Author Archive

Crystal growth control via orientated aggregation.

A recent paper in CrystEngComm details a new synthetic method to create magnenite (iron oxide) nanoparticles (NPs), based on the orientated aggregation of particles using a calixarene macrocycle. The new method allows for control of the type of NPs produced and could potentially be applied to the growth of other nanomaterials.

Magnetite has promising biomedical applications due to its interesting magnetic and electrochemical properties and has been studied for drug delivery, biosensing and cancer treatment.  The NPs can reduce oxidative stress from electromagnetic radiation and raise temperature around the tumour cells in the presence of an applied magnetic field, killing cancer cells through localised heating. In contrast to traditional strategies of crystal growth, orientated aggregation is a mediated approach in which primary crystallites assemble into secondary crystals. The mediator can be other particles, specific molecules or an applied field. NPs grown this way often exhibit different morphologies and properties to the starting material.

Images of multicore (a,b) and octahedral (d,e) NPs

The authors postulated that the use of an organic molecule that complexes with iron could be used to induce aggregation and chose p-tert-butylcalix[8]arene,  calixarene molecules are used in host-guest chemistry to induce efficient and selective hosts.  A reaction mixture of the calixarene, iron(III) acetylacetonate and oleic acid was heated at 200°C for 2 hours, before being refluxed for one hour to promote crystal growth. The initial ratio of the reactants (0.5:1:2) produced multicore NPs with an average size of 40nm and primary crystallites of 7nm. Raising the iron:calixarene ratio to 1:1 resulted in a new morphology being produced, octahedral NPs were now produced exclusively with an average size of 50nm. An experiment without the calixarene produced different NPs again, this time much smaller (7nm) single core NPs. Further experiments varying the heating time and ratios resulted in defect octahedral NPs.

The colloidal and magnetic properties of the NPs were then measured with the multicore structures exhibiting excellent properties. The authors conclude that their synthesis method is easy to perform, reproducible and controllable.

For more information, read the full paper at:

Tuning morphology and magnetism of magnetite nanoparticles by calix[8]arene-induced oriented aggregation

Francesco Vita,  Helena Gavilán, Francesca Rossi, César de Julián Fernández, Andrea Secchi, Arturo Arduini, Franca Albertini and  M. Puerto Morales

CrystEngComm, 2016, Advance Article

DOI: 10.1039/C6CE01252C

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Novel photocatalytic heterojunctions

A recent paper published in CrystEngComm details the successful development of BiOBr/WO3 p–n heterojunctions. These novel photocatalysts display higher activity than the individual components across a range of organic molecule pollutants and remain stable for further cycles.

Semiconducting photocatalysts offer a potentially green way of removing organic pollutants from water. Initial development of these photocatalysts focused on TiO2, which shows excellent performance for the decomposition of many organic compounds. However, TiO2 only exhibits this performance under UV light and the development of visible light driven (VLD) photocatalysts is highly desirable. WO3, an n-type semiconductor, possesses many properties needed for a good VLD, but encounters problems related to the recombination of charge carriers.

It is known that the creation of p-n heterojunctions can enhance performance. Enter bismuth oxyhalides, p-type semiconductors which exhibit excellent performance under both UV and visible light. BiOBr in particular, has good chemical stability, acts against a wide range of pollutants, and has never been combined with WO3 before.

Flower-like structures of BiOBr/WO3
Flower-like structures of BiOBr/WO3
The heterojunctions were prepared by solvothermally treating a solution of WO3, Bi(NO3)3 and CTAB. Three different molar ratios were prepared (1/0.5, 1/1 and 1/2) creating flower-like structures. The individual components were also prepared for comparative measurements. Photocatalytic activity was measured by the decomposition of three organic compounds, rhodamine B, methyl orange and para-chlorophenol. The 1/1 compound showed the greatest removal efficiency across all the mock pollutants with all heterojunction ratios performing better than the individual components and a mixture of the two with the same weight of components. The authors explain the excellent performance of BiOBr/WO3 is due to two reasons; firstly the flower-like superstructures of the material with their many pores and channels increase the absorption of small molecules and secondly the nature of the p-n heterojunction allows for efficient charge collection and separation.

The authors conclude the 1/1 compound is the best potential visible light driven photocatalyst with efficient performance and good stability for water environmental purification.

Read the full article here:

Synthesis of BiOBr/WO3 p–n heterojunctions with enhanced visible light photocatalytic activity
Junlei Zhang, Lisha Zhang, Xiaofeng Shen, Pengfei Xu and Jianshe Liu
CrystEngComm, 2016,18, 3856-3865, DOI: 10.1039/C6CE00824K

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Josh Campbell is a PhD student, currently at the University of Southampton, UK studying crystal structure prediction of organic semiconductors. He received his BSc from the University of Bradford.
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