Green Chemistry Blog

The European Commission has established a target for EU member states to obtain 20% of their energy from renewable sources by the year 2020. Although production of electricity from solar energy and hydropower are crucial technologies in achieving this goal, liquid hydrocarbon fuels are seemingly irreplaceable in certain heavy transportation sectors (specifically sea freight and aviation).

Scientific advances are now being made in the use of non-food crops to produce liquid hydrocarbon fuels, complementing the established oxygenated biofuels made of ethanol and bio-diesel. The latest research demonstrates that pine wood can be successfully converted into a mixture of liquid hydrocarbons. The resulting fuel has a similar calorific value to diesel, and contains less than 5% oxygen.

The necessary catalyst is made through a simple wet impregnation technique to give copper and ruthenium supported on phosphotungstic acid, which is then calcined. The transformation of the lignocellulosic biomass is conducted under hydrogen at an elevated temperature to produce the liquid fuel (30 wt%), which separates from an aqueous phase and any residual solid. The organic liquid was found to contain a number of mostly cyclic aliphatic hydrocarbons and also aromatic compounds, and thus is an attractive option as a next generation biofuel.

Direct thermocatalytic transformation of pine wood into low oxygenated biofuel
Walid Al Maksoud, Cherif Larabi, Anthony Garron, Kai C. Szeto, Jean J. Walter and Catherine C. Santini
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC42596G

Here are the latest hot papers published in Green Chemistry, as recommended by the referees:

Water at elevated temperatures (WET): reactant, catalyst, and solvent in the selective hydrolysis of protecting groups
Wilmarie Medina-Ramos, Mike A. Mojica, Elizabeth D. Cope, Ryan J. Hart, Pamela Pollet, Charles A. Eckert and Charles L. Liotta  
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC42569J

Laccase/TEMPO-mediated system for the thermodynamically disfavored oxidation of 2,2-dihalo-1-phenylethanol derivatives
Kinga Kędziora, Alba Diaz-Rodriguez, Iván Lavandera, Vicente Gotor-Fernández and Vicente Gotor  
Green Chem., 2014, Accepted Manuscript, DOI: 10.1039/C4GC00066H

Multicomponent Reactions: Advanced Tools for Sustainable Organic Synthesis
Razvan Cioc, E. Ruijter and Romano Orru  
Green Chem., 2014, Accepted Manuscript, DOI: 10.1039/C4GC00013G

 All the papers listed above are free to access for the next 4 weeks!

Utilization of renewable materials, such as carbon dioxide and cellulose, is a prevailing goal of green chemistry. Homogenous conditions promote the use of cellulose, but finding solvent systems that appreciably dissolve this robust polymer is a difficult task. Processing cellulose with minimal waste and economic cost are additional considerations, and existing methods warrant improvement in these regards. In another fashion, the utilization of carbon dioxide is dependent upon novel methods for capture and storage (CCS). Researchers at the Dalian National Laboratory for Clean Energy, China, have integrated the goals of CCS and cellulose dissolution in their latest research effort.

It is well known that mixtures of organic liquids, comprised of a strong base and an alcohol, form reversible ionic compounds upon the introduction of carbon dioxide. By using 1,1,3,3-tetramethyl guanidine in combination with dimethylsulfoxide (DMSO) and ethylene glycol, in particular, they observed microcrystalline cellulose dissolution of up to 10 wt% under mild conditions. The presence of the co-solvent DMSO was integral to achieve this extent of dissolution, and cellulose regeneration and recovery could be accomplished by several methods.

Learn more about their exciting results here:

Capturing CO₂ for cellulose dissolution
Haibo Xie, Xue Yu, Yunlong Yang, and Zongbao Kent Zhao
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC42395F 
 

Jenna Flogeras obtained her B.Sc. and M.Sc. in Chemistry from the University of New Brunswick (Fredericton), Canada. She is currently working towards her Ph.D. at Memorial University of Newfoundland, under the supervision of Dr. Francesca Kerton. Her research is focused on the synthesis of biodegradable polymers using main-group metal complexes as catalysts.

Here are the latest hot papers published in Green Chemistry, as recommended by the referees:

Physical properties and hydrolytic degradability of polyethylene-like polyacetals and polycarbonates
Patrick Ortmann, Ilona Heckler and Stefan Mecking  
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC42592D

Efficient chemical fixation of CO2 promoted by a bifunctional Ag2WO4/Ph3P system
Qing-Wen Song, Bing Yu, Xue-Dong Li, Ran Ma, Zhen-Feng Diao, Rong-Guan Li, Wei Li and Liang-Nian He 
Green Chem., 2014,16, 1633-1638, DOI: 10.1039/C3GC42406E

Water at elevated temperatures (WET): reactant, catalyst, and solvent in the selective hydrolysis of protecting groups
Wilmarie Medina-Ramos, Mike A. Mojica, Elizabeth D. Cope, Ryan J. Hart, Pamela Pollet, Charles A. Eckert and Charles L. Liotta  
Green Chem., 2014, Advance Article. DOI: 10.1039/C3GC42569J

All the papers listed above are free to access for the next 4 weeks!

Research by French scientists has identified 18 vanillin derived chemicals for application in the synthesis of bio-based polymers. Vanillin is interesting as a chemical intermediate because of its different functional groups, and because it is manufactured in different ways. Extraction of natural vanillin and fermentation of bio-based ferulic acid are high cost options compared to the petroleum derived synthesis from guaiacol. An alternative route to vanillin has recently been proposed starting from p-cresol, but this approach is also based on non-renewable feedstocks. Another procedure that presently has a minority share of global vanillin production is the valorisation of lignin. This process had fallen out of favour somewhat, but cleaner technologies have revitalised research into vanillin derived from Kraft lignin, benefiting from the growing interest in producing chemicals from lignin more generally.

Polymers of vanillin are known, but are not often significantly diversified from the parent molecule. This latest work lead by Sylvain Caillol has resulted in the synthesis of difunctionalised epoxides, carbonates, alkenes, alcohols, amines and carboxylic acids, all with obvious potential as monomers for bio-based polymers. Different polymer types have been targeted, including epoxy resins, polyesters and polyurethanes. Through this research a number of opportunities for new and interesting renewable polymers have been opened up, which utilise the abundant resource of lignin via the important chemical intermediate vanillin.

Vanillin, a promising biobased building-block for monomer synthesis
Maxence Fache, Emilie Darroman, Vincent Besse, Auvergne Rémi, Sylvain Caillol and Bernard Boutevin
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC42613K

Shrimp shells that would otherwise be thrown away by the seafood industry have been turned into tough fibres that can harvest valuable metals from water.

Robin Rogers, and his team at the University of Alabama in the US, had long been interested in using ionic liquids to process cellulose but the Deepwater Horizon oil spill in 2010 encouraged them to try something similar with chitin, the structural biopolymer that makes up the shells of various crustaceans. ‘We started working with the Gulf Coast Agricultural and Seafood Co-Op in Bayou La Batre, looking at uses for their shrimp shell waste, about the same time as the moratoriums on shrimping. It was quite clear that new products and profits were needed.’

Read the full article in Chemistry World»

Read the original journal article in Green Chemistry – it’s free to access until 9th April:
Surface modification of ionic liquid-spun chitin fibers for the extraction of uranium from seawater: seeking the strength of chitin and the chemical functionality of chitosan
Patrick S. Barber, Steven P. Kelley, Chris S. Griggs, Sergei Wallace and Robin D. Rogers  
Green Chem., 2014, Advance Article, DOI: 10.1039/C4GC00092G, Paper