Breaking the temperature barrier: Unveiling the potential of ceria nanorods for low temperature thermochemical water splitting

Abstract

Thermochemical Water-Splitting (TCWS) is a promising approach for generating clean hydrogen (H₂) by employing the waste heat originating from different sources. High-temperature requirements and temperature swing approach hinder the widespread adoption of TCWS for clean hydrogen production. This study explores ceria nanorods (CeNRs) as a potential solution for overcoming these limitations. Herein, we report, the TCWS in a fixed bed reactor using CeNRs at low and constant temperature of 400 °C. We systematically explore the influence of synthesis parameters on the resulting CeNRs, including the selection of ceria precursor, effect of calcination, and their impact in TCWS. It was found that CeNRs prepared using cerium chloride as the precursor exhibited enhanced TCWS activity, resulting significantly higher total H₂ yield 4.74 mL/g, at a constant temperature of 400 °C in three redox cycles. Moreover, X-ray Photoelectron Spectroscopy (XPS) analysis confirms the presence of both Ce³⁺ and Ce⁴⁺ states within the structure, with Ce³⁺ constituting approximately 30 % and Ce⁴⁺ accounting for approximately 70 % of the total cerium content. Additionally, Raman spectroscopy corroborates the presence of a higher concentration of oxygen vacancy which are beneficial for increasing the hydrogen production. We demonstrate that ceria in its nanorod structure having exposed higher proportions of (110) and (100) planes and higher concentration of oxygen vacancies is beneficial for lowering TCWS temperature as well as increasing the hydrogen yield.