Posts Tagged ‘Dalton’

Using the ‘multicomponent’ strategy to improve hydrogen storage materials

The need for a hydrogen storage material that can store hydrogen reversibly, with little or no kinetic barrier, and at ambient conditions remains a great challenge for researchers in this field. In order to progress towards a future hydrogen economy, hydrogen storage materials must also be practical for mobile applications and of course be economically viable.

Many different materials have been proposed for hydrogen storage. These range from physisorption materials such as activated carbons, zeolites and Metal Organic Frameworks (MOFs) to materials based on chemisorption such as metal hydrides, ammonia boranes and alanates. The hydrogen binding mechanism of chemisorption materials is through the formation of strong covalent bonds with hydrogen and so even though they have high hydrogen storage capacities, the drawback is that due to their high hydrogen binding enthalpies, the materials must be heated to remove H2.

To improve the unfavorable thermodynamics and poor kinetics of complex hydrides, researchers have successfully applied a ‘multicomponent’ strategy whereby  two compounds are mixed together to form a multinary phase.  The mixed LiNH2–MgH2 system is a successful example of the employment of the ‘multicomponent’ strategy to improve the characteristics of complex hydrides for hydrogen storage. Applying this method to metal amidoborane systems is an exciting prospect.

With this in mind, Chen et al. synthesized a Li–Na mixed amidoborane, Na[Li(NH2BH3)2] using a wet-chemical method. Using first-principles techniques, the team were able to explore the likelihood of the existence of multicomponent Li–Na amidoboranes with varying  Li/Na ratios. They discovered that the dehydrogenation temperature of Na[Li(NH2BH3)2] is lower than that of lithium or sodium amidoboranes and determined that this could be due to a stronger dihydrogen bond interaction and  a moderate hydrogen atom removal energy. They also proposed the mechanism for the first-step dehydrogenation.

To find out more, read the Dalton Transactions full paper…

Li–Na ternary amidoborane for hydrogen storage: experimental and first-principles study

Wen Li, Ling Miao, Ralph H. Scheicher, Zhitao Xiong, Guotao Wu, C. Moysés Araújo, Andreas Blomqvist, Rajeev Ahuja, Yuanping Feng and Ping Chen

DOI: 10.1039/C2DT11819J

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RSC Solid State Chemistry Group Christmas Meeting

This year’s meeting was a great success and we are proud to announce the winner of the Dalton Transactions Poster Prize was John Clark from the University of Bath. His poster detailed research into new lithium battery technology working with Grahame Gardiner and M. Saiful Islam and was titled ‘Lithium Ion Transport and Defect Chemistry of Mixed-Metal Phosphate Materials for Lithium Battery Applications’. Well done John.

This was the 31st RSC solid state meeting, you can find out more about the group by visiting their webpage or joining them at MyRSC.

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Hot Article: The difference a solvent makes

Zinc alkyl complexes have an interesting role in a wide variety of stoichiometric and catalytic transformations and understanding how the ligands affect reactivity is important in understanding these structures and their reactivity. This Hot Article from Andrew Wheatley and Janusz Lewinski et al. details experiments involving the reactions of Et2Zn with a bicyclic guanidine.

 

Exposure of the produced complex (EtZn(hpp)) to undried air alters the composition depending on whether THF or CH2Cl2 is used as the solvent (displayed above). You can read the full details of the teams investigation by downloading their article below, which is free to access for 4 weeks.

Synthesis, structure and unique reactivity of the ethylzinc derivative of a bicyclic guanidine
Karolina Zelga, Michał Leszczyński, Iwona Justyniak, Arkadiusz Kornowicz, Maciej Cabaj, Andrew E. H. Wheatley and Janusz Lewiński
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT11959E

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Hot Communication: Magnesium MOF

Most metal organic frameworks are based on 3-d or 4-f elements such as Zn, Cu, Co, Ni and there are notably fewer containing lighter metals such as Li, Be, B, Mg, and Al. This Hot Communication by Pingyun Feng and Xianhui Bu et al. reports the first Mg-MOF example constructed from the [Mg33-OH)(CO2)6] trimer and opens up the possibility of further Mg-MOF systems.

The porous crystal shows relatively high H2 uptake (1.37% at 77 K and 1 atm) showing that Mg-MOF systems may have great potential. The applications of MOFs include gas storage, separation, purification and catalysis, undoubtedly developing these applications requires the design and improvement of new MOFs.

You can download this Dalton Transactions Hot Article below, which is free to access for 4 weeks.

Induction of trimeric [Mg3(OH)(CO2)6] in a porous framework by a desymmetrized tritopic ligand
Quanguo Zhai, Qipu Lin, Tao Wu, Shou-Tian Zheng, Xianhui Bu and Pingyun Feng
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12215D

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HOT Article: Role of the activator in dimerization catalysis

Despite the fact that the catalytic activity of Cr and W imido complexes in ethylene dimerization processes has been studied by various authors, to date the analogous Mo catalysts have not been studied.  In this HOT article, Dyer et al. set out to fill this gap in our knowledge and several molybdenum bis(imido) complexes were tested for ethylene dimerization catalysis in combination with EtAlCl2, showing moderate activity when bulky aryl substituents at the imido ligand are employed. In contrast, when MeAlCl2 is used the activity of the catalyst decreases considerably. To understand the role of the activator in these processes the authors have determined the molecular structures of several complexes derived of the reaction of bis(imido) molybdenum compounds with different aluminium halide reagents.

Read more for FREE about the role of the activator in dimerization catalysis until 20th February 2012 at:

Application of molybdenum bis(imido) complexes in ethylene dimerisation catalysis
William R. H. Wright, Andrei S. Batsanov, Antonis M. Messinis, Judith A. K. Howard, Robert P. Tooze, Martin J. Hanton and Philip W. Dyer
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12061E

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HOT Article: Metallocyclic mechanisms at work?

In this HOT article, several new Ti(IV) complexes bearing aryloxy or alkoxy ligands have been prepared and evaluated as catalysts for the oligomerization/polymerization of ethylene. Obviously, polyethylene is the major product but ethylene oligomers also result, ranging from dimers to higher oligomers. The results indicate a number of different active species are formed upon activation, with oligomers likely arising through a metallacyclic mechanism.

Read more about the possible mechanism for FREE until 20th February 2012 at:

Preparation and structures of aryloxy- and alkoxy-Ti(IV) complexes and their evaluation in ethylene oligomerisation and polymerisation
James A. Suttil, David S. McGuinness, Markus Pichler, Michael G. Gardiner, David H. Morgan and Stephen J. Evans
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT11737A

See also the authors previous work providing further evidence for metallocyclic mechanisms at work at:

J. A. Suttil, D. S. McGuinness and S. J. Evans, Dalton Trans., 2010, 39,
5278

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Top ten most accessed articles in December

This month sees the following articles in Dalton Transactions that are in the top ten most accessed:-

Neutral cuprous complexes as ratiometric oxygen gas sensors 
Xiaohui Liu, Wei Sun, Luyi Zou, Zhiyuan Xie, Xiao Li, Canzhong Lu, Lixiang Wang and Yanxiang Cheng 
Dalton Trans., 2012, 41, 1312-1319 DOI: 10.1039/C1DT11777G  
  

A porous metal–organic framework (MOF) with unusual 2D→3D polycatenation based on honeycomb layers 
Xiaoliang Zhao, Jianmin Dou, Di Sun, Peipei Cui, Daofeng Sun and Qingyin Wu 
Dalton Trans., 2012, 41, 1928-1930 DOI: 10.1039/C2DT11898J  

Crystal growth of nanoporous metal organic frameworks 
Martin P. Attfield and Pablo Cubillas 
Dalton Trans., 2012, Advance Article DOI: 10.1039/C2DT12006B  
  

Water oxidation catalysed by manganese compounds: from complexes to ‘biomimetic rocks’ 
Mathias Wiechen, Hans-Martin Berends and Philipp Kurz 
Dalton Trans., 2012, 41, 21-31 DOI: 10.1039/C1DT11537E    

Nitrogen-rich porous covalent imine network (CIN) material as an efficient catalytic support for C–C coupling reactions 
Manas K. Bhunia, Swapan K. Das, Pradip Pachfule, Rahul Banerjee and Asim Bhaumik 
Dalton Trans., 2012, 41, 1304-1311 DOI: 10.1039/C1DT11350J    

Two novel 3-D coordination polymers with 5-methoxyisophthalate and flexible N-donor co-ligands showing pentanuclear or alternate mono/binuclear Cu(ii) units 
Lu-Fang Ma, Jun-Wei Zhao, Min-Le Han, Li-Ya Wang and Miao Du 
Dalton Trans., 2012, 41, 2078-2083 DOI: 10.1039/C1DT11206F    

A pair of 3D homochiral metal–organic frameworks: spontaneous resolution, single-crystal-to-single-crystal transformation and selective adsorption properties 
Xiao-Dan Zheng, Mei Zhang, Long Jiang and Tong-Bu Lu 
Dalton Trans., 2012, 41, 1786-1791 DOI: 10.1039/C1DT11825K    

New photoluminescence acylhydrazidate-coordinated complexes 
Juan Jin, Fu-Quan Bai, Ming-Jun Jia, Yu Peng, Jie-Hui Yu and Ji-Qing Xu 
Dalton Trans., 2012, Advance Article DOI: 10.1039/C1DT11846C    

Unusual coordination mode of tetradentate Schiff base cobalt(iii) complexes 
Anish Cyriac, Jong Yeob Jeon, Jobi Kodiyan Varghese, Ji Hae Park, Soo Young Choi, Young Keun Chung and Bun Yeoul Lee 
Dalton Trans., 2012, 41, 1444-1447 DOI: 10.1039/C2DT11871H    

A highly selective and sensitive BODIPY-based colourimetric and turn-on fluorescent sensor for Hg2+ ions 
Xiong-Jie Jiang, Cheok-Lam Wong, Pui-Chi Lo and Dennis K. P. Ng 
Dalton Trans., 2012, 41, 1801-1807 DOI: 10.1039/C1DT11546D    

Why not take a look at the articles today and blog your thoughts and comments below.

Fancy submitting an article to Dalton Transactions? Then why not submit to us today or alternatively email us  your suggestions.

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Carboxylate complexes going for gold!

Gold nanoparticles (Au-NPs) are attractive for applications in important technological fields as components of biosensors, novel catalysts and new optical, magnetic or electrical devices. Traditional techniques for their preparation include thermal decomposition of organometallic precursors, chemical reduction of Au(I) ions, and electrochemical and photochemical processes. Methods based on reduction by sodium borohydride or citrate ions have been used successfully as the reducing agent acts also as a stabilizer and prevents further aggregation.

As an alternative, Heinrich Lang, from Chemnitz University of Technology, and coworkers have developed a family of gold(I) carboxylate complexes which can be used as precursors for the preparation of Au-NPs in a single step. The ligand works as the reducing and stabilizing part, simultaneously, in one molecule. After thermally induced decomposition of the complexes, Au-NPs are obtained with sizes in the range from 3.3 to 6.5 nm, and almost homogenous size distribution. The ethylene glycol-functionalized carboxylates were obtained from easy chemical reactions using available ethylene gycol or directly from commercial suppliers, and the complexes obtained by a two step procedure.  The authors report than larger chain lengths increased stability and slowed particle growth.

To find out more about it, read the full paper in Dalton Transactions.

Gold nanoparticles generated by thermolysis of “all-in-one” gold(I) carboxylate complexes
André Tuchscherer, Dieter Schaarshmidt, Steffen Schulze, Michael Hietschold, Heinrich Lang,
Dalton Transactions, 2012, Advance Article
DOI: 10.1039/c2dt11748g

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Bacteria are not welcome here: antibacterial surfaces produced in glass

To catch a bacterial infection after a visit to a hospital for a health checkup is not a funny way to become sick. Even worse is when the infection came from a device which was supposed to help you to get better, not sicker, such as a medical device. Intra-hospital infections are difficult to avoid as some viruses or bacterias deposit on any surface available, which may become in contact with a healthy person, with potential health consequences.  Numerous approaches have been looked at in order to create materials with anti-bacterial capabilities. In this direction, silver and copper nanoparticles (AgNP and CuNP) are attractive as they may be able to avoid propagation of several microorganisms, including E. coli and S. aureus. Several methods have been tried to successfully immobilize the nanoparticles to a surface.

Giacomo Dacarro and coworkers at the Università degli Studi di Pavia at Italy, have devised a new way to chemically modify Si-OH terminated surfaces (glass, quartz, SiO2) by using a novel silane-derivatized polyethylenimine (PEI) and testing its ability to coordinate Ag+ and Cu2+ ions, and silver nanoparticles. The functionalized glasses are very effective in fighting against E. coli and S. aureus propagation, and may be an novel platform for use in designing smart, hybrid multifunctional materials.

Read more about his paper published in Dalton Transactions.

Monolayers of polyethilenimine on flat glass: a versatile platform for cations coordination and nanoparticles grafting in the preparation of antibacterial surfaces
Giacomo Dacarro, Lucia Cucca, Pietro Grisoli, Piersandro Pallavicini, Maddalena Patrini and Angelo Taglietti
Dalton Trans., Advance Article, 2012.
DOI: 10.1039/c1dt11373a 

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Nano strikes again! Cross coupling catalytic activity of copper nanoparticles supported on silicon nanowires

Noble metals are highly regarded as unique catalysts for use in several reactions, many of them of interest for the pharmaceutical industry. However, their cost may be a reason why not to be considered in several applications.  When used in the form of nanoparticles, an increase of their activity is expected as a result of their large specific surface area, even when small amounts are used, which can save money and time. In the search for more efficient ways to form C-N bonds, a variety of homogenous catalysts such as Cu, Pd and Rh have been investigated in order to tune them and improve their ability to promote cross-coupling reactions among aryl halides and amines. Specifically, copper mediated Ullmann condensation is attractive as it is cheaper than Pd or Rh.

Zhenhui Kang and his group at the Institute of Functional Nano and Soft Materials and the Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices at Soochow University have developed a new catalyst based on copper nanoparticles inmovilized on silicon nanowires (CuNPs@SiNWs). This catalyst is able to enhance the coupling reaction at 110 °C among benzene halides and aniline in good yields, without the use of any ligand or additive. Even deactivated aryl bromides and inert chlorobenzene were reactive under the action of this novel catalysts. The authors suggest that the use of SiNWs as an alternative substrate support may be of interest of other researchers in the quest of superior heterogeneous catalysts.  

For further information, read the work by Zhenhui Kang and coworkers published in Dalton Transactions.

Copper nanoparticles modified silicon nanowires with enhanced cross-coupling catalytic ability
Keming Pan, Hai Ming, Hang Yu, Hui Huang, Yang Liu, Zhenhui Kang
Dalton Trans., Advance Article, 2012.
DOI: 10.1039/c2dt12182d

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