Volume 162, 2013
From the journal:

Faraday Discussions

Semi-hydrogenation of alkynes at single crystal, nanoparticle and biogenic nanoparticle surfaces: the role of defects in Lindlar-type catalysts and the origin of their selectivity

G. A. Attard,*a   J. A. Bennett,b   I. Mikheenko,c   P. Jenkins,a   S. Guan,a   L. E. Macaskie,c   J. Woodb  and  A. J. Waind  

* Corresponding authors

a School of Chemistry, Cardiff University, Park Place, Cardiff CF10 3AT, UK
E-mail: attard@cardiff.ac.uk
Fax: +44 (0) 2920 874030
Tel: +44 (0) 2920 874069

b School of Chemical Engineering, University of Birmingham, Birmingham B15 2TT, UK

c School of Biosciences, University of Birmingham, Birmingham B15 2TT, UK

d National Physical Laboratory, Teddington, UK

Abstract

For the first time, the method of shell-isolated nanoparticle Raman spectroscopy (SHINERS) is used in combination with cyclic voltammetry (CV) and reactivity studies to investigate the adsorption behaviour of a series of three alkynes undergoing hydrogenation on nanoparticle, single crystal and bacteria/graphite-supported platinum surfaces. It is found that a strong association of alkynes with defect sites to produce a long-lived di-sigma/pi-alkene surface complex allows for deep hydrogenation of this intermediate to the alkane product. In contrast, when platinum surface defect sites are blocked by either bismuth or polyvinylpyrrolidone (PVP) (and thus leaving behind only Pt{111} terrace adsorption sites), large increases in selectivity to the semi-hydrogenation product are observed for all three alkynes. This finding is consistent with SHINERS collected from both well-ordered and roughened Pt{111} electrodes which revealed that the di-sigma/pi-bonded surface intermediate is hardly formed at all on Pt{111} unless defect sites are introduced via electrochemical roughening. As a general method of producing selective catalysts, the elimination of toxic heavy metals from Lindlar-type catalyst, used commonly in organic chemistry, and their replacement by more benign, organic species adsorbed at defect sites is discussed.

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Article information

DOI
https://doi.org/10.1039/C3FD00007A
Article type
Paper
Submitted
22 Jan 2013
Accepted
24 Jan 2013
First published
22 Apr 2013

Faraday Discuss., 2013,162, 57-75

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Semi-hydrogenation of alkynes at single crystal, nanoparticle and biogenic nanoparticle surfaces: the role of defects in Lindlar-type catalysts and the origin of their selectivity

G. A. Attard, J. A. Bennett, I. Mikheenko, P. Jenkins, S. Guan, L. E. Macaskie, J. Wood and A. J. Wain, Faraday Discuss., 2013, 162, 57 DOI: 10.1039/C3FD00007A

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