Establishing Relationships Between the Geometric Structure and Chemical Reactivity of Alloy Catalysts Based on Their Measured Electronic Structure
- 788 Downloads
While it is fairly straightforward to predict the relative chemical reactivity of pure metals, obtaining similar structure-performance relationships for alloys is more challenging. In this contribution we present experimental analysis supported with quantum chemical DFT calculations which allowed us to propose a simple, physically transparent model to predict the impact of alloying on the local electronic structure of different sites in alloys and on the local chemical reactivity. The model was developed through studies of a number of Pt alloys. The central feature of the model is that hybridization of d-orbitals in alloys does not lead to significant charge transfer between the constituent elements in the alloy, and therefore the width of the local density of d-states projected on a site, which is easily calculated from tabulated parameters, is an excellent descriptor of the chemical reactivity of the site.
KeywordsMetal alloys Predictive model Relating geometric structures to reactivity Pt alloys XANES DFT d-band model Structure–property relationships
We gratefully acknowledge the support of the US Department of Energy DOE-BES, Division of Chemical Sciences (FG-02-05ER15686), NSF (CTS-CAREER 0543067 and NSF CBET 0756255), and ONR (N000140810122) S. Linic also acknowledges the DuPont Young Professor grant by DuPont corporation and the Camille Dreyfus Teacher-Scholar Award for the Camille & Henry Dreyfus Foundation.
- 1.Kaufman JG, Rooy EL (2004) Aluminum alloy castings: properties, processes and applications. Illustrated edition. ASM International. Materials Park, OH, USAGoogle Scholar
- 14.Harrison WA (1980) Solid state theory. Dover Publications, New YorkGoogle Scholar
- 20.Gracia FJ, Guerrero S, Wolf EE, Miller JT, Kroph AJ (2005) J Cata 233:372–387Google Scholar
- 30.Pettifor DG (1995) Bonding and structure of molecules and solids. Oxford University Press, USAGoogle Scholar
- 35.Hammer B, Nørskov JK (1997) In: Lambert RM, Pacchioni G (eds) Chemisorption and reactivity on supported clusters and thin films. Kluwer, Dordrecht, pp 331–351Google Scholar