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Study the performance of photogalvanic cells for solarenergy conversion and storage: Rose Bengal– D-Xylose–NaLS system

K.M. Gangotri a,*, Mahesh Kumar Bhimwal b,1

a Department of Chemistry, Jai Narain Vyas University, Jodhpur, Rajasthan 342 033, Indiab Solar Energy Laboratory, Department of Chemistry, Jai Narain Vyas University, Jodhpur, Rajasthan 342 033, India

Received 21 November 2009; received in revised form 3 April 2010; accepted 10 April 2010Available online 14 May 2010

Communicated by: Associate Editor Nicola Romeo

Abstract

The Rose Bengal is used as photosensitizer with D-Xylose as reductant and sodium lauryl sulphate (NaLS) as surfactant for theenhancement of the conversion efficiency and storage capacity of photogalvanic cell for its commercial viability. The observed valueof the photogeneration of photopotential was 885.0 mV and photocurrent was 460.0 lA whereas maximum power of the cell was407.10 lW. The observed power at power point was 158.72 lW and the conversion efficiency was 1.52%. The fill factor 0.3151 was exper-imentally determined at the power point of the cell. The rate of initial generation of photocurrent was 63.88 lA minÀ1. The photogal-vanic cell so developed can work for 145.0 min in dark on irradiation for 165.0 min, i.e. the storage capacity of the photogalvanic cell is87.87%. A simple mechanism for the photogeneration of photocurrent has also been proposed.Ó 2010 Elsevier Ltd. All rights reserved.

Keywords: Rose Bengal; D-Xylose; Sodium lauryl sulphate; Conversion efficiency; Storage capacity; Photocurrent

1. Introduction

The development of viable and long-term solution tomeet our energy needs, that also maintains the quality of our environment which remains one of the most criticalchallenge is being facing by the scientific community. Thesolution of this challenge increasingly depend on electro-chemical processes in solids. The solar energy is easily avail-able, cheaper, environmental friendly source and has thepotential to provide energy with almost zero emission.The novel approach for renewable sources of energy hasled to an increasing interest in photogalvanic cells becauseof their reliable solar energy conversion and storage capac-ity. In present work, the photons of sunlight are used as

driving force for the conversion and storage of sunlight inphotogalvanic cell. The photogalvanic effect was first ofall observed by Rideal and Williams (1925) but it was sys-tematically investigated by Rabinowitch (1940a,b) and lateron Clark and Eckert (1975), and Hall et al. (1977). Wildes(1977), Murthy et al. (1980), Suda et al. (1978), Dixit andMackay (1982), Hamdi and Aliwi (1996) and Bayer et al(2001) have reported the various systems in photogalvaniccell for solar energy conversion and storage. Jinting et al(2008) have observed the performance of dye-sensitizedsolar cells based on nanocrystals TiO2 film prepared withmixed template method. The performance of photogalvaniccells for the conversion of solar energy into electrical energyand storage capacity depends on the photochemistry of thecell. According to Albery and Archer (1977), the conversionefficiency of the photogalvanic cell could be as large as 18%but it is unlikely that all the necessary conditions can bemet. A more reliable estimate of the maximum power conversion efficiency that could be achieved from a photogal-vanic cell is between 5% and 9%. Memming (1980) and

0038-092X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.

doi:10.1016/j.solener.2010.04.006

* Corresponding author. Address: C-38, University Jaswant Campus,Jodhpur, Rajasthan 342 001, India. Tel.: +91 291 251 3899; fax: +912912614162.

E-mail addresses: [email protected] (K.M. Gangotri), [email protected] (M.K. Bhimwal).1 Tel.: +91 9460435421; fax: +91 2912614162.

www.elsevier.com/locate/solene

Available online at www.sciencedirect.com

Solar Energy 84 (2010) 1294–1300

the

storage capacity



Bhardwaj et al. (1981) have suggested the process of solarenergy conversion by photoelectrochemical process andchloroplast photoelectrochemical cells, respectively. Groe-nen et al. (1984) have observed micelles effect in the fer-rous/thionine photogalvanic cell.

Recently the photogalvanic effects have been observedin various systems by Dube and Sharma (1994), Dube(2007), Lal (2007), Pramila and Gangotri (2007), Kumariet al. (2009), Genwa et al. (2009), Gangotri and Bhimwal(in press), Gangotri and Gangotri (2009) and Gangotriand Indora (2010) for solar energy conversion and stor-age in photogalvanic cells. They have used differentphotosensitizers, micellar species and reductants inphotogalvanic system, but no attention has been paidto use of the Rose Bengal– D-Xylose–NaLS system toenhance the electrical output i.e. 460.0 lA and storagecapacity i.e. 87.87% of the photogalvanic cells and toreduce the cost of the cell to gain commercial viability.Therefore, the present work was undertaken and the var-

iation of the power output with the concentrations of thereductant, surfactant, sodium hydroxide, variation of dif-fusion length and other parameters of the cell is found tobe quite sensitive.

2. Experimental method

A glass tube of H-shape was used containing knownamount of the solutions of the photosensitizer – Rose Ben-gal (Merck) with reductant-D-Xylose (Loba), surfactant-sodium lauryl sulphate (s.d. fine) and sodium hydroxide(Merck) in the present work. The total volume of the mix-ture was always kept 25.0 ml making up by doubly distilled

water. All the solutions were kept in amber coloured con-tainers to protect them from sunlight. A platinum electrode(1.0 Â 1.0 cm2) was dipped in one limb having a window

and a saturated calomel electrode (SCE) was immersedanother limb of the H-tube. The terminals of the electrowere connected to a digital pH meter (Systronics mod335) and the whole cell was placed in the dark. The potetial (mV) was measured in dark when the photogalvancell attained a stable potential. Then, the limb containiplatinum electrode was exposed to a 200 W tungsten lam(Sylvania) as light source. Employing lamps of differewattage varies the light intensity. A water filter was placbetween the illuminated chamber and the light sourcecut-off infrared radiations. On illumination, the phochemical bleaching of Rose Bengal was studied potentmetrically. The photopotential and photocurrgenerated by the system was measured with the help the digital pH meter and microammeter (Ruttonsha Simson), respectively. The current–voltage characteristics photogalvanic cell have been studied by applying an extnal load with the help of a carbon pot (log 470 K) conected in the circuit through a key to have close circu

and open circuit device. The experimental set-up of phogalvanic cell is given in Fig. 1.

3. Results and discussion

3.1. Effect of variation of photosensitizer (Rose Bengal)

concentration on the system

With the increase in concentration of the photosensiti(Rose Bengal) in present system, the photopotential aphotocurrent were found to increase until it reaches a maimum value. On further increase in concentration of phosensitizer a decrease in electrical output of the cell w

found. The effect of variation of Rose Bengal concentration photopotential and photocurrent are reported Table 1.

Fig. 1. Experimental set-up of photogalvanic cell.

K.M. Gangotri, M.K. Bhimwal / Solar Energy 84 (2010) 1294–1300 1



On the lower side of the concentration range of photo-sensitizer, there are a limited number of photosensitizermolecules to absorb the major portion of the light in thepath and, therefore, there is low electrical output, whereashigher concentration of the photosensitizer does not permitthe desired light intensity to reach the molecules near theelectrodes and hence, there is corresponding fall in the

power of the cell.

3.2. Effect of variation of reductant (D-Xylose)

concentration on the system

With the increase in concentration of the reductant (D-Xylose) in present system, the photopotential was foundto increase till it reaches a maximum value. On furtherincrease in concentration of reductant, a decrease in theelectrical output of the cell was observed. The effect of var-iation of reductant concentration on the photopotentialand photocurrent of system are reported in Table 2.

The fall in power output was also resulted with decreasein concentration of reductant due to less number of mole-cules available for electron donation to the cationic form of dye. On the other hand, the movement of dye moleculesmay be hindered by the higher concentration of reductantto reach the electrode in the desired time limit and it willalso result into a decrease in electrical output.

3.3. Effect of variation of surfactant (NaLS) concentration

on the system

The effect of surfactant-sodium lauryl sulphate (NaLS)concentration was also investigated in the present system.

The surfactant was used to increase the solubility of photo-sensitizer. It was observed that electrical output of the cellwas found to increase on increasing the concentration ofsurfactant reaching a maximum value. On further increasein their concentrations, a fall in photopotential, photocur-rent and power of the photogalvanic cell was observed. Theresults are reported in Table 3.

3.4. Effect of pH on the system

The photogalvanic system is quite sensitive for pH var-iation. The electrical output of the photogalvanic cell waschanged by the variation of pH on the system. It can beobserved from the Table 4 that there is an increase in elec-trical output of the cell with the increase in pH values. AtpH 12.83 a maxima was obtained. On further increase inpH, there was a decrease in photopotential and photocur-rent. Thus, photogalvanic cells containing the Rose Bengal– D-Xylose–NaLS system were found to be quitesensitive to the pH of the solutions. The effect of variationof pH on photopotential and photocurrent are reported inTable 4.

3.5. Effect of diffusion length on the system

The effect of variation of diffusion length (distancebetween the two electrodes i.e. saturated calomel electrodeand Pt electrodes) on the current parameters of the photogalvanic cell was studied using H-cells of different dimen-sions. It was observed that there was a sharp increase inphotocurrent (i max) in the first few minutes of illuminationand then, there was a gradual decrease to a stable value of

Table 1Effect of variation of photosensitizer (Rose Bengal) concentration on the system.

Concentration of photosensitizer(Rose Bengal Â 10À5 M)

Rose Bengal– D-Xylose–NaLS system

Photopotential(mV)

Photocurrent(lA)

Power(lW)

Conversionefficiency (%)

Storage capacityin dark (min)

9.52 792.0 335.0 265.32 0.93 65.09.68 828.0 390.0 322.92 1.37 75.0

9.84 885.0 460.0 407.10 1.52 145.010.00 836.0 378.0 316.00 1.34 90.010.16 802.0 352.0 282.00 1.26 70.0

[D-Xylose] = 1.20 Â 10À3 M; light intensity = 10.4 mW cmÀ2; [NaLS] = 6.80 Â 10À3 M; temperature = 299 K; pH = 12.83.

Table 2Effect of variation of reductant (D-Xylose) concentration on the system.

Concentration of reductant(D-Xylose Â 10À3 M)


Photopotential(mV)

Photocurrent(lA)

Power(lW)


Storage capacityin dark (min)

0.98 795.0 348.0 276.66 1.14 60.01.08 825.0 386.0 318.45 1.52 65.01.20 885.0 460.0 407.10 1.52 145.01.31 812.0 378.0 306.93 1.15 70.01.42 780.0 340.0 265.20 1.11 80.0

[Rose Bengal] = 9.84 Â 10À5 M; light intensity = 10.4 mW cmÀ2; [NaLS] = 6.80 Â 10À3 M; temperature = 299 K; pH = 12.83.

1296 K.M. Gangotri, M.K. Bhimwal/ Solar Energy 84 (2010) 1294–1300



photocurrent. This photocurrent at equilibrium is repre-sented as (i eq). This kind of photocurrent behaviour isdue to an initial rapid reaction followed by a slow rate-determining step at a later stage.

On the basis of the effect of diffusion path length on thecurrent parameters, as investigated by Kaneko and Yam-ada (1977), it may be concluded that the leuco or semireduced form of dyes, and the dyes itself are the main elec-troactive species at the illuminated and the dark electrodes,respectively. However, the reducing agents and their oxi-dized products behave as the electron carriers in the celldiffusing through the path. The results are graphically rep-resented in Fig. 2.

3.6. Effect of light intensity on the system

We have used different light intensity sources for changein the intensity of light and it was found that photocurrent

showed a linear increasing behaviour with the increase inlight intensity whereas photopotential increases in a loga-rithmic manner. Whereas, the light intensity was measuredin term of mW cmÀ2 with the help of solarimeter (CELModel SM 203). The results are graphically representedin Fig. 3.

3.7. Current–voltage (i–V) characteristics of the

photogalvanic cell

The short circuit current (i sc) and open circuit voltage(V oc) of the photogalvanic cells were measured with the

Table 3Effect of variation of surfactant (NaLS) concentration on the system.

Concentration of surfactant(NaLS Â 10À3 M)


Photopotential(mV)

Photocurrent(lA)

Power(lW)


Storage capain dark (min)

6.48 792.0 348.0 275.61 1.23 60.06.64 822.0 382.0 314.00 1.09 75.0

6.80 885.0 460.0 407.10 1.52 145.06.96 834.0 378.0 315.25 1.14 60.07.12 785.0 342.0 268.47 0.87 70.0

[Rose Bengal] = 9.84 Â 10À3 M; light intensity = 10.4 mW cmÀ2; [D-Xylose] = 1.20 Â 10À3 M; temperature = 299 K; pH = 12.83.

Table 4Effect of variation of pH on the system.

pH Rose Bengal– D-Xylose–NaLS system

Photopotential(mV)

Photocurrent(lA)

Power(lW)

Conversionefficiency(%)

Storagecapacityin dark(min)

12.79 790.0 352.0 278.08 1.00 55.0

12.81 845.0 405.0 342.22 1.06 65.012.83 885.0 460.0 407.10 1.52 145.012.85 822.0 382.0 314.00 1.24 80.012.87 790.0 335.0 264.65 1.07 65.0

[Rose Bengal] = 9.84 Â 10À3 M; light intensity = 10.4 mW cmÀ2; [D-Xylose] = 1.20 Â 10À3 M; temperature = 299 K; [NaLS] = 6.80 Â 10À3 M.

Fig. 2. Variation of current parameters with diffusion length on system.

Fig. 3. Variation of photocurrent and log V with light intensity.




help of a microammeter (keeping the circuit closed) andwith a digital pH meter (keeping the other circuit open),respectively. The current and potential values in betweenthese two extreme values were recorded with the help of a carbon pot (log 470 K) connected in the circuit of mic-roammeter, through which an external load was applied.The Current–Voltage (i – V ) characteristics of the photogal-vanic cell containing Rose Bengal– D-Xylose–NaLS systemis graphically represented in Fig. 4.

It was observed that i – V curve deviated from their reg-ular rectangular shapes. A point in i – V curve, called powerpoint (pp) is determined where the product of current andpotential was maximum and the fill factor is calculatedusing the following formula:

Fill factorðgÞ ¼V pp Â i pp

V oc Â i scð1Þ

where as V pp and i pp represent the value of photopotentialand photocurrent at power point, respectively and V oc, i screpresent open circuit voltage and short circuit current,

respectively. The value of fill factor (g) = 0.3151 was ob-tained and the power point of cell (pp) = 158.72 lW wasdetermined on the system.

3.8. Storage capacity of the photogalvanic cell

The storage capacity of the photogalvanic cell wasobserved by applying an external load (necessary to havecurrent at power point) after termination the illuminationas soon as the potential reaches a constant value. The stor-age capacity was determined in terms of t1/2, i.e., the timerequired in fall of the electrical output (power) to its half at power point in dark. It was observed that the photogal-

vanic cell can be used in dark for 145.0 min on irradiationfor 165.0 min, so observed storage capacity is 87.87%. Theresults are graphically represented in Fig. 5.

3.9. Conversion efficiency of the photogalvanic cell

The conversion efficiency of system containing RoseBengal as photosensitizer is calculated using the electrical

output at power point and the power of incident radiations

The conversion efficiency of the photogalvanic cell is deter-mined as 1.52% using the following formula.

Conversion efficiency

¼V pp Â i pp

10:4 mW cmÀ2 Â Electrode area ðcm2ÞÂ 100% ð2Þ

The systems (at the optimum conditions) were alsoexposed to sunlight, and the conversion efficiency and sun-light conversion data for this system are reported inTable 5

3.10. The performance of photogalvanic cell

The overall performance of the photogalvanic cell was

observed and reached to remarkable level in the perfor-mance of photogalvanic cells with respect to electrical out-put, initial generation of photocurrent, conversionefficiency and storage capacity of the photogalvanic cellThe results so obtained in Rose Bengal– D-Xylose–NaLSsystem are summarized in Table 6.

4. Mechanism

On the basis of these observations, a mechanism hasbeen suggested for the generation of photocurrent in thephotogalvanic cell as given below.

Fig. 4. Current–voltage (i – V ) curve of the photogalvanic cell.

Fig. 5. Storage capacity of the photogalvanic cell.

Table 5Conversion efficiency of the photogalvanic cell.

Concentration of photosensitizer(RoseBengal Â 10À5 M)


Fillfactor(g)

Conversionefficiency(%)

Sunlight conversion data

Photopotential(mV)

Photocurren(lA)

9.52 0.3037 0.93 1980.0 840.09.68 0.3062 1.37 2070.0 980.09.84 0.3151 1.52 2210.0 1150.0

10.00 0.3093 1.34 2090.0 945.010.16 0.3061 1.26 2005.0 880.0

[Rose Bengal] = 9.84 Â 10À3 M; light intensity = 10.4 mW cmÀ2; [D

Xylose] = 1.20 Â 10À3 M; temperature = 299 K; [NaLS] = 6.80 Â 10À3 M




4.1. Illuminated chamber

On irradiation, dye molecules get excited.

RB !hm

RBÃ ð3Þ

The excited dye molecules accept an electron fromreductant and converted into semi or leuco form of dye,and the reductant into its oxidized form

RBÃ þ R ! RBÀðsemi or leucoÞ þ Rþ ð4Þ

4.1.1. At platinum electrode

The semi or leuco form of dye loses an electron to elec-trode and converted into original dye molecule.

RBÀ ! RB þ eÀ ð5Þ

4.2. Dark chamber

4.2.1. At counter electrode

Dye molecules accept an electron from electrode andconverted in semi or leuco form.

RB þ eÀ ! RBÀðsemi or leucoÞ ð6Þ

Finally leuco/semi form of dye and oxidized form of reduc-tant combine to give original dye and reductant moleculeand the cycle will go on

RBÀ þ Rþ ! RB þ R ð7Þ

where RB, RBÃ

, RBÀ

, R and R+ are the dye (Rose Bengal),excited form of dye, semi or leuco form of dye, reductantand oxidized form of the reductant, respectively.

5. Conclusion

The photogalvanic cells have the promising storagecapacity. In present research work the Rose Bengal as pho-tosensitizer, D-Xylose as reductant and sodium lauryl sul-phate as surfactant have been used in the system and thehigher values of conversion efficiency and storage capacityhave been observed in comparison to earlier reported

photogalvanic systems i.e. DSS/CTAB/Triton X-10Rohodamine–Oxalic acid system by Genwa and Gen(2008) and Brij-35-DTPA system by Genwa and Kha(2009). They have reported conversion efficiency is 0.20.86% and 0.2707–0.643% respectively, in comparisonthe present photogalvanic system consisting of Rose Begal– D-Xylose–NaLS, the conversion efficiency is 1.52and the storage capacity of the cell is 145.0 min on the irrdiation for 165.0 min in the so developed photogalvansystems.

In view of these observations, it can be concluded thRose Bengal is better photosensitizer with D-Xylose reductant and sodium lauryl sulphate as surfactant photogalvanic cell for solar energy conversion and storaHowever, the considerable research and development ffurther improvement in results for solar energy conversiand storage is still need.

Acknowledgement

The authors are thankful to Professor P.K. Sharma (MHead, Department of Chemistry, J.N.V. University, Jodpur for providing all necessary facilities. One of the auth(Mahesh Kumar Bhimwal) is thankful to Indian goverment for providing financial assistance for the researpurpose.

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Table 6The performance of photogalvanic cell.

S.N. Parameters Observed results

1 Dark potential 210.0 mV2 Open circuit voltage (V OC ) 1095.0 mV3 Photopotential (DV) 885.0 mV4 Initial generation of photocurrent 63.88 lA minÀ1

5 Equilibrium photocurrent (i eq) 460.0 lA6 Maximum photocurrent (i max) 575.0 lA7 Time of illumination 165.0 min8 Storage capacity (t1/2) 145.0 min9 Conversion efficiency (CE) 1.52%10 Fill factor (g) 0.3151

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