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Hollow and filled with potential

(Nanowerk News) Catalytic nanocages, which are tiny, open structures with reactive surfaces that could boost key chemical processes, are notoriously difficult to synthesize. Scientists recently succeeded in a new approach: they built the hollow structures by depositing platinum onto a palladium template and then etching away the template. The result? Tiny cages with catalytic surfaces inside and out.
With well-defined facets and high catalytic activity, these nanocages can be engineered to meet future needs. The hollow nanocages also use less amount of palladium, a scarce noble metal.
Improving the efficiency of catalysts could enhance many chemical reactions used in industry and research laboratories. To improve efficiency, researchers have created nanocages (open nanostructures composed of multiple facets and thus, catalysts with tunable activity and selectivity). However, engineering these structures with specific crystallographic facets was difficult.
To improve the catalysts, researchers from Georgia Tech, University of Wisconsin-Madison, Arizona State University, and Oak Ridge National Laboratory developed their own synthesis technique to create hollow, shape-selected nanocages. The cages can be shaped with a template to create various desired facets, thus solving the major problem with the previous structures.
To produce the nanocages, platinum is deposited onto a palladium template at high temperatures. Platinum atoms form a relatively uniform shell around the palladium core, typically around 6 atomic layers thick. An intermixing of palladium occurs in the platinum shell during platinum deposition, causing the formation of palladium channels connecting the surface with the interior of the nanocages. A palladium-specific etching technique is used to remove the core of the structures, starting with the palladium channels. These channels widen and restructure through the etching process, allowing for the majority of the palladium core to be removed.
The structure that remains is the platinum shell with the facets from the template preserved. Both octahedral and cubic nanocages have been synthesized, each with greater catalytic activity for the oxygen reduction reaction, the fundamental reaction occurring at a fuel cell cathode, than a standard platinum/carbon catalyst. In particular, the octahedral structures have more than five times the oxygen reduction reaction activity of the platinum/carbon catalyst.
The nanocages have catalytic surfaces both inside and outside their structure, which likely is the reason for the increased activity. In addition to the two types of nanocages that have already been synthesized, the nanocages can be engineered to have many different catalytic facets. This versatility should allow the platinum nanocages to selectively catalyze a broad range of chemical reactions.
S. Xie, S. I. Choi, N. Lu, L. T. Roling, J. A. Herron, L. Zhang, J. Park, J. Wang, M. J. Kim, Z. Xie, M. Mavrikakis, and Y. Xia, “Atomic layer-by-layer deposition of Pt on Pd nanocubes for catalysts with enhanced activity and durability toward oxygen reduction.” Nano Letters 14, 3570 (2014). [DOI: 10.1021/nl501205j]
J. Park, L. Zhang, S. Choi, L. T. Roling, N. Lu, J. A. Herron, S. Xie, J. Wang, M. J. Kim, M. Mavrikakis, and Y. Xia, “Atomic layer-by-layer deposition of platinum on palladium octahedra for enhanced catalysts toward the oxygen reduction reaction.” ACS Nano 9, 2635 (2015). [DOI: 10.1021/nn506387w]
X. Wang, S. I. Choi, L. T. Roling, M. Luo, C. Ma, L. Zhang, M. Chi, J. Liu, Z. Xie, J. A. Herron, M. Mavrikakis, and Y. Xia, “Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction.” Nature Communications 6, 7594 (2015). [DOI: 10.1038/ncomms8594]
L. Zhang, L. T. Roling, X. Wang, M. Vara, M. Chi, J. Liu, S. I. Choi, J. Park, J. A. Herron, Z. Xie, M. Mavrikakis, and Y. Xia, “Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets.” Science 349, 412 (2015). [DOI: 10.1126/science.aab0801]
Source: Department of Energy
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