1900

Experimental Challenges in Studying Hydrogen Absorption in Ultrasmall Metal Nanoparticles

Abstract

Recent advances on synthesis, characterization, and hydrogen absorption properties of ultrasmall metal nanoparticles (defined here as objects with average size ≤3 nm) are briefly reviewed in the first part of this work. The experimental challenges encountered in performing accurate measurements of hydrogen absorption in Mg- and noble metal-based ultrasmall nanoparticles are addressed. The second part of this work reports original results obtained for ultrasmall bulk-immiscible Pd–Rh nanoparticles. Carbon-supported Pd–Rh nanoalloys in the whole binary chemical composition range have been successfully prepared by liquid impregnation method followed by reduction at 300°C. EXAFS investigations suggested that the local structure of these nanoalloys is partially segregated into Rh-rich core and Pd-rich surface coexisting within the same nanoparticles. Downsizing to ultrasmall dimensions completely suppresses the hydride formation in Pd-rich nanoalloys at ambient conditions, contrary to bulk and larger nanosized (5–6 nm) counterparts. The ultrasmall Pd90Rh10 nanoalloy can absorb hydrogen-forming solid solutions under these conditions, as suggested by in situ X-ray diffraction (XRD). Apart from this composition, common laboratory techniques, such as in situ XRD, DSC, and PCI, failed to clarify the hydrogen interaction mechanism: either adsorption on developed surfaces or both adsorption and absorption with formation of solid solutions. Concluding insights were brought by in situ EXAFS experiments at synchrotron: ultrasmall Pd75Rh25 and Pd50Rh50 nanoalloys absorb hydrogen-forming solid solutions at ambient conditions. Moreover, the hydrogen solubility in these solid solutions is higher with increasing Pd content, and this trend can be understood in terms of hydrogen preferential occupation in the Pd-rich regions, as suggested by in situ EXAFS. The Rh-rich nanoalloys (Pd25Rh75 and Pd10Rh90) only adsorb hydrogen on the developed surface of ultrasmall nanoparticles. In summary, in situ characterization techniques carried out at large-scale facilities are unique and powerful tools for in-depth investigation of hydrogen interaction with ultrasmall nanoparticles at local level.

Funding source: French National Research Agency
Related subjects: Production & Supply Chain
Countries: France
Loading

Article metrics loading...

/content/journal1654
2016-06-27
2021-07-24
http://instance.metastore.ingenta.com/content/journal1654
Loading
This is a required field
Please enter a valid email address
Approval was a Success
Invalid data
An Error Occurred
Approval was partially successful, following selected items could not be processed due to error