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Adsorption of croconate dyes on TiO2 anatase (101) surface: A periodic DFT study to understand the binding of diketo groups#

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Abstract

The adsorption of model croconate dyes on the stoichiometric TiO2 anatase (101) surface has been studied by means of periodic density functional calculations to understand the adsorption of the diketo (-COCO-) groups. Past experimental and theoretical results have shown the strong binding ability of the acid group (-COOH) to the TiO2 surface but here the theoretical studies predicts the binding strength of the diketo group to be also significant and comparable with that of the -COOH group. This may cause a competitive binding between the keto groups and the acid groups on the TiO2 surface in the case of croconate dyes and cause a reduction in the efficiency of the DSSC.

Adsorption of diketo groups of model croconates in bidentate bridging fashion on the TiO2 anatase (101) surface has binding energy of 23.2 kcal/mol and 28.7 kcal/mol which is competitive to the carboxylic acid binding. There is a decrease in charge transfer to the TiO2 due to the biradical nature of the molecules leading to lesser efficiency.

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  1. AVINASH L PUYAD

    Present address: School of Chemical Sciences, SRTMU, Nanded, 431 606, India

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  1. Inorganic and Physical Chemistry Division, Indian Institute of Chemical Technology, Hyderabad, 500 007, India

    AVINASH L PUYAD, CH RAMESH KUMAR & K BHANUPRAKASH

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#Dedicated to Prof. N Sathyamurthy on his 60th birthday

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PUYAD, A.L., KUMAR, C.R. & BHANUPRAKASH, K. Adsorption of croconate dyes on TiO2 anatase (101) surface: A periodic DFT study to understand the binding of diketo groups# . J Chem Sci 124, 301–310 (2012). https://doi.org/10.1007/s12039-012-0229-1

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