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Cu–Cl Thermochemical Water Splitting Cycle: Probing Temperature-Dependent CuCl2 Hydrolysis and Thermolysis Reaction Using In Situ XAS

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Abstract

Recently, we reported detailed investigations on a hydrolysis step of Cu–Cl thermochemical cycle (Singh et al. in Int J Energy Res 44:2845–2863, 2020) where we demonstrated CuCl2 hydrolysis using a fixed-bed reactor under optimized conditions. Thermolysis of CuCl2 and oxide formation are associated hindrances in achieving 100% phase-pure hydrolysis product, Cu2OCl2. With an objective to understand the thermolysis and hydrolysis processes at molecular level, both these reactions were investigated independently in the present study using in situ XAS as a probe. The progress of both the reactions was recorded from RT to 400 °C by monitoring temperature-dependent evolution of Cu species using Cu K-edge XAS measurements at BL-09, Indus-2 SRS, RRCAT, Indore, India. XAS results are also corroborated with ex situ analysis by XRD and TG of samples containing various compositions of CuCl2 mixed with boron nitride (pellets employed for XAS). Besides LCF, hydrolysis product Cu2OCl2 yield was further supported by chemical titrations. EXAFS revealed that with increasing temperature, coordination of Cu atoms in reactant CuCl2 progressively decreased during thermolysis. For hydrolysis process, coordination of Cu atoms in Cu–Cu, Cu–O and Cu–Cl linkages approached towards that of Cu2OCl2 and CuO. CuCl2 diminished and transformed into CuCl (88 mass%) at 350 °C during thermolysis and ~ 60 mass% of Cu2OCl2 and 40 mass% of CuO during hydrolysis reaction. Based on in situ investigations in the present study, the most probable reactions taking place during CuCl2 hydrolysis at different temperatures are proposed for S/Cu of 14.6.

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Acknowledgements

We thank Dr. A. K. Tyagi, Head, Chemistry Division, Associate Director, Chemistry Group, BARC, for keen support and encouragement.

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Authors and Affiliations

  1. Chemistry Division, Bhabha Atomic Research Centre, Mumbai, 400085, India

    Rajendra V. Singh, Mrinal R. Pai, Atindra M. Banerjee, Suhas Phapale & Arvind K. Tripathi

  2. Atomic and Molecular Physics Division, Bhabha Atomic Research Centre, Mumbai, 400085, India

    Chandrani Nayak & Dibyendu Bhattacharyya

  3. Homi Bhabha National Institute, Anushaktinagar, Mumbai, 400094, India

    Rajendra V. Singh, Mrinal R. Pai, Atindra M. Banerjee, Dibyendu Bhattacharyya & Arvind K. Tripathi

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Singh, R.V., Pai, M.R., Banerjee, A.M. et al. Cu–Cl Thermochemical Water Splitting Cycle: Probing Temperature-Dependent CuCl2 Hydrolysis and Thermolysis Reaction Using In Situ XAS. J Therm Anal Calorim 147, 7063–7076 (2022). https://doi.org/10.1007/s10973-021-10969-y

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