Surface Functionalization of Metal Chalcogenides and their Bio-organic Derivatives

Supervisor : Ass. Professor Dr. Florinel Gabriel Banica.

Muhammad Ali Mohsin.

PhD Student, Deparment of Chemistry. Norwegian University of Science and Technology (NTNU), Trondheim, Norway.

Outline
Introduction / Background. What are Chalcogenides? Surface Modification Methods. Recent research results. Properties and Applications. Potential for improvements. Conclusion.

Surface Functionalization
The term surface functionalization denotes a controlled modification of the surface for the specialized tasks and applications.i.e; Catalysis. Chemical Sensing. Bio-technology. Nano-tecnology. Semiconductors. Environmental and industrial applications.

Properties and Applications

As far as a surface modified materials at the nanometer scale, these can be adapted to build up storage of information devices or arrays of chemical sensors.

Chalcogenide glasses can be used as active devices such as fiber amplifiers and lasers.

Transition metal chalcogenide have a wide range of interesting physical properties (catalysis , lubricants, semi- and superconducting properties).

Why metal chalcogenides?

Bio-organic chalcogens derivatives (such as cysteamine, cysteine, homocysteine) are employed to prepare self-assembled monolayers on metal surfaces for bio-sensing applications.
NH 2 HO S S O NH2 OH O

cystine

The key step is the interaction of the chalcogen moiety with the metal surface. Investigation of chalcogen ions (S2-, Se2-) interaction with metals (Au, Ag, Hg) will substantiate the mechanism of bio-organic derivatives behaviour in such a process.

Metal Chalcogenides and their derivatives

Chalcogenide is the collective name ascribed to the compounds of sulfur, selenium and tellurium. They play a particular role in nature and living organisms. Example: the amino acid cysteine contains a thiol group which can function as anchor bridge for enzyme immobilization on metal surface. Metal chalcogenides have relevance for natural aqueous environment. For example, the iron sulfides constitute a diverse group of solids and dissolved complexes many play key roles in marine systems.

Aims
New advances in the thermodynamic and kinetic theory of electrical reactions involving metal chalcogenides in the form of molecular layers on the metal electrode surface. Investigating the properties of the above-mentioned compounds by electrochemistry, piezoelectric nanogravimetry and surface analysis methods. Development of new electrochemical methods for the preparation of metal chalcogenides and their bio-organic derivatives in various aggregation forms, from surface mono-layers to nanoparticles.

Envisaged research methods

Electrochemical methods with liquid and solid electrodes for performing:
Electrode surface modification by inorganic or organic layers based on chalcogene derivatives. Investigation of the physical and chemical properties of the chalcogenide-based surface layers.

Piezoelectric nano-gravimetry for:

Investigation of the kinetics of the metal chalcogenide growth on metal surfaces. Biosensor applications using electrochemical methods for the synthesis of the receptor layer.

Surface analysis methods (atomic force microscopy, photoelectron spectroscopy, micro-Raman spectroscopy) for investigating chemical structure and composition of surface layer prepared by electrochemical methods.

HgS formation and reduction

Two steps experiment
3. Constant potential anodic reaction of Hg in the presence of thiourea leading to a HgS surface layer 4. Linear potential scan HgS reduction (peak A)

Effect of deposition potential. 2 M thiourea; pH 6.5; Depos. time, 30 s. Curves 1 to 6: Ed = 0; 0.02; 0.04; 0.06; 0.08; 0.10 V, respectively.

Reaction scheme

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Recent Results
A study of mercury sulphide layer formation by anodic polarization of a mercury electrode at a constant potential in the presence of sulphur releasing compound, such as thiourea, was carried out. AIM This work was aimed to :
Improve the theoretical approach in order to alleviate the effect of errors resulting from approximations in the theoretical approach. Improving data processing methods in order to extract relevant kinetic and thermodynamic parameters.

Assumptions Consider a reversible electron transfer reaction coupled with chemical reaction at equilibrium, such as;

HgS + n e

Hg + S-2

Critical assumption in this derivation was invariability of the surface activity of the mercury sulphide.

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Previous theory
An available approximation theoretical approach for the electrochemical reaction of a mercury sulphide surface layer was previously developed [1,2]. According to this theory following relationship was obtained : Eq. 1 E p = E o RT RT RT ln v ln Q + ln(A R T nFD )E p 2nF nF nF

Ep = peak A potential Eo = formal potential for HgS reduction Qt = total charge consumed in HgS reduction v= potential sweep rate A = electrode surface area D = diffusion coefficient of S(2-) n= number of electrons per HgS molecule F= Faraday constant T = absolute temperature MAIN DRAWBACK: the approximation of constant HgS amount does not hold at E= Ep

2. 3.

J. P. Haberman, PhD Thesis, University of Wisconsin, 1967. F. G. Banica, M. Galk, I. Svancara, K. Vytras, Electroanalysis 2009, 21, 332.

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New equations
Eq.2 Eq.3

ln i = k 3 + k 4 ln Q - (nF / R T )E
ln Q = k 5 - 0.5 ln v - (nF / R T )E

Where: i = current measured at the potential E Q = amount of electricity consumed by HgS reduction up till the potential E
k3 = k2 + 0.5ln v

k 4=an empirical fitting const.

k 5 = ln(FA ) + 0.5 ln(nR T D / F ) + (nR T / F )E o

ADVANTAGE: this approach involves i and Q values at E>>Ep where the approximation of invariable HgS amount is fairly fulfilled.

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Data analysis method

Three-dimensional data plot and fitting based on Equations 2 and 3.

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Results: lni plot vs. E and ln(Qt) (Eq. 2)

Figure 1. Thiourea, 1.0 M; deposition time, 100; 150; 200; 250; 300; 350; 400; 450; 500; 550; 600 s; scan rate, 0.02 V/s. Conclusion: Very good fit; fair agreement between theoretical and experimental fitting parameters

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Results:

3D Plot of lnQ vs. lnv and E

Figure 2. Data fitting according to Equation (3). Experimental conditions as in Figure 1. Conclusion: Some deviations from predicted behavior. Theory refinement is needed.
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Next steps
Improving the theoretical approach. Investigating mercury selenide. Investigating mercury salts with bio-thiols (cysteine and its derivatives and analogous, including seleno-cysteine). Investigating analogous Ag compounds by electrochemistry, piezoelectric nano-gravimetry and surface analysis methods.

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Conclusion
This work focuses on inorganic and bio-organic derivatives of two chalcogenides elements, namely sulfur and selenium and aims at investigating the interaction of chalcogenide ions and derivatives with metal ions. Thanks to:
Associate Prof.Dr.Florinel Gabriel Banica. University of Bartislava and Summer School organizers. Norwegian University of Science and Technology.

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Thank you for your kind attention!

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