From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids.

The continued increase in the atmospheric concentration of carbon dioxide due to anthropogenic emissions is predicted to lead to significant changes in climate. About half of the current emissions are being absorbed by the ocean and by land ecosystems, but this absorption is sensitive to climate as well as to atmospheric carbon dioxide concentrations, creating a feedback loop. General circulation models have generally excluded the feedback between climate and the biosphere, using static vegetation distributions and CO2 concentrations from simple carbon-cycle models that do not include climate change. Here we present results from a fully coupled, three-dimensional carbon–climate model, indicating that carbon-cycle feedbacks could significantly accelerate climate change over the twenty-first century. We find that under a 'business as usual' scenario, the terrestrial biosphere acts as an overall carbon sink until about 2050, but turns into a source thereafter. By 2100, the ocean uptake rate of 5 Gt C yr-1 is balanced by the terrestrial carbon source, and atmospheric CO2 concentrations are 250 p.p.m.v. higher in our fully coupled simulation than in uncoupled carbon models, resulting in a global-mean warming of 5.5 K, as compared to 4 K without the carbon-cycle feedback.

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Acceleration of global warming due to carbon-cycle feedbacks in a coupled climate model

The escalating level of atmospheric carbon dioxide is one of the most pressing environmental concerns of our age. Carbon capture and storage (CCS) from large point sources such as power plants is one option for reducing anthropogenic CO(2) emissions; however, currently the capture alone will increase the energy requirements of a plant by 25-40%. This Review highlights the challenges for capture technologies which have the greatest likelihood of reducing CO(2) emissions to the atmosphere, namely postcombustion (predominantly CO(2)/N(2) separation), precombustion (CO(2)/H(2)) capture, and natural gas sweetening (CO(2)/CH(4)). The key factor which underlies significant advancements lies in improved materials that perform the separations. In this regard, the most recent developments and emerging concepts in CO(2) separations by solvent absorption, chemical and physical adsorption, and membranes, amongst others, will be discussed, with particular attention on progress in the burgeoning field of metal-organic frameworks.

Carbon Dioxide Capture: Prospects for New Materials

Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has seen widespread success involves the use of a proximal heteroatom that serves as a directing group for the selective functionalization of a specific C-H bond. In a survey of examples of heteroatom-directed Rh catalysis, two mechanistically distinct reaction pathways are revealed. In one case, the heteroatom acts as a chelator to bind the Rh catalyst, facilitating reactivity at a proximal site. In this case, the formation of a five-membered metallacycle provides a favorable driving force in inducing reactivity at the desired location. In the other case, the heteroatom initially coordinates the Rh catalyst and then acts to stabilize the formation of a metal-carbon bond at a proximal site. A true test of the utility of a synthetic method is in its application to the synthesis of natural products or complex molecules. Several groups have demonstrated the applicability of C-H bond functionalization reactions towards complex molecule synthesis. Target-oriented synthesis provides a platform to test the effectiveness of a method in unique chemical and steric environments. In this respect, Rh-catalyzed methods for C-H bond functionalization stand out, with several syntheses being described in the literature that utilize C-H bond functionalization in a key step. These syntheses are highlighted following the discussion of the method they employ.

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Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

Core/Shell Nanoparticles: Classes, Properties, Synthesis Mechanisms, Characterization, and Applications

The storage of large quantities of hydrogen at safe pressures is a key factor in establishing a hydrogen-based economy. Previous strategies--where hydrogen has been bound chemically, adsorbed in materials with permanent void space or stored in hybrid materials that combine these elements--have problems arising from either technical considerations or materials cost. A recently reported clathrate hydrate of hydrogen exhibiting two different-sized cages does seem to meet the necessary storage requirements; however, the extreme pressures (approximately 2 kbar) required to produce the material make it impractical. The synthesis pressure can be decreased by filling the larger cavity with tetrahydrofuran (THF) to stabilize the material, but the potential storage capacity of the material is compromised with this approach. Here we report that hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to approximately 4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability. The tuning mechanism is quite general and convenient, using water-soluble hydrate promoters and various small gaseous guests.

Tuning clathrate hydrates for hydrogen storage

Clathrate hydrates, ice-like host–guest systems containing guest molecules in cages of hydrogen-bonded water molecules exist in three well-characterized cubic forms, and a less well-characterized tetragonal form1,2 On the basis of 2H and l29Xe NMR measurements and X-ray and neutron powder diffraction results, we now report a new hexagonal hydrate structure requiring both large and small guest molecules to stabilize the structure This hydrate is expected to be isostructural with the hexagonal clathrasil dodecasil-lH (see ref 14 for clathrasil nomenclature) As for the cubic clathrate hydrates, the new hydrate structure may occur naturally

A new clathrate hydrate structure

Recovering Methane from Solid Methane Hydrate with Carbon Dioxide

Supramolecular Control of Reactivity in the Solid State Using Linear Molecular Templates

Natural gas hydrates — ice-like solids that consist of 'guest' molecules trapped in cages of water molecules — are a potential source of energy and may play a role in climate change and seafloor collapse. Experiments have shown that there are three common gas hydrate structures — sI, sII and sH — but only sI and sII hydrate have been found in the natural environment. Now sH hydrate (in close association with sII hydrate) has been identified in seafloor samples from Barkley canyon, 80 km off Vancouver Island. This complex gas hydrate can trap larger guest molecules than sI or sII, and is more stable than sI hydrate, indicating that gas hydrates could be more widely distributed than previously thought. The discovery of sH hydrate in a sample from Barkley Canyon marks the first time this hydrate has been found in the natural environment. This complex gas hydrate can trap larger guest molecules than sI or sII hydrate, and is stable at higher temperatures and pressures than sI hydrate, indicating that gas hydrates could be more widely distributed than previously thought. Natural gas hydrates are a potential source of energy1 and may play a role in climate change2 and geological hazards3. Most natural gas hydrate appears to be in the form of ‘structure I’, with methane as the trapped guest molecule4, although ‘structure II’ hydrate has also been identified, with guest molecules such as isobutane and propane, as well as lighter hydrocarbons5,6. A third hydrate structure, ‘structure H’, which is capable of trapping larger guest molecules, has been produced in the laboratory7, but it has not been confirmed that it occurs in the natural environment. Here we characterize the structure, gas content and composition, and distribution of guest molecules in a complex natural hydrate sample recovered from Barkley canyon, on the northern Cascadia margin8. We show that the sample contains structure H hydrate, and thus provides direct evidence for the natural occurrence of this hydrate structure. The structure H hydrate is intimately associated with structure II hydrate, and the two structures contain more than 13 different hydrocarbon guest molecules. We also demonstrate that the stability field of the complex gas hydrate lies between those of structure II and structure H hydrates, indicating that this form of hydrate is more stable than structure I and may thus potentially be found in a wider pressure–temperature regime than can methane hydrate deposits.

John A. Ripmeester

Papers

Tuning clathrate hydrates for hydrogen storage

A new clathrate hydrate structure

Recovering Methane from Solid Methane Hydrate with Carbon Dioxide

Supramolecular Control of Reactivity in the Solid State Using Linear Molecular Templates

Complex gas hydrate from the Cascadia margin