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. 2013 May 17;3(2):303-316.
doi: 10.3390/nano3020303.

Nano-Electrochemistry and Nano-Electrografting With an Original Combined AFM-SECM

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Free PMC article

Nano-Electrochemistry and Nano-Electrografting With an Original Combined AFM-SECM

Achraf Ghorbal et al. Nanomaterials (Basel). .
Free PMC article

Abstract

This study demonstrates the advantages of the combination between atomic force microscopy and scanning electrochemical microscopy. The combined technique can perform nano-electrochemical measurements onto agarose surface and nano-electrografting of non-conducting polymers onto conducting surfaces. This work was achieved by manufacturing an original Atomic Force Microscopy-Scanning ElectroChemical Microscopy (AFM-SECM) electrode. The capabilities of the AFM-SECM-electrode were tested with the nano-electrografting of vinylic monomers initiated by aryl diazonium salts. Nano-electrochemical and technical processes were thoroughly described, so as to allow experiments reproducing. A plausible explanation of chemical and electrochemical mechanisms, leading to the nano-grafting process, was reported. This combined technique represents the first step towards improved nano-processes for the nano-electrografting.

Keywords: AFM; AFM-SECM; SECM; interface; nano-electrochemistry; nano-electrografting; nano-functionalization; nano-process; surface.

Figures

Scheme 1
Scheme 1
Chemical structure of agarose.
Figure 1
Figure 1
(a) Scanning electron microscopy image of the homemade AFM-SECM-electrode after insulation with electrophoretic paint. Beam energy was 15 kV and working distance 31 mm; (b) Scanning electron microscopy image of the tip apex. The apex radius was around 130 nm. Beam energy was 5 kV and working distance 8 mm.
Figure 2
Figure 2
Steady-state voltammogram of the AFM-SECM-electrode in aqueous solution containing 1 mM ferrocenedimethanol and 0.1 M KH2PO4. The forward and backward traces are superimposed. The potential scan rate was 50 mV s−1.
Figure 3
Figure 3
Schematic drawing of AFM setups (a) for the AFM-SECM/Agarose system; (b) for the nano-electrografting system.
Figure 4
Figure 4
Steady-state voltammogram of the PtIr-tip in contact with the agarose surface. Agarose was previously immersed in aqueous solution containing 5 mM ferricyanure and 0.1 M KCl, during 1 h. The potential scan rate was 50 mV s−1.
Figure 5
Figure 5
Scanning electron microscopy image of the homemade AFM-SECM-electrode after collision with the surface during nano-electrochemical grafting attempts. Beam energy was 15 kV and working distance 16 mm.
Figure 6
Figure 6
(a) Topographic AFM image in tapping mode of the line pattern drawn with the AFM-SECM-electrode on the gold surface with direct aryl diazonium salt/acrylic acid reduction (chronoamperometry: −0.8 V); (b) Horizontal cross section of the electrografted line. Line width and height are about 180 nm and 40 nm, respectively.
Figure 7
Figure 7
Schematic representation of the electric field between the AFM-SECM-electrode and the substrate.
Figure 8
Figure 8
A simplified schematic representation of chemical and electrochemical reactions leading to the line grafting. (1) Reduction of the diazonium salt on the substrate to form a polynitrophenylene-like film; (2) Water oxidation at the AFM-SECM-electrode; (3) Concomitant reduction of protons on the substrate and formation of a localized grafted coating onto the top of the primer polynitrophenylene (PNP) film by radical reaction. (3a) Formation of a phenyl radical and reaction with PNP film; (3b) Phenyl radical initiates the first vinylic (plausible) radical polymerization. Reaction of the formed macroradicals with the grafted layer; (3c) Formation of radical monomer, initiation of the second (plausible) vinylic radical polymerization and reaction of the formed macroradicals with the grafted layer.

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References

    1. Bard A.J., Mirkin M.V. Scanning Electrochemical Microscopy. Marcel Dekker; New York, NY, USA: 2001.
    1. Mirkin M.V., Horrocks B.R. Electroanalytical measurements using the scanning electrochemical microscope. Anal. Chim. Acta. 2000;406:119–146. doi: 10.1016/S0003-2670(99)00630-3. - DOI
    1. Jones C.E., Macpherson J.V., Barber Z.H., Somekh R.E., Unwin P.R. Simultaneous topographical and amperometric imaging of surfaces in air: Towards a combined scanning force-scanning electrochemical microscope (SF-SECM) Electrochem. Commun. 1999;1:55–60.
    1. Kranz C., Kueng A., Lugstein A., Bertagnolli E., Mizaikoff B. Mapping of enzyme activity by detection of enzymatic products during AFM imaging with integrated SECM-AFM probes. Ultramicroscopy. 2004;100:127–134. doi: 10.1016/j.ultramic.2003.10.004. - DOI - PubMed
    1. Macpherson J.V., Unwin P.R. Noncontact electrochemical imaging with combined scanning electrochemical atomic force microscopy. Anal. Chem. 2001;73:550–557. doi: 10.1021/ac001072b. - DOI - PubMed
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