INTERNATIONAL JOURNAL OF ENERGY RESEARCH

Int. J. Energy Res., 23, 229 — 233 (1999)

INVESTIGATION OF MANGANESE—MOLYBDENUM—
DIETHYLDITHIOCARBAMATE COMPLEX AS A POTENTIAL
SYSTEM FOR SOLAR ENERGY CONVERSION

EDWIN SURESH, JOHN PRAGASAM, FRANCIS P. XAVIER AND K. S. NAGARAJA*

Department of Chemistry and Loyola Institute of Frontier Energy, Loyola College, Chennai 600 034, India

SUMMARY
Manganese—molybdenum—diethyldithiocarbamate [MnMoO (Et dtc) (H O)] +Et dtc"diethyldithiocarbamate,
complex has exhibited reversible photogalvanic behaviour in aqueous  dimethylformamide
  medium when studied in
a Honda cell. The photogalvanic behaviour has been further investigated by varying the pH, temperature and
photosensitizers. UV, visible and sunlight were used as the radiation sources. A maximum potential of 345 mV was
obtained at 80°C in visible light. The system was found to be reversible for several cycles. A photoelectrochemical cell was
constructed by coupling a charged nickel electrode with the complex electrode which incorporates the experimental
compound in acetylene black on a nickel substrate. A maximum potential of 1)08 V with 80 lA current was obtained
when irradiated with tungsten lamp. Copyright  1999 John Wiley & Sons, Ltd.

KEY WORDS: manganese—molybdenum—diethyldithiocarbamate; photogalvanic cell; photoelectrochemical cell; solar

energy

INTRODUCTION
Rabinowitch (1940), first studied the photogalvanic effect in iron—thionine system. This kind of work was
followed by various workers (Potter and Thaller, 1959; Clark and Eckert, 1975; Gomer, 1975; Kaneko and
Yamada, 1977; Kamat et al., 1979; Murthy et al., 1980; Fox and Kabir-Ud-Din, 1980; Albery et al., 1980
Ameta et al., 1985, 1987, 1991; Lodha et al., 1991; Dube et al., 1993; Gangotri et al., 1996). In the present
study the construction of a photogalvanic cell and thereby extension to solar cell using heterobinuclear
manganese—molybdenum—diethyldithiocarbamate in aqueous dimethylformamide medium is reported.
Photoelectrochemical studies were carried out by coupling the complex electrode which incorporates the
experimental complex in acetylene black on a nickel substrate, with nickel electrode.

EXPERIMENTAL
MnMoO was prepared by mixing manganese(II) chloride (0)7 g in 20 cm of water) with ammonium

molybdate (6)17 g in 30 cm of water). The resulting pale yellow crystals of manganese molybdate was filtered
off and dried well in a desiccator. To 0)25 g of MnMoO , 5 ml con. HCl and 20 cm of dimethylformamide

was added and digested over a water bath for 30 min and then filtered. Sodium diethyldithiocarbamate (1)5 g
in 60 cm of water) was added to the filtrate with constant stirring under ice-cold conditions. The resultant
brown-coloured complex is filtered off, washed with methanol and dried. Thus, the experimental complex
[MnMoO (Et dtc) (H O)] was prepared and stored in dark.
   
* Correspondence to: K. S. Nagaraja, Department of Chemistry and Loyola Institute of Frontier Energy, Loyola College, Chennai
600 034, India. Email: francisx@xlweb.com

CCC 0363-907X/99/030229—05$17.50 Received 3 February 1998

Copyright  1999 John Wiley & Sons, Ltd. Accepted 1 May 1998
230 E. SURESH E¹ A¸.

The photogalvanic studies were carried out in a Honda Cell with ‘U’-shaped glass compartments of
200 cm capacity with the columns separated by a frit of 2)5 cm diameter. The entire cell was surrounded by
a glass jacket to circulate water and thereby to maintain the system at constant temperature. Platinum
electrode of 1)0 cm diameter was used in both the compartments which were impregnated with mercury and
electrically connected to a digital multimeter in series, the distance between the two electrodes was 20 cm.
During the investigation one limb was kept in dark while the other was irradiated either with sunlight or
a 250 W tungsten lamp.
Photoelectrochemical studies were carried out by using the manganese—molybdenum—diethyldithiocarba-
mate complex as the active material with acetylene black to improve the electrical conductivity and nickel
mesh as the substrate. [MnMoO (Et dtc) (H O)] (0)3 g) was added to acetylene black (0)06 g) and polyvinyl
   
alcohol (0)06 g), mixed thoroughly, moistened with distilled water to form a slurry, and was uniformly
applied on a nickel mesh (5;5 cm). The electrode was encapsulated into a porous cellophane paper and
pressed under a pressure of 0)2 tons/sq.in. This electrode is used as the complex electrode.

RESULTS AND DISCUSSIONS

The structure of the experimental complex (Venkatraman and Nagaraja, 1996) is given in Figure 1. The
complex in dimethylformamide shows an absorption maximum at 430 nm. The investigations were carried
out in 80% aqueous DMF medium using 7)7;10\ M complex and 0)092 M potassium chloride as
electrolyte. Manganese—molybdenum—diethyldithiocarbamate complex in N,N-dimethyl formamide is
brown in colour. On irradiation with sunlight for about 30 min, the colour of the complex changed to pale
yellow and in about 4 h the colour turned to pale green where the potential of the system reached a maximum
value. When this solution was kept in dark for about 9 h, the colours are reversed from green to brown. Thus
the system exhibits photochemical reversibility. A cycle of maxima and minima (Figure 2) was observed
corresponding to the irradiation and darkness and the maximum photpotential generated was 70)3 mV with
a photocurrent of 7 lA. When the experiments were repeated with benzophenone as UV sensitizer no
significant changes were noticed, implying that UV component in sunlight is not contributing to the
potential generation.

Effect of pH
The photogalvanic studies were carried out in different pH ranges. The pH of the solution was maintained
by using either perchloric acid or sodium hydroxide. The system was found to be most active in the pH range
4)5—5)5 corresponding to the maximum potential generation of 120 mV. The system showed reversibility in
this pH range and the time taken for reversibility was also shorter. When the system was made more acidic
the colour of the system bleached, the maximum potential decreased and ultimately the system lost its
reversibility. When the system was made alkaline, precipitation of the complex occurred.

Figure 1. Structure of [MnMoO (Et dtc) (H O)]

   

Copyright  1999 John Wiley & Sons, Ltd. Int. J. Energy Res., 23, 229—233 (1999)
 MANGANESE—MOLYBDENUM—DIETHYLDITHIOCARBAMATE FOR SOLAR ENERGY CONVERSION 231

Figure 2. Photogalvanic behaviour of [MnMoO (Et dtc) (H O)]

   

Figure 3. Variation of the maximum potential with temperature

Effect of temperature
The investigations were carried out in the temperature range 10—90°C. The maximum photopotential
gradually increases with the increase in temperature and a peak potential of 345 mV was observed at 80°C
with a photocurrent of 20 lA (Figure 3). When the temperature is gradually decreased the maximum
potential fell and the system underwent reversible potential generation.

Effect of H O
 
Since the system is capable of undergoing redox reaction, hydrogen peroxide (6%) was added in varying
proportions. The system developed a maximum potential of 180 mV in the initial stages, but this maximum
potential was not observed in the subsequent cycles. This may be due to that the hydrogen peroxide would
have undergone decomposition and hence in the subsequent cycles the photopotential falls down. In order to
confirm the effect of hydrogen peroxide on the complex, a blank study was made under the same conditions
using hydrogen peroxide alone, without the complex. The maximum potential observed was only 9 mV,
suggesting that hydrogen peroxide is involved in the redox cycle of the complex.

Copyright  1999 John Wiley & Sons, Ltd. Int. J. Energy Res., 23, 229—233 (1999)
232 E. SURESH E¹ A¸.

Effect of dyes
Dyes such as methyl red, methylene blue and malachite green were used in the cell to ensure the maximum
harnessing of light energy. The addition of methylene blue increased the photopotential initially to 109 mV,
but it gradually decreased and reached a stable value of 49 mV. Malachite green and methyl red showed
a peak potential of 49 and 17 mV, respectively, but gradually decreased to a lower value. The addition of
these dyes to the complex did not help the system to reach a higher potential and made the system irreversible
(Figure 4).

Mechanism
Studies were done using molybdenum—diethyldithiocarbamate [Mo O (Et dtc) ] and manganese—die-
   
thyldithiocarbamates [Mn(Et dtc) ] complexes in a Honda cell under identical conditions, to understand
 
the role played by the individual metal centers in the heterobinuclear complex. Molybdenum—diethyl-
dithiocarbamate in aqueous DMF had a purple-yellow colour and on exposure to light it changed to bluish
green. The initial potential of 165 mV dropped to 85 mV and the system was not reversible. Neither voltage
generation nor colour change was observed for manganese—diethyldithiocarbamate system at various pH.
Thus, the irradiation of molybdenum—diethyldithiocarbamate resulted in photochromism with potential
generation whereas manganese—diethyldithiocarbamate was found to be photochemically inactive. Hence, it
can be concluded that in the manganese—molybdenum—diethyldithiocarbamate complex, the photo-
chromism and potential generation could be attributed to the molybdenum centre and the reversibility to the
manganese centre. When the experiments were carried out in nitrogen atmosphere the system lost its
reversibility, but reversed when oxygen was introduced.
An intramolecular electron transfer mechanism is proposed for the redox behaviour of the complex in
aqueous dimethylformamide, shown in Figure 5. On irradiation with light, Mo(V) undergoes photoreduction
to Mo(IV). Mn(III) oxidizes Mo(IV) back to Mo(V), thereby itself getting reduced to Mn(II). The aerial

Figure 4. Effect of dyes on the photogalvanic behaviour of the complex

Figure 5. Mechanism of the photogalvanic behaviour of the complex

Copyright  1999 John Wiley & Sons, Ltd. Int. J. Energy Res., 23, 229—233 (1999)
 MANGANESE—MOLYBDENUM—DIETHYLDITHIOCARBAMATE FOR SOLAR ENERGY CONVERSION 233

oxygen, in turn, oxidizes Mn(II) back to Mn(III) and is a slow process. Thus, in the photogalvanic behaviour
the redox reaction is responsible for the potential generation.

Construction of photoelectrochemical cell

In the construction of the photoelectrochemical cell, the complex electrode, was made positive, and
coupled with nickel electrode. Both the electrodes were dipped in a glass container containing sodium
chloride solution (3%) as the electrolyte. The complex electrode was irradiated with 250 W tungsten lamp.
Experiments were carried out by coupling the complex electrode with charged nickeloxyhydroxide electrode,
using sodium chloride as the electrolyte. In this system the maximum potential observed was 1)08 V and the
current was 80 lA. When sodium chloride electrolyte was replaced with ammonium chloride (3%), a lower
potential was observed. The same experiment was repeated under identical conditions without the manga-
nese—molybdenum complex. A maximum potential of 0)67 V and a maximum current of 40 lA were
measured. The system is considered to be photovoltaic as the light energy is directed over the solid electrode
and the electron—hole formalism will be more suitable rather than the photoredox galvanic electrochemistry
to explain the potential generation. Thus, the system may be considered for the construction of photo-
electrochemical cell, as it gives a substantial voltage of 1)08 V.

CONCLUSION
It is concluded that the manganese—molybdenum—diethyldithiocarbamate is reversibly photosensitive with
redox action. The complex exhibits pH dependence with optimum potential in the pH range of 4)5 and 5)5
(with 120 mV). Further it is temperature dependent showing a maximum of 345 mV at 80°C. In the
photoelectrochemical cell when the complex electrode is coupled with charged nickeloxyhydroxide electrode
in sodium chloride electrolyte solution, a maximum potential of 1)08 V with a current of 80 lA was obtained.
Thus, the manganese—molybdenum—diethyldithiocarbamate complex is a promising candidate for photogal-
vanic and photoelectrochemical cells which can be extended to solar energy conversion.

ACKNOWLEDGEMENTS
The authors thank Dr. Dakshinamoorthy and Dr. Anand, CECRI, Chennai, for their assistance in the
construction of the photoelectrochemical cells. Thanks are also due to Anto Regis Inigo and Dr. K.
Swaminathan for their encouragement and technical support.

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Copyright  1999 John Wiley & Sons, Ltd. Int. J. Energy Res., 23, 229—233 (1999)