed star-shaped crystals…

A VO-seeded approach for the growth of star-shaped VO2 and V2O5 nanocrystals: facile synthesis, structural characterization, and elucidation of electronic structure
Luisa Whittaker, Jesus M. Velazquez and Sarbajit Banerjee
CrystEngComm, 2011, 13, 5328-5336