Brookhaven National Laboratory – Searching for More Cost Efficient Catalysts for Hydrogen Fuel Cells – Illuminating Nanoparticle Growth With X-Rays


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Brookhaven Lab scientists Mingyuan Ge, Iradwikanari Waluyo, and Adrian Hunt are pictured left to right at the IOS beamline, where they studied the growth pathway of an efficient catalyst for hydrogen fuel cells. Credit: Brookhaven National Laboratory

Hydrogen fuel cells are a promising technology for producing clean and renewable energy, but the cost and activity of their cathode materials is a major challenge for commercialization. Many fuel cells require expensive platinum-based catalysts–substances that initiate and speed up chemical reactions–to help convert renewable fuels into electrical energy. To make hydrogen fuel cells commercially viable, scientists are searching for more affordable catalysts that provide the same efficiency as pure platinum.

“Like a battery, hydrogen fuel cells convert stored chemical energy into electricity. The difference is that you’re using a replenishable fuel so, in principle, that ‘battery’ would last forever,” said Adrian Hunt, a scientist at the National Synchrotron Light Source II(NSLS-II), a U.S. Department of Energy (DOE) Office of Science User Facility at DOE’s Brookhaven National Laboratory. “Finding a cheap and effective catalyst for hydrogen fuel cells is basically the holy grail for making this technology more feasible.”

Taking part in this worldwide search for fuel cell cathode materials, researchers at the University of Akron developed a new method of synthesizing catalysts from a combination of metals–platinum and nickel–that form octahedral (eight-sided) shaped nanoparticles. While scientists have identified this catalyst as one of the most efficient replacements for pure platinum, they have not fully understood why it grows in an octahedral shape. To better understand the growth process, the researchers at the University of Akron collaborated with multiple institutions, including Brookhaven and its NSLS-II.

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Schematic diagram of the oxygen reduction reaction (reduction of O2 into H2O) on the Pt(110) surface of the PtPb/Pt nanoplates, with purple representing Pt atoms and orange representing Pb atoms. Credit: Brookhaven National Laboratory

“Understanding how the faceted catalyst is formed plays a key role in establishing its structure-property correlation and designing a better catalyst,” said Zhenmeng Peng, principal investigator of the catalysis lab at the University of Akron. “The growth process case for the platinum-nickel system is quite sophisticated, so we collaborated with several experienced groups to address the challenges. The cutting-edge techniques at Brookhaven National Lab were of great help to study this research topic.”

Using the ultrabright x-rays at NSLS-II and the advanced capabilities of NSLS-II’s In situ and Operando Soft X-ray Spectroscopy (IOS) beamline, the researchers revealed the chemical characterization of the catalyst’s growth pathway in real time. Their findings are published in Nature Communications.

“We used a research technique called ambient-pressure x-ray photoelectron spectroscopy (AP-XPS) to study the surface composition and chemical state of the metals in the nanoparticles during the growth reaction,” said Iradwikanari Waluyo, lead scientist at IOS and a co-corresponding author of the research paper. “In this technique, we direct x-rays at a sample, which causes electrons to be released. By analyzing the energy of these electrons, we are able to distinguish the chemical elements in the sample, as well as their chemical and oxidation states.”

Hunt, who is also an author on the paper, added, “It is similar to the way sunlight interacts with our clothing. Sunlight is roughly yellow, but once it hits a person’s shirt, you can tell whether the shirt is blue, red, or green.”

Rather than colors, the scientists were identifying chemical information on the surface of the catalyst and comparing it to its interior. They discovered that, during the growth reaction, metallic platinum forms first and becomes the core of the nanoparticles. Then, when the reaction reaches a slightly higher temperature, platinum helps form metallic nickel, which later segregates to the surface of the nanoparticle. In the final stages of growth, the surface becomes roughly an equal mixture of the two metals. This interesting synergistic effect between platinum and nickel plays a significant role in the development of the nanoparticle’s octahedral shape, as well as its reactivity.

“The nice thing about these findings is that nickel is a cheap material, whereas platinum is expensive,” Hunt said. “So, if the nickel on the surface of the nanoparticle is catalyzing the reaction, and these nanoparticles are still more active than platinum by itself, then hopefully, with more research, we can figure out the minimum amount of platinum to add and still get the high activity, creating a more cost-effective catalyst.”

The findings depended on the advanced capabilities of IOS, where the researchers were able to run the experiments at gas pressures higher than what is usually possible in conventional XPS experiments.

“At IOS, we were able to follow changes in the composition and chemical state of the nanoparticles in real time during the real growth conditions,” said Waluyo.

Additional x-ray and electron imaging studies completed at the Advanced Photon Source (APS) at DOE’s Argonne National Laboratory–another DOE Office of Science User Facility–and University of California-Irvine, respectively, complemented the work at NSLS-II.

“This fundamental work highlights the significant role of segregated nickel in forming the octahedral-shaped catalyst. We have achieved more insight into shape control of catalyst nanoparticles,” Peng said. “Our next step is to study catalytic properties of the faceted nanoparticles to understand the structure-property correlation.”

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Breakthrough in Nanotechnology is a BIG DEAL for Electronics


201306047919620University of Akron researchers have developed new materials that function on a nanoscale, which could lead to the creation of lighter laptops, slimmer televisions and crisper smartphone visual displays.

 

Known as “giant surfactants” – or surface films and liquid solutions – the researchers, led by Stephen Z.D. Cheng, dean of UA’s College of Polymer Science and Polymer Engineering, used a technique known as nanopatterning to combine functioning molecular nanoparticles with polymers to build these novel materials.

The giant surfactants developed at UA are large, similar to macromolecules, yet they function like molecular surfactants on a nanoscale, Cheng says. The outcome? Nanostructures that guide the size of electronic products.

More efficient designs possible Nanopatterning, or self-assembling molecular materials, is the genius behind the small, light and fast world of modern-day gadgetry, and now it has advanced one giant step thanks to the UA researchers who say these new materials, when integrated into electronics, will enable the development of ultra-lightweight, compact and efficient devices because of their unique structures.

During their self-assembly, molecules form an organized lithographic pattern on semiconductor crystals, for use as integrated circuits. Cheng explains that these self-assembling materials differ from common block copolymers (a portion of a macromolecule, comprising manyunits, that has at least one feature which is not present in the adjacent portions) because they organize themselves in a controllable manner at the molecular level.

“The IT industry wants microchips that are as small as possible so that they can manufacture smaller and faster devices,” says Cheng, who also serves as the R.C. Musson and Trustees Professor of Polymer Science at UA.

He points out that the current technique can produce the spacing of 22 nanometers only, and cannot go down to the 10 nanometers or less necessary to create tiny, yet mighty, devices. The giant surfactants, however, can dictate smaller-scale electronic components.

“This is exactly what we are pursuing – self-assembling materials that organize at smaller sizes, say, less than 20 or even 10 nanometers,” says Cheng, equating 20 nanometers to 1 /4,000th the diameter of a human hair.

Team work has commercial applications

An international team of experts, including George Newkome, UA vice president for research, dean of the Graduate School, and professor of polymer science at UA; Er-Qiang Chen of Peking University in China; Rong-Ming Ho of National Tsinghua University in Taiwan; An-Chang Shi of McMaster University in Canada; and several doctoral and postdoctoral researchers from Cheng’s group, have shown how well-ordered nanostructures in various states, such as in thin films and in solution, offer extensive applications in nanotechnology.

The team’s study is highlighted in a pending patent application through the University of Akron Research Foundation and in a recent journal article, “Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering” published in Proceedings of the National Academy of Sciences of the United States of America (110, 10078-10083, 2013).

“These results are not only of pure scientific interest to the narrow group of scientists, but also important to a broad range of industry people,” says Cheng, noting that his team is testing real-world applications in nanopatterning technologies and hope to see commercialization in the future.

Gadget Genius: Nanotechnology Breakthrough Is Big Deal for Electronics


201306047919620July 26, 2013 — University of Akron researchers have developed new materials that function on a nanoscale, which could lead to the creation of lighter laptops, slimmer televisions and crisper smartphone visual displays

Known as “giant surfactants” — or surface films and liquid solutions — the researchers, led by Stephen Z.D. Cheng, dean of UA’s College of Polymer Science and Polymer Engineering, used a technique known as nanopatterning to combine functioning molecular nanoparticles with polymers to build these novel materials.

The giant surfactants developed at UA are large, similar to macromolecules, yet they function like molecular surfactants on a nanoscale, Cheng says. The outcome? Nanostructures that guide the size of electronic products.

More efficient designs possible

Nanopatterning, or self-assembling molecular materials, is the genius behind the small, light and fast world of modern-day gadgetry, and now it has advanced one giant step thanks to the UA researchers who say these new materials, when integrated into electronics, will enable the development of ultra-lightweight, compact and efficient devices because of their unique structures.

During their self-assembly, molecules form an organized lithographic pattern on semiconductor crystals, for use as integrated circuits. Cheng explains that these self-assembling materials differ from common block copolymers (a portion of a macromolecule, comprising manyunits, that has at least one feature which is not present in the adjacent portions) because they organize themselves in a controllable manner at the molecular level.

“The IT industry wants microchips that are as small as possible so that they can manufacture smaller and faster devices,” says Cheng, who also serves as the R.C. Musson and Trustees Professor of Polymer Science at UA.

He points out that the current technique can produce the spacing of 22 nanometers only, and cannot go down to the 10 nanometers or less necessary to create tiny, yet mighty, devices. The giant surfactants, however, can dictate smaller-scale electronic components.

“This is exactly what we are pursuing — self-assembling materials that organize at smaller sizes, say, less than 20 or even 10 nanometers,” says Cheng, equating 20 nanometers to 1 /4,000th the diameter of a human hair.

Team’s work has commercial applications

An international team of experts, including George Newkome, UA vice president for research, dean of the Graduate School, and professor of polymer science at UA; Er-Qiang Chen of Peking University in China; Rong-Ming Ho of National Tsinghua University in Taiwan; An-Chang Shi of McMaster University in Canada; and several doctoral and postdoctoral researchers from Cheng’s group, have shown how well-ordered nanostructures in various states, such as in thin films and in solution, offer extensive applications in nanotechnology.

The team’s study is highlighted in a pending patent application through the University of Akron Research Foundation and in a recent journal article, “Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering” published in Proceedings of the National Academy of Sciences of the United States of America (110, 10078-10083, 2013).

“These results are not only of pure scientific interest to the narrow group of scientists, but also important to a broad range of industry people,” says Cheng, noting that his team is testing real-world applications in nanopatterning technologies and hope to see commercialization in the future.