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About the Cover: The molecular models shown are a portion of the chemical structure of a porous crystal developed by Professor O. M. Yaghi and colleagues at the University of California-Berkeley. Porous crystals are a type of extended structures within which molecules and ions can be trapped and stored, which has potential in applications for clean energy and environmental issues. This structure shown is an example of a metal-organic frameworks (MOF), in which organic fragments are linked together by bonding to metal ions. The MOF shown is synthesized by linking methyl imidazolate with Co(II) or Zn(II). The result is a very open structure with a large internal space (yellow and green spheres) in which other molecules, such as hydrogen, methane, or carbon dioxide, can be inserted. The very open structure of MOFs leads to extremely high effective surface areas and therefore very large storage capacities, In fact, one gram of the material shown has an effective surface area equivalent to that of a football field! (Illustration courtesy of Dr. F. Gandara)
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The new BASF-video covering recent progress in MOF development is now available at youtube. You will find the movie following the link below:
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Incorporating cyclic polyethers into metal-organic frameworks permits specific binding of organic molecules in the porous materials.
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Docking in Metal-Organic Frameworks, Q. Li, W. Zhang, O. Š. Miljanić, C.-H. Sue, Y.-L. Zhao, L. Liu, C. B. Knobler, J. F. Stoddart, O. M. Yaghi, Science, 2009, 325, 855-859
To capture the carbon dioxide generated by coal plants, chemical companies like Dow Chemical Co. and energy giants like Alstom SA have been betting big on liquid solvents like amine, a corrosive derivative of ammonia that has a thirst for binding with CO2.
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Yaghi is featured in the Chronicle of Higher Education on May 8, 2009.
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The IV joint International Symposium on Macrocyclic & Supramolecular Chemistry, 21-25 June 2009, Maastricht, The Netherlands.
Visit the conference website.The data was provided by Thomson Reuters from its Essential Science Indicators database, 1 January 1998 to 30 June 2008.
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Dr. Omar Yaghi featured on UCLA Spotlight.
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Geometry is at the heart of chemistry, and in the work of Omar M. Yaghi, this year's winner, the marriage of chemical form and function is blatant and welcome. In his metal organic framework (MOF) crystals and related networklike structures, which Yaghi, 43, collectively refers to as reticular chemistry, geometry becomes beautifully real.
Green technology was hot in 2008. Barack Obama won the presidential election promising green jobs to Rust Belt workers. Investors poured $5 billion into the sector just through the first nine months of the year. And even Texas oilmen like T. Boone Pickens started pushing alternative energy as a replacement for fossil fuels like petroleum, coal and natural gas.
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Molecular sponges- is there a limit to the spectacular catalytic and storage abilities of MOFs? Jon Evan investigates, an article in C&EN.
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"Omar Yaghi and colleagues at the University of California at Los Angeles applied high throughput chemistry to make a series of highly porous crystalline materials called zeolitic imidazolate frameworks (ZIFs)."
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For Metal-Organic frameworks, lab-scale research is brisk as commercialization begins.
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The German chemical company BASF is marketing metal organic frameworks, first invented in the Yaghi labs, under the trade name Basolite Mofs. The compound, of which one gram has the surface area of several football fields, can store and release small molecules such as energy-rich gases with its open framework structure and is being sold through Aldrich Chemicals.
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Developed by Omar Yaghi and colleagues at the University of California at Los Angeles (UCLA), the new compounds are made from zeolitic imidazolate frameworks (ZIFs) - porous crystalline materials with a cage-like structure that resembles natural aluminosilicate zeolites.
Read here about this super-sized molecular sponges that can boost carbon capture.
With their high thermal and chemical stability and ease of fabrication, ZIFs are promising materials for strategies aimed at ameliorating increasing atmospheric carbon dioxide levels. The materials are chemically and thermally stable, yet have the long-sought-after design flexibility offered by functionalized organic links and a high density of transition metal ions.
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Yaghi's lab employs automation techniques frequently found in the biotech and pharmaceutical industry to rapidly test crystal samples on a scale not previously possible, which has led to an avalanche of new discoveries.
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A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390?C) and chemical stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square meters per gram), and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2: 1 liter of ZIF-69 can hold ~83 liters of CO2 at 273 kelvin under ambient pressure.
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Porous solids have become a rich playground for chemists, who can tailor the materials' makeup for use in gas storage, filtering, and catalysis. ZIFs developed in the Yaghi labs excel at these applications.
Researchers in the Yaghi labs have developed porous materials that can soak up 80 times their volume of carbon dioxide, offering the tantalizing possibility that the greenhouse gas could be cheaply scrubbed from power-plant smokestacks. The results published in Science Magazine are garnering the attention of the global science and tech community.
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http://www.ucla.edu/, under "News & Notices," and on the UCLA News web site: http://www.newsroom.ucla.edu/. It is permanently archived at http://www.newsroom.ucla.edu/portal/ucla/new-materials-can-selectively-45139.aspx and has been sent to the national and international media.
Dr. Omar Yaghi and members of his lab win the American Association for the Advancement of Science 2007 Newcomb Cleveland Prize for their paper in Science Magazine "Designed synthesis of 3D covalent organic frameworks, H. M. El-Kaderi, J. R. Hunt, J. L. Mendoza-Cortes, A.P. Cote, R.E. Taylor, M. O'Keefe, O.M. Yaghi, Science, 2007, 316, 268-272".
The Yaghilab's highly porous organic framework known as COF-105 is chosen to grace the cover of the December issue of C&EN. The Yaghilab's pioneering work in the area of COFs is highlighted in the 2007 Chemical Year in Review.
"Essential Science Indicators ranks Omar Yaghi as the 15th most-cited chemist with a total of 10,408 citations from 75 papers at an impressive frequency of 138.77 citations per paper for the ten-year plus six-month period, January 1997 - June 30, 2007." Omar has risen from # 22 in December of 2006 up from #28 in November 2005.
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The article, "Metal-Organic Frameworks with Exceptionally High Capacity for Storage of Carbon Dioxide at Room Temperature", published in the Journal of the American Chemical Society is being featured on the ACS Publications website as a "Hot Paper" as defined by Thomson Scientific (ISI) Essential Science Indicators. Hot Papers are articles published within the last two years receiving the most citations over the most recent two-month period.
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The article, "Effects of Functionalization, Catenation, and Variation of the Metal Oxide and Organic Linking Units on the Low-Pressure Hydrogen Adsorption Properties of Metal-Organic Frameworks", published in the Journal of the American Chemical Society is being featured on the ACS Publications website as a "Hot Paper" as defined by Thomson Scientific (ISI) Essential Science Indicators. Hot Papers are articles published within the last two years receiving the most citations over the most recent two-month period.
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As featured in the Accounts of Chemical Research article the unique structure MOF-3:
(a) Building unit in the crystal structure of Zn3(BDC)3⋅6CH3OH (MOF-3), in which each carboxylate carbon of four BDC units and an oxygen from each of the remaining BDC links form. (b) Octahedral (Oh) SBU, that assembles into (c) a primitive cubic-like decorated diamond net topology. (Structures were drawn using single-crystal X-ray diffraction data.)
Space Invaders
Space exploration usually means leaving Earth's orbit. But chemists are now burrowing inside solids to open new vistas. Katharine Sanderson reports from the internal frontier.
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COF-108 is built from tetrahedral and planar triangular building blocks joined by C2O2B rings. Carbon is blue; oxygen, red; and boron yellow.
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Microporous materials contain pores or channels with diameters of less than 2 nm- only a little bigger than many molecules. These pores or channels may be used as filters that allow some species through but not others, as containers to isolate or store specific molecules, or as tiny chemical reactors. Chemists have found ways to prepare a wide variety of porous materials, but it has proved difficult to form organic polymer networks with perfectly controlled pore dimensions- until now.
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Professor Omar M. Yaghi was presented with the 2007 DOE Hydrogen Program R & D Award in Recognition of Outstanding Achievement in Storage Research and Development in Arlington, VA on May 16th 2007 at the Department of Energy Hydrogen Program Annual Merit Review.
Professor Yaghi's lecture "Metal Organic Reticular Frameworks" was presented to the Council of Scientific Society Presidents on May 6th , 2007 in Washington, D.C. As a guest speaker for the Frontiers of 21st Century Science Forum, he was awarded the 2007 Certificate of Appreciation for Outstanding Contributions to the Understanding of "Reticular Chemistry" by the National Council.
Professor Yaghi's lecture, titled "Crystals of Pores Without Walls for Clean Energy," was presented on April 3. As a guest speaker at the 2006-07 Annual Science Faculty Research Colloquium Series, he has been awarded Dean's Recognition Award at the College of Letters and Science, UCLA.
The covalent organic frameworks, or COFs (pronounced "coffs"), one of these new classes of materials, are the first crystalline porous organic networks. A member of this series, COF-108, has the lowest density reported of any crystalline material.
"These are the first materials ever made in which the organic building blocks are linked by strong bonds to make covalent organic frameworks," Yaghi said. "The key is that COFs are composed of light elements, such as boron, carbon and oxygen, which provide thermal stability and great functionality."
COF-108, the latest advance in reticular chemistry development, has a high surface area, with more than 4,500 meters per gram.
"One gram, unraveled, could cover the surface area of approximately 30 tennis courts," Yaghi said.
In the push to develop methods to control greenhouse gas emissions, some of the biggest challenges have been finding ways to store hydrogen for use as a fuel, to use methane as an alternative fuel, and to capture and store carbon dioxide from power plant smokestacks before it reaches the atmosphere. Yaghi and his colleagues believe COFs are uniquely suited for all these applications because of their functional flexibility and their extremely light weight and high porosity.
Through reticular chemistry, Yaghi has developed a process whereby it is possible to utilize the arsenal of organic building blocks to construct a large number of new COF structures whose components can be easily designed to suit a particular application. The pore size and pore functionality of these materials can be varied at will.
Yaghi, whose research overlaps chemistry, materials science and engineering, is a member of the California NanoSystems Institute (CNSI) at UCLA, which encourages cross-disciplinary collaboration to solve problems in nanoscience and nanotechnology. Yaghi is also the director of the Center for Reticular Chemistry at the CNSI.
"I have long been interested in making materials in a rational way," Yaghi said. "At the beginning of my career, I always thought it should be possible to create a predetermined chemical structure by linking together well-defined molecules as building blocks, just as an architect creates a blueprint prior to construction on buildings."
A year ago, Yaghi made national headlines when he and his team at UCLA, along with colleagues at the University of Michigan, conducted research that could lead to a hydrogen fuel that powers not only cars but laptop computers, cellular phones, digital cameras and other electronic devices. The findings were reported in the Journal of the American Chemical Society in March 2006.
The materials used in that research, invented by Yaghi in the early 1990s, are called metal-organic frameworks, or MOFs, which have been described as crystal sponges. These frameworks have nanoscale-size openings, or pores, in which Yaghi and his colleagues can store gases ? such as hydrogen and methane ? that are generally difficult to store and transport.
BASF, a global chemical company based in Germany, has licensed the technology and is moving forward on commercialization of MOFs.
In the fall of 2006, Yaghi was named one of the "Brilliant 10" by Popular Science magazine, which described him as a "hydrogen nano-architect" whose "research papers rank among the most influential in his field." At the age of 42, Yaghi is already ranked No. 22 on the list of the Top 100 most-cited chemists by Thomson Scientific.
Rankings of Most-Cited Articles listed are based on data from Thomson ISI? Web of Science. Yaghi group members contributed two of the top ten most-cited articles.
8. Exceptional H2 Saturation Uptake in Microporous Metal-Organic Frameworks, Antek G. Wong-Foy, Adam J. Matzger, and Omar M. Yaghi, J. Am. Chem. Soc., 2006, 128(11), 3494 - 3495; Full Article
10. Effects of Functionalization, Catenation, and Variation of the Metal Oxide and Organic Linking Units on the Low-Pressure Hydrogen Adsorption Properties of Metal-Organic Frameworks, Jesse L. C. Rowsell and Omar M. Yaghi, J. Am. Chem. Soc., 2006, 128(4), 1304 - 1315; Full Article
View the entire list of top twenty Most-Cited articles of 2006 of the Journal of the American Chemical Society.
Metal-organic frameworks (MOFs) were invented by the McCoy Award winner in the early 90s. MOFs have crystal structures that resembles a scaffold made of linked rods ? a solid-state structure that gives them a multitude of nanoscale pores and a correspondingly vast internal surface area where gas molecules can accumulate. A pinch of a MOF has roughly the surface area of a football field. An analysis of seven new MOFs, reported in a communication in the Journal of the American Chemical Society earlier this year, revealed two of them that exhibit a combination of substantial H2 uptake and moderate densities. These approach the 2010 DOE target of 45 g of H2/L volume, demonstrating that the volumetric capacity of MOFs is feasible as a storage medium for stationary and mobile fueling applications. 45 g is 22.5 moles and would occupy more than 500 liters!
The Herbert Newby McCoy Award was established in 1964 by Mrs. Ethel Terry McCoy in honor of her husband. He wrote Introduction to General Chemistry (1919) with his wife-to-be, Ethel Terry, and contributed to numerous papers on physical chemistry, radioactivity and rare earths. To support her husband's life-long interest in science, Mrs. McCoy designated that this annual award be made to a student or faculty member in the chemistry department making the greatest contribution of the year to science.
December 6, 2006 - For the period January 1996 to June 30, 2006, Omar Yaghi is ranked by the Institute for Scientific Information as the 22nd most-cited chemist with a total of 8,632 citations from 73 papers at an impressive frequency of 118 citations per paper. Omar has risen from #28 in November 2005 and from #59 in November 2004.
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Please Visit the ACS Publications website for more information.
Hot Papers are articles published within the last 2 years receiving the most citations over the most recent 2-month period. For the current two month period, the ISI® recognizes 244 total Hot Papers in chemistry alone, with ACS Publications accounting for 41 of the top 100, or more than 40% of the 'hottest' papers in chemistry! At the top of the list is Hydrogen Sorption in Functionalized Metal-Organic Frameworks.
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The National Nanotechnology Initiative (NNI) provides a multi-agency framework to ensure U.S. leadership in nanotechnology that will be essential to improved human health, economic well being and national security. The NNI invests in fundamental research to further understanding of nanoscale phenomena and facilitates technology transfer.
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Omar Yaghi, 41; UCLA-Los Angeles; materials science
Compressing gas usually takes very high pressure or very low temperature. Yaghi used molecular building blocks to create tiny, honeycombed scaffolding, which draws gas molecules close together, potentially making hydrogen-fueled cars feasible.
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April 2006 - Responding to the U.S. Energy Department's "Grand Challenge" for better hydrogen storage technologies (H&FCL July '03), researchers at the Universities of California Los Angeles (UCLA) and Michigan have developed a material that exceeds DoE current targets.
Storing gaseous amounts in handheld electronic devices powered by small fuel cells is a key issue in and obstacle to the commercialization of hydrogen energy technology.
UCLA chemistry professor Omar Yaghi and Michigan's Adam Matzger and Antek Wong-Foy have developed a new family of metal organic frameworks (MOFs) that can adsorb up to 7.5% by weight (Yaghi moved to UCLA from Michigan only recently). These materials, also described as "crystal sponges," so far store about one percent more than the 6.5% by weight that DoE estimates is needed to make hydrogen fuel practical for cars, according to UCLA's release.
Some phrases just ring with a futuristic tone, despite our inescapable presence already in the 21st century. One of them is "crystal engineering." It suggests, for example, high-tech diamond merchants mindful of a plan that goes beyond digging for their wares. In truth, crystal engineering is a technology that's already arrived, with a host of applications from fuel cells on a chip to nanosensors and molecular electronics.
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Chemistry professor's interest in molecules leads to storage of gases:
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Metal-organic framework materials (MOFs) have attracted great attention since they were first synthesized in 1999 because their extraordinary level of porosity and large surface area hold promise for gas adsorption and storage.
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New materials and methods are improving hydrogen storage and production technology, but significant challenges remain.
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Professor Omar M. Yaghi, Making an impact on fuel cell technology.
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The notion seems almost inconceivable: develop a material with so much storage capacity that less than half an ounce of the stuff covers the surface area of a football field.
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University of Michigan chemist Omar Yaghi is shown with a model of a metal-organic framework. His lab got a boost from a pair of federal grants.
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$350 Million in help from government announced in Detroit
Private sector chips in $225 million
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"At first glance, the crystal looks like a diamond," said Dr. Omar M. Yaghi, a professor of chemisty at the University of Michigan.
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Design strategy yields porous crystals with record-breaking surface area.
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"SPACIOUS and amply proportioned with plenty of storage space" If MOF-177 were an apartment, that's probably how the vendor's patter would go.
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A class of materials called Metal-Organic Frameworks (MOF), which are able to store large quantities of hydrogen that is easily accessible to fuel cells, is under development at the University of Michigan.
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Microporous Materials
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A new class of materials can store large amounts of hydrogen at normally encountered temperatures and pressures, without the problems associated with other approaches, according to chemists at the University of Michigan working in collaboration with researchers from the University of California at Santa Barbara, Los Alamos National Laboratory and Arizona State University.
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Article in the Process Technology section.
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BASF unit makes fourth investment in start-up businesses
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Molecular design leads to materials with large H2 storage capacity.
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Cover Image!
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Fundamental Physics, Chemistry and Materials Science R&D required Proposals due in September 2003.
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Crystals full of Nothing: An Inevitable Outcome of Molecular Design and a New Opportunity for Materials and Inorganic Chemistry.
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Modern crystal engineering has emerged as a rich discipline whose success requires an iterative process of synthesis, crystallography, crystal structure analysis, and computational methods.
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Porous metal-organic frameworks offer useful properties for gas storage.
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Some chemists worry plenty about nothing.. Well, almost nothing. It's the holes inside solid materials that are on their minds.
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Scientists attempting to make crystals with large pores- desirable for separations, catalysis, sensing and storage- usually have to contend with loss of stablility as pore size increases.
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The importance of porous materials to the world/s chemical industry is reflected by their near US $350 billion sector of the global economy.
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Guest Co-Editors: Omar M. Yaghi & M. O'Keefe
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For years, chemists have fantasized about molecular scaffolds that would catalyze the tricky chemistry that enzymes foster. The structures would provide a framework for assembling and dissecting organic molecules. Toward this goal, researchers have attempted to make gauzy crystals that are themselves organic.
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Chemistry may not grab the kind of headlines that computers do, but it's what makes modern life happen, from gasoline to plastics to the material of computer chips. Chemical catalysts are special molecules that encourage chemical processes and are one of the most critical components of our technological culture. These chemical movers and shakers are the unsung heroes of our chemistry-based civilization.
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