Enhancing photocatalytic properties of a tungsten oxide hydrate by microwave-assisted synthesis

Posted on behalf of Gwenda Kyd, web writer for CrystEngComm

Tungsten oxide hydrates (like WO3•nH2O, n=0-2) show promising photocatalytic properties. They efficiently oxidise a range of organic compounds including textile dyes and bacterial pollutants when irradiated with blue light and also have potential use in the treatment of acid polluted solutions. An understanding of the structure dependent nature of the activities is required to fully develop them and new preparation methods can facilitate this. Microwave heating methods are attractive as they increase reaction rates and improve the yields and purity of products.

This new paper shows how microwave assisted synthesis of WO3•0.33H2O can efficiently produce orthorhombic crystallites. The products of syntheses with and without microwave heating via three different methods were compared. In each case, different particle sizes and morphologies were formed. For each of the pairs (with or without microwave heating), the photocatalytic properties were enhanced for the products of the microwave-assisted synthesis. Authors suggest this is due to the preferential growth along the (100) face exposing more of the highly acidic (010) faces.

Microwave-assisted growth of WO3·0.33H2O micro/nanostructures with enhanced visible light photocatalytic properties

For more details see the paper at:

Microwave-assisted growth of WO3·0.33H2O micro/nanostructures with enhanced visible light photocatalytic properties
Jiayin Li, Jianfeng Huang, Jianpeng Wu, Liyun Cao, Qijia Li and Kazumichi Yanagisawa
CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE41005F, Paper


Gwenda KydGwenda Kyd has a PhD in metallocarborane chemistry from the University of Edinburgh. Other research work includes the spectroscopic study of the structure of glasses and organometallic electron-transfer reactions and the preparation of new inorganic phosphors. Currently she works as a scientific database editor.

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CrystEngComm Editor’s choice

In this Editor’s choice post, Professor Rahul Banerjee, an Associate Editor for CrystEngComm, talks about his favourite articles published by the journal in the past year.

Effect of dehydration on the mechanical properties of sodium saccharin dihydrate probed with nanoindentation
M. S. R. N. Kiran, Sunil Varughese, U. Ramamurty and Gautam R. Desiraju
CrystEngComm, 2012,14, 2489-2493

In this paper by Desiraju et al., an excellent study was carried out on the effects of dehydration on the mechanical properties of sodium saccharin dihydrate. These effects were probed with nanoindentation. The paper describes several novel features including a thorough study of the mechanical behaviour of sodium saccharin hydrate using nanoindentation with respect to the dehydration process. Time-dependent nanoindentation experiments were carried out to evaluate the variation in the mechanical behaviour of the crystals, initiated by the dehydration process, and the observed variations were correlated with the possible structural changes.

Effect of dehydration on the mechanical properties of sodium saccharin dihydrate probed with nanoindentation

Large organic single crystal sheets grown from the gas–liquid and gas–liquid–solid interface
Hui Shang, Huan Wang, Na Gao, Fangzhong Shen, Xianjie Li and Yuguang Ma
CrystEngComm, 2012,14, 869-874

In this paper, Shang et al. described how large organic single crystal sheets can be grown from the gas–liquid and gas–liquid–solid interface, and highlighted following novel points:

1. A new gas–liquid interface technique is presented for the growth of anthracene (AN) and its doped single crystals.

2. The balanced force and isothermal evaporation of the solvent result in the expansion of the crystal into a three-dimensional stacked structure.

3. The results of X-ray diffraction and optical measurements indicated that such laminated films exhibited higher crystallinity and photoluminescence (PL) efficiency than those obtained by physical vapor transport (PVT) method or original solution growth (SG) method.

4. This crystal growth technique can be extended to the gas–liquid–solid interface to directly grow AN single crystals on electrodes (such as silicon wafers and gold substrates), which may be valuable for the preparation of organic single crystal based devices including light-emitting diodes and field effect transistors.

Large organic single crystal sheets grown from the gas–liquid and gas–liquid–solid interface

Hofmeister effects of ionic liquids in protein crystallization: Direct and water-mediated interactions
Magdalena Kowacz, Abhik Mukhopadhyay, Ana Luísa Carvalho, José M. S. S. Esperança, Maria J. Romão and Luís Paulo N. Rebelo
CrystEngComm, 2012,14, 4912-4921

Rebelo et al. have presented an interesting work on ionic liquid assisted crystallization of two proteins, lysozym and ribonuclease A. This paper showcases following interesting points:

1. They have shown experiments on the crystallization of two positively charged proteins, lysozyme and ribonuclease A, using ionic liquids as either crystallization additives or, in particular cases, as precipitating agents.

2. They thoroughly study the effect of Hofmeister anions on stabilizing the positively charged protein and followed by crystallization.

3. The mechanism of crystallization at low and high ionic strength has been nicely described.

Hofmeister effects of ionic liquids in protein crystallization: Direct and water-mediated interactions

Sonocrystallization of zeolitic imidazolate frameworks (ZIF-7, ZIF-8, ZIF-11 and ZIF-20)
Beatriz Seoane, Juan M. Zamaro, Carlos Tellez and Joaquin Coronas
CrystEngComm, 2012,14, 3103-3107

Seoane et al. describes in this paper the synthesis of Zeolitic Imidazolate Frameworks (ZIFs) via sonocrystallization. In comparison to the traditional solvothermal method, this process is a greener approach and requires less energy, as it occurs at a lower temperature. Using this method authors could convert ZIF-7 into ZIF-11 in-situ and obtain a pure phase of ZIF-11, which was not possible by the solvothermal method.

Sonocrystallization of zeolitic imidazolate frameworks (ZIF-7, ZIF-8, ZIF-11 and ZIF-20)

The role of mechanochemistry and supramolecular design in the development of pharmaceutical materials
Amit Delori, Tomislav Friščić and William Jones
CrystEngComm
, 2012,14, 2350-2362

In this interesting Highlight, Jones et al. discussed the different aspects of the synthesis of pharmaceutical co-crystals by mechanochemical grinding. The authors provided a nice overview of the topic in a very lucid way and it shows a definite direction of synthesis of pharmaceutical co-crystals. Moreover they have shown that in some cases much variations and freedom can be enjoyed based on the procedure. The authors’ critical review on time-dependent co-crystallization and how grinding a co-crystal with one of the components of the co-crystal to obtain different co-crystals is also worth noting.

The role of mechanochemistry and supramolecular design in the development of pharmaceutical materials

Facile synthesis of germanium–graphene nanocomposites and their application as anode materials for lithium ion batteries
Jinsheng Cheng and Jin Du
CrystEngComm
, 2012,14, 397-400

This paper by Cheng et al., describes a simple and low-cost method to synthesize Ge nanoparticles/graphene (Ge NPs/GR) nanocomposites under mild conditions. The reduction of sugarcane bagasse (SB) derived graphene oxide nanosheets were accompanied by generation of Ge NPs in one step. This simple and straightforward synthetic approach is likely to find many practical applications. Interesting features of this paper include:

1. A simple, convenient and low-cost method to fabricate GeNPs/GR nanocomposites under mild conditions.

2. Enhancing their electronic conductivity.

3. High-capacity anode material for lithium ion batteries (LIBs).

4. Superior capacity retention of 90% after 15 cycles.

5. Potential application in the development of low-cost and high-performance LIBs.

Facile synthesis of germanium–graphene nanocomposites and their application as anode materials for lithium ion batteries

Facet-selective growth of Cu–Cu2O heterogeneous architectures
Shaodong Sun, Chuncai Kong, Hongjun You, Xiaoping Song, Bingjun Ding and Zhimao Yang
CrystEngComm, 2012,14, 40-43

In this recent report, Zhimao Yang and co-workers reported a facet-selective growth of Cu–Cu2O heterogeneous architectures for photodegradation of dye. The authors have demonstrated a facile protocol for the synthesis of facet selective growth of low-cost Cu nanoparticles on the {111} facets of polyhedral 26-facet Cu2O architectures to form polyhedral 26-facet Cu-Cu2O architectures, in a simple one pot synthesis reaction. The Cu–Cu2O architectures prepared with this method also showed better adsorption and photo-degradation of methyl orange as compared to the pristine Cu2O architectures.

Facet-selective growth of Cu–Cu2O heterogeneous architectures

Self-assembled porous hierarchical-like CoO@C microsheets transformed from inorganic–organic precursors and their lithium-ion battery application
Jun Liu, Yichun Zhou, Chunping Liu, Jinbin Wang, Yong Pan and Dongfeng Xue
CrystEngComm, 2012,14, 2669-2674

In an important development towards material synthesis for energy storage, Liu et al. reported a simple, easy, one-step synthesis of interconnected CoO@C micro sheets using a solution phase technique. The porous hierarchical-like CoO@C nanohybrid has been well characterized and judiciously used as an anode material, which is found to exhibit highly reversible capacity along with excellent cycling performance and good rate capability. The hybrid takes advantage of the uniformly encapsulated crystalline CoO within two-dimensional thin carbon layers thereby resulting in an effective intercalation of Li+ ions. Here, the synergistic effect of the hierarchical nano-architecture and conducting carbon layer is found to result in an enhanced electrochemical performance of the hybrid.

Self-assembled porous hierarchical-like CoO@C microsheets transformed from inorganic–organic precursors and their lithium-ion battery


Rahul BanerjeeRahul Banerjee received his PhD degree from University of Hyderabad, Hyderabad in 2006 under the supervision of Prof. Gautam R. Desiraju. After postdoctoral work in UCLA with Prof. Omar M. Yaghi (2006-2008), he joined CSIR-National Chemical Laboratory, Pune, India in 2008 as a Scientist. His research interests include the study of structural chemistry with a focus on chemical synthesis to design new materials for hydrogen storage, carbon sequestration and catalysis. Additionally, his group is also engaged in design and synthesis of lightweight materials for storage, capture and proton conduction. Dr. Banerjee is an Editorial board member and an Associate Editor of CrystEngComm. He also served as a co-editor of Acta Crystallographica Section E till 2012.

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More HOT articles for August

Put these articles on your reading list— they are recommended by our referees!

Supramolecular 1D ribbons in complexes between a bicyclic-guanidine derivative and di- or monocarboxylic acids
Vitthal N. Yadava and Carl Henrik Görbitz  
CrystEngComm, 2013,15, 7321-7326
DOI: 10.1039/C3CE40960K

 

 


How to monitor guest exchange in host–guest systems
Luigi R. Nassimbeni and Hong Su  
CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE40675J


Nd:MgO:LiTaO3 crystal for self-doubling laser applications: growth, structure, thermal and laser properties
Dehui Sun, Yanhua Leng, Yuanhua Sang, Xueliang Kang, Shande Liu, Xiaoyong Qin, Kun Cui, Bin Kamaruddin Wan Hairul Anuar, Hong Liu and Yong Bi  
CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE40966J


Iodine-templated assembly of an In(III) complex with a single-crystal-to-single-crystal transition
Yuan-Chun He, Wei-Qiu Kan, Jiao Guo, Yan Yang, Peng Du, Ying-Ying Liu and Jian-Fang Ma  
CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE41337C

 


Effect of sodium citrate on the shape and photoluminescence properties of CaWO4:Eu3+ superstructures synthesized by the hydrothermal method
Yeqing Chen, Sung Wook Park, Byung Kee Moon, Byung Chun Choi, Jung Hyun Jeong and Chongfeng Guo  
CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE40872H

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A new format for our crystal clear feature

We are tweaking our crystal clear posts, and instead of featuring just one crystal per post, we will be highlighting a selection of images organised along a theme. For this first post, I have chosen a selection of plant-like crystals:

Influence of indium doping on the morphology of ZnS nanostructures grown by a vapor–solid method

ZnS nanocrystals

Growth of silver dendritic nanostructures via electrochemical route

Silver nanostructures

Hierarchical rh-In2O3 crystals derived from InOOH counterparts and their sensitivity to ammonia gas

Hierarchical rh-In2O3 crystals

Find out more about each crystal from the original papers:

Influence of indium doping on the morphology of ZnS nanostructures grown by a vapor–solid method
Belén Sotillo, Yanicet Ortega, Paloma Fernández and Javier Piqueras
CrystEngComm, 2013,15, 7080-7088 DOI: 10.1039/C3CE40920A

Growth of silver dendritic nanostructures via electrochemical route
Mohanrao V. Mandke, Sung-Hwan Han and Habib M. Pathan
CrystEngComm, 2012,14, 86-89 DOI: 10.1039/C1CE05791J

Hierarchical rh-In2O3 crystals derived from InOOH counterparts and their sensitivity to ammonia gas
Haihui Jiang, Lichun Zhao, Ligang Gai, Li Ma, Yun Ma and Mei Li
CrystEngComm, 2013,15, 7003-7009 DOI: 10.1039/C3CE40465J

For more fascinating images, go to our  Pinterest board

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Giant Quantum Dots

Posted on behalf of Josh Campbell, web writer for CrystEngComm

Quantum dots combine nanocrystals and semiconductors to create materials small enough to show quantum mechanical properties. The excitons (a bound state of an electron and an electron hole) are squeezed together, and if this confinement is in three dimensions, a quantum dot is formed; for two dimensions, a quantum wire,  and in one dimension, a quantum well. This squeezing together results in the bandgap of the material becoming highly size dependent, thus tunable and usually blue-shifted. Chalcogenide materials have always drawn research in semiconducting materials, with ternary and quarternary alloys offering even more control over the bandgap while also improving stability or size selectivity.

This new paper shows the synthesis of AgBiS2 monodispersed quantum dots that show an extremely high dielectric constant. They were synthesized via the hot injection method, with an average diameter of 8.5nm ± 1.2nm, and the optical band gap energy measured confirmed that strong quantum confinement was taking place. Due to the small size of the nanoparticles, grain boundary effects were expected to dominate the electronic properties. The dielectric constant of the pellets is on the order of 105 and the authors confirmed grain boundaries with large resistances and capacitances gave rise to the huge dielectric constant which has significant implications in the design of similar materials.

The synthesis of monodispersed AgBiS2 quantum dots with a giant dielectric constant

Read the paper to find out more:

The synthesis of monodispersed AgBiS2 quantum dots with a giant dielectric constant
Chao Chen, Xiaodong Qiu, Shulin Ji, Chong Jia and Changhui Ye

CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE41304G, Communication


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

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Size-controlled synthesis of MOF nanoparticles

Posted on behalf of Gwenda Kyd, web writer for CrystEngComm

Porous metal-organic frameworks (MOFs) have potential applications ranging from gas storage to chemical sensing. To fully realise these, the ability to cast into a given form, such as a thin film, is important. Nanometre (nm) sized particles are an attractive target, potentially allowing properties to be fine-tuned precisely. Formation of MOF nanoparticles has previously been achieved but obtaining sizes below 100nm is difficult and can lack reproducibility.

A new paper shows how the MOFs HKUST-1 and IRMOF-3 can be produced using additive-mediated syntheses. These involve mixing a polymer (for the synthesis of HKUST-1) or polymer-surfactant combination (for IRMOF-3) with the metal and ligand sources. This produces nanoparticles of the MOF between 30nm and 300nm, depending on the reaction temperature, reaction time and the quantities of additives used. The synergy of the polymer and surfactant gives the best control over size and monodispersity, i.e. the particles produced are within a narrow size range. This method could potentially be useful in producing MOFs for drug delivery or sensing where ultra-small particles or films are required.

Additive-mediated size control of MOF nanoparticles

For more information see the full paper:

Additive-mediated size control of MOF nanoparticles
Annekathrin Ranft, Sophia B. Betzler, Frederik Haase and Bettina V. Lotsch

CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE41152D, Communication


Gwenda KydGwenda KydGwenda Kyd has a PhD in metallocarborane chemistry from the University of Edinburgh. Other research work includes the spectroscopic study of the structure of glasses and organometallic electron-transfer reactions and the preparation of new inorganic phosphors. Currently she works as a scientific database editor.

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Highlights from the upcoming Coordination Polymers themed issue

We will shortly be publishing a themed issue titled “Structural Design of Coordination Polymers” in CrystEngComm. As a taster of what is coming, the following is a selection of articles from the issue that is recommended as HOT by our referees.


Self-assembly of a chiral three-dimensional manganese(II)–copper(II) coordination polymer with a double helical architecture
Thais Grancha, Clarisse Tourbillon, Jesús Ferrando-Soria, Miguel Julve, Francesc Lloret, Jorge Pasán, Catalina Ruiz-Pérez, Oscar Fabelo and Emilio Pardo

CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE41022F, Communication

Self-assembly of a chiral three-dimensional manganese(II)–copper(II) coordination polymer with a double helical architecture


Coordination polymers of alkali metal trithiocyanurates: structure determinations and ionic conductivity measurements using single crystals
Satoshi Tominaka, Sebastian Henke and Anthony K. Cheetham

CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE41150H, Paper

Coordination polymers of alkali metal trithiocyanurates: structure determinations and ionic conductivity measurements using single crystals


Solvent-free synthesis of supported ZIF-8 films and patterns through transformation of deposited zinc oxide precursors
Ivo Stassen, Nicolò Campagnol, Jan Fransaer, Philippe Vereecken, Dirk De Vos and Rob Ameloot

CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE41025K, Communication

Solvent-free synthesis of supported ZIF-8 films and patterns through transformation of deposited zinc oxide precursors


The influence of nitro groups on the topology and gas sorption property of extended Zn(II)-paddlewheel MOFs
Phuong V. Dau and Seth M. Cohen

CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE41124A, Communication

The influence of nitro groups on the topology and gas sorption property of extended Zn(II)-paddlewheel MOFs


Linker extensions in metal–organic frameworks: a way to isoreticular networks or new topologies?
Daniela Frahm, Frank Hoffmann and Michael Fröba

CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE40594J, Paper

Linker extensions in metal–organic frameworks: a way to isoreticular networks or new topologies?


Studying fluorous interactions in a series of coordination compounds derived from mono-pyridyl ligands equipped with hydrogen bonding functionality: exploiting anion•••πF interaction in separating ClO4 anion from a competing mixture of anions
Subhabrata Banerjee and Parthasarathi Dastidar

CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE40359A, Paper

Studying fluorous interactions in a series of coordination compounds derived from mono-pyridyl ligands equipped with hydrogen bonding functionality: exploiting anionπF interaction in separating ClO4− anion from a competing mixture of anions

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Rare-earth fluoride upconversion nanoparticles and their applications in bioimaging

Posted on behalf of Josh Campbell, web writer for CrystEngComm

Rare earth metals and their compounds are some of the most important elements in modern economies and science. They can be found in superconductors, catalytic converters and lasers. Most rare earth ions also show the phenomenon of upconversion (UC). UC is the emission of light at shorter wavelengths than initially absorbed at for example the conversion of infrared to visible light. UC effects show great promise in the bioimaging field, providing narrow emission bandwidths and high-signal to noise ratio due to being able to use near infra-red sources of excitation. Rare earth halides are known to increase UC luminescence but chlorides and bromides are usually sensitive to moisture and not suitable for labelling biomolecules.

A new highlight shows the most popular way of synthesizing rare earth fluorides and their applications as luminescent labels. Thermal decomposition is the most common synthesis method and gives nanocrystals with well-defined shapes and good size selectivity. However there are drawbacks (such as the strict experimental conditions) which have led to the development of coprecipitation and microwave assisted methods among others. These nanoparticles with UC properties have also recently shown promise being used as multimodal imagers. Multimodal imaging uses more than one technique and work is being done to integrate magnetic components into UC nanocrystals to combine MRI and luminescent imaging.

Rare earth fluorides upconversion nanophosphors: from synthesis to applications in bioimaging

Find out more from the article:

Rare earth fluorides upconversion nanophosphors: from synthesis to applications in bioimaging
Song Wang, Jing Feng, Shuyan Song and Hongjie Zhang
CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE40679B, Highlight


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

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In-situ generation of supported MOF films and patterns

Posted on behalf of Gwenda Kyd, web writer for CrystEngComm

Metal-organic frameworks (MOFs) are porous networks with a wide range of potential applications including gas storage and sensing. For their potential to be fully realised in integrated systems, efficient methods of producing thin films and patterns are crucial. Although methods exist for MOFs, these are are less developed than for other materials such as ZnO.

A new paper shows how thin films or patterns of the MOF ZIF-8 can be produced by melting the required ligand, 2-methylimidazole , in contact with a ZnO film or pattern. If the process is carried out under vacuum with an excess of ligand, it is totally solvent- and waste-free. Using this method with ZnO supported films and patterns is demonstrated to replicate the morphologies in the resulting ZIF-8, as shown in the diagram below. ZIF-8 is highly stable and has many possible uses including molecular separation and as an insulator in microelectronics. The reported strategy could allow new applications for ZIF-8 films to be developed.

Solvent-free synthesis of supported ZIF-8 films and patterns through transformation of deposited zinc oxide precursors

For more information see the paper at:

Solvent-free synthesis of supported ZIF-8 films and patterns through transformation of deposited zinc oxide precursors
Ivo Stassen, Nicolò Campagnol, Jan Fransaer, Philippe Vereecken, Dirk De Vos and Rob Ameloot
CrystEngComm, 2013, Advance Article
DOI: 10.1039/C3CE41025K, Communication


Gwenda KydGwenda KydGwenda Kyd has a PhD in metallocarborane chemistry from the University of Edinburgh. Other research work includes the spectroscopic study of the structure of glasses and organometallic electron-transfer reactions and the preparation of new inorganic phosphors. Currently she works as a scientific database editor.

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Human enamel mimic whitens teeth

Over time, gleaming teeth become stained by repeated exposure to vices such as coffee, red wine or cigarettes. Current whitening methods include replacing the crown of the tooth or etching off stained enamel using chemical abrasives like hydrogen peroxide. These require the removal of part of a healthy tooth, and can lead to gum irritation and sensitive teeth.

Fluorapatite, polyethylene oxide and a polymer derived from the neurotoxin acrylamide have been combined by Chinese scientists to make a film that can restore teeth to their natural colour.

Read the full story at Chemistry World

PEO-assisted precipitation of human enamel-like fluorapatite films for tooth whitening

PEO-assisted precipitation of human enamel-like fluorapatite films for tooth whitening
Shize Liu, Yujing Yin and Haifeng Chen

CrystEngComm, 2013,15, 5853-5859
DOI: 10.1039/C3CE40388B, Paper

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