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SURFACE SCIENCE ESPIONAGE AT THE ATOMIC SCALE Microscopy probes nanofiber growth process with angstrom resolution L IKE INTELLIGENCE AGENTS armed with high-tech sur- veillance gear, scientists in Denmark are using sophisticat- ed lab tools to uncover the clan- destine side of chemical reaction dynamics related to the growth of carbon nanofibers. The atom- ic-scale spying has revealed sur- prising nanoparticle behavior that may prove useful in under- standing a wide range of catalyt- ic surface reactions and other mo- lecular processes. Growing carbon nanofibers by decomposing hydrocarbon gases on solid catalysts has intrigued re- searchers for decades. But prob- ing the fundamental steps that drive the growth process has proven difficult to carry out with high resolution, in part because of the high temperature and pressure required to sustain the reaction. Now, researchers at catalyst manufacturer HaldorTbpsoe and at the Technical University of Denmark, both in Lyngby, have tracked the carbon nanofiber growth process in real time and in unprecedented spatial detail. Us- ing a specially designed trans- mission electron microscope, the team, which includes Stig Helveg, physics professor Jens K. Nor- skov, and their coworkers, ex- posed nanometer-sized nickel particles dispersed on MgAl 2 0 4 to a methane-hydrogen mixture at roughly 500 °C. They record- ed the results in angstrom-reso- lution videos [Nature, 427, 426 (2004)}. The images capture a lively re- action scenario in which nano- fiber growth is seen to be medi- ated by continuous and sudden changes in the shape of the nick- el particles. (Videos can be viewed at C&ENOnline, http://wwwcen- online.org.) Reactions of the gas on the catalyst cause the approx- imately 10-nm spherical particles to become highly elongated, then abruptly return to a spherical shape, while nanofibers grow spontaneously from the particle's surface. From a detailed inspection of the images and quantum me- chanical calculations, the re- searchers conclude that nucle- ation and growth of the fibers' graphene layers occur at tiny de- fects in the nickel crystals known as single-atom step edges. The angstrom-sized imperfections are observed to form and then dis- appear repeatedly during the course of the reaction. Based on the experimental and computa- tional results, the researchers pro- pose that the growth mechanism depends on surface diffusion of carbon and nickel atoms. Commenting in the same is- sue of Nature, PulickelM. Ajayan, a professor of materials science and engineering at Rensselaer Polytechnic Institute, remarks that the study "has overcome EYE OF THE FIBER An electron micrograph recorded under reaction conditions reveals the dynamic role of 10-nm nickel catalyst particles (blue) in forming carbon nanofibers (green) via hydrocarbon decomposition. some major experimental stum- bling blocks to provide the first direct glimpses of nanofibers as they grow" Ajayan notes that the experiments show the impor- tance of shape transformations in particles used as nanoscale growth catalysts. He adds that the work "should lead to better con- trol over fiber synthesis for nano- technology"—MITCH JACOBY FERTILIZER IMC P Cargill Merge Crop Nutrient Business I MC Global and agribusiness giant Cargill have signed a definitive agreement to com- bine their phosphate, potash, and nitrogen assets to create the second largest global fertil- izer operation, with $4.1 billion in annual sales. When the deal closes later this summer- subject to regulatory approval—the new, as- yet-unnamed publicly owned company will be larger than number three Potash Corp. of Saskatchawan, with estimated annual sales of $2.6 billion. Number one Yara, the Norsk Hydro fertilizer business to be spun off to shareholders later this year, has sales of about $4.9 billion. In return for two-thirds of the new firm's shares, Cargill is to contribute its fertilizer operations with $2 billion in sales and $50 million in debt. IMC turns over a business with $2.1 billion in sales and $2.1 billion in debt. IMC shareholders will own one-third of the new firm, which is to be headed by Fritz Corrigan, now Cargill executive vice president. For IMC, the merger means allying with a strong partner after years of losses caused by industry overcapacity and a farm reces- sion. Executives say the fertilizer industry is poised for a recovery. For Cargill, the largest U.S. privately held firm, the deal means enlarging its position in fertilizers at the expense of going public—the first time an operation of the secretive fami- ly-owned business will be open to public scrutiny—MARC REISCH HTTP://WWW.CEN-ONLINE.ORG C&EN / FEBRUARY 2, 2004 7

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S U R F A C E S C I E N C E

ESPIONAGE AT THE ATOMIC SCALE Microscopy probes nanofiber growth process with angstrom resolution

L IKE INTELLIGENCE AGENTS

armed with high-tech sur­veillance gear, scientists in

Denmark are using sophisticat­ed lab tools to uncover the clan­destine side of chemical reaction dynamics related to the growth of carbon nanofibers. The atom­ic-scale spying has revealed sur­prising nanoparticle behavior that may prove useful in under­standing a wide range of catalyt­ic surface reactions and other mo­lecular processes.

Growing carbon nanofibers by decomposing hydrocarbon gases on solid catalysts has intrigued re­searchers for decades. But prob­ing the fundamental steps that drive the growth process has proven difficult to carry out with high resolution, in part because of the high temperature and pressure required to sustain the reaction.

Now, researchers at catalyst manufacturer HaldorTbpsoe and at the Technical University of Denmark, both in Lyngby, have tracked the carbon nanofiber growth process in real time and in unprecedented spatial detail. Us­ing a specially designed trans­mission electron microscope, the team, which includes Stig Helveg, physics professor Jens K. Nor-skov, and their coworkers, ex­posed nanometer-sized nickel particles dispersed on MgAl204

to a methane-hydrogen mixture at roughly 500 °C. They record­ed the results in angstrom-reso­lution videos [Nature, 427, 426 (2004)}.

The images capture a lively re­action scenario in which nano­fiber growth is seen to be medi­ated by continuous and sudden changes in the shape of the nick­el particles. (Videos can be viewed at C&ENOnline, http://wwwcen-online.org.) Reactions of the gas on the catalyst cause the approx­

imately 10-nm spherical particles to become highly elongated, then abruptly return to a spherical shape, while nanofibers grow spontaneously from the particle's surface.

From a detailed inspection of the images and quantum me­chanical calculations, the re­searchers conclude that nucle-ation and growth of the fibers' graphene layers occur at tiny de­fects in the nickel crystals known as single-atom step edges. The angstrom-sized imperfections are observed to form and then dis­appear repeatedly during the course of the reaction. Based on the experimental and computa­tional results, the researchers pro­pose that the growth mechanism depends on surface diffusion of carbon and nickel atoms.

Commenting in the same is­sue of Nature, PulickelM. Ajayan, a professor of materials science and engineering at Rensselaer Polytechnic Institute, remarks that the study "has overcome

EYE OF T H E F IBER An electron micrograph recorded under reaction conditions reveals the dynamic role of 10-nm nickel catalyst particles (blue) in forming carbon nanofibers (green) via hydrocarbon decomposition.

some major experimental stum­bling blocks to provide the first direct glimpses of nanofibers as they grow" Ajayan notes that the experiments show the impor­tance of shape transformations in particles used as nanoscale growth catalysts. He adds that the work "should lead to better con­trol over fiber synthesis for nano-technology"—MITCH JACOBY

F E R T I L I Z E R

IMCP Cargill Merge Crop Nutrient Business

IMC Global and agribusiness giant Cargill have signed a definitive agreement to com­bine their phosphate, potash, and nitrogen

assets to create the second largest global fertil­izer operation, with $4.1 billion in annual sales.

When the deal closes later this summer -subject to regulatory approval—the new, as-yet-unnamed publicly owned company wil l be larger than number three Potash Corp. of Saskatchawan, with estimated annual sales of $2.6 billion. Number one Yara, the Norsk Hydro fertilizer business to be spun off to shareholders later this year, has sales of about $4.9 billion.

In return for two-thirds of the new firm's shares, Cargill is to contribute its fertilizer operations with $2 billion in sales and $50

million in debt. IMC turns over a business with $2.1 billion in sales and $2.1 billion in debt. IMC shareholders wil l own one-third of the new firm, which is to be headed by Fritz Corrigan, now Cargill executive vice president.

For IMC, the merger means allying with a strong partner after years of losses caused by industry overcapacity and a farm reces­sion. Executives say the fertilizer industry is poised for a recovery.

For Cargill, the largest U.S. privately held firm, the deal means enlarging its position in fertilizers at the expense of going public—the first time an operation of the secretive fami­ly-owned business wil l be open to public scrutiny—MARC REISCH

HTTP: / /WWW.CEN-ONLINE.ORG C & E N / F E B R U A R Y 2 , 2 0 0 4 7