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A Density Functional Theory and Experimental Study of CO2 Photoreduction to Methanol over α-Sulfur-TiO2 Composite

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Abstract

CO2 reduction is an attractive way for the production of sustainable environment-friendly chemicals. Using the density functional theory employed by DMol3, we calculated the electronic properties of α-sulfur-modified surface of TiO2 (111). We report α-sulfur-TiO2 composite material for selective CO2 reduction to methanol. The α-sulfur-TiO2 catalyst showed higher adsorption for CO2 molecule (reactant) and lower adsorption for methanol (product) as compared to TiO2 catalyst. The introduction of the α-sulfur molecule in the TiO2 catalyst leads to redistribution of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO). The DFT studies showed that the α-sulfur-TiO2 catalyst reduced the band gap to 2.06 eV from 2.88 (α-sulfur) and 3.2 eV (TiO2). The experimental study was done using photoelectrochemical CO2 reduction. The sulfur-TiO2 catalyst showed higher methanol production (17 mM/h) under visible light as compared to α-sulfur catalyst (8.5 mM/h).

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Acknowledgments

RY and AM are thankful to the Council of Scientific and Industrial Research (CSIR), New Delhi, India, for the research fellowship. VV thanked the Department of Science and Technology (DST), New Delhi, India, for INSPIRE research fellowship. NP and AK thanked the CSIR-Indian Institute of Petroleum (IIP), Dehradun, India, for the research funding.

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Authors and Affiliations

  1. Bio-Fuels Division, CSIR-Indian Institute of Petroleum (IIP), Mohkampur, Dehradun, 248005, India

    Rajkumar Yadav, Gangeshwar Singh, Ankit Mishra, Vikas Verma, Azeem Khan, Neeraj Pal & Anil Kumar Sinha

  2. Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India

    Rajkumar Yadav, Ankit Mishra, Vikas Verma, Azeem Khan, Neeraj Pal & Anil Kumar Sinha

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  1. Rajkumar Yadav
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Contributions

The work plan was demonstrated by RY and AKS. RY contributed in performing the experimental reactions and DFT calculation. AM, VV, AK, NP, and HS helped in the catalyst synthesis and characterization. The manuscript was co-written by RY and AKS. All authors have approved the final version of the manuscript.

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Correspondence to Anil Kumar Sinha.

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Yadav, R., Singh, G., Mishra, A. et al. A Density Functional Theory and Experimental Study of CO2 Photoreduction to Methanol over α-Sulfur-TiO2 Composite. Electrocatalysis 12, 56–64 (2021). https://doi.org/10.1007/s12678-020-00631-w

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