Surface-enhanced Raman spectroscopic study of 1,4-phenylene diisocyanide adsorbed on gold and platinum-group transition metal electrodes

The Journal of Physical Chemistry. B
Scott M GruenbaumShouzhong Zou

Abstract

Self-assembled monolayers of 1, 4-phenylene diisocyanide (PDI) were formed on Au and Pt-group transition metals and examined by surface-enhanced Raman spectroscopy under controlled applied potential. On all of the metals examined, PDI adsorbs in an edge-on manner, with one NC group bound to the surface and the other pointing away from the surface. The N-C stretching frequency (nu(NC)) suggests that depending on the metal, PDI adsorbs on different binding sites: terminal sites on Au, both terminal and bridging on Rh and Pt, and predominantly 3-fold hollow sites for Pd. This binding site preference can be understood in terms of the difference in d-band center energy and d-orbital filling among the metals. The applied potential affects the N-C bonding differently as inferred from the potential dependence of nu(NC). On Au, Rh, and Pd, the nu(NC) increases linearly with the applied potential, yielding a Stark tuning slope, dnu(NC)/dE, of 25, 12, and 10 cm(-1)/V, respectively. On Pt, the nu(NC) is nearly independent of the applied potential. On all of the metals studied, the frequencies of benzene ring vibration modes are not dependent on the applied potential, consistent with the edge-on orientation in which the ring does not direct...Continue Reading

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Citations

Dec 22, 2009·Physical Chemistry Chemical Physics : PCCP·Ryan P SteeleGiulia Galli
Nov 23, 2011·Langmuir : the ACS Journal of Surfaces and Colloids·Jianbo ZengShouzhong Zou
Mar 20, 2010·Physical Chemistry Chemical Physics : PCCP·Mikio ItoKohei Uosaki
Aug 18, 2010·Physical Chemistry Chemical Physics : PCCP·Jorge A BoscoboinikWilfred T Tysoe
Aug 28, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Leslie RegueraEdilso Reguera
Oct 4, 2018·Journal of the American Chemical Society·Shu HuBin Ren
Sep 1, 2006·The Journal of Physical Chemistry. B·Hongzhou YangShouzhong Zou
Dec 1, 2007·The Journal of Physical Chemistry. B·Cantwell G CarsonRina Tannenbaum
Nov 21, 2021·Nature Communications·Jack GriffithsJeremy J Baumberg

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