Redox Kinetics and Nonstoichiometry of Ce0.5Zr0.5O2−δ for Water Splitting and Hydrogen Production

Zhenlong Zhao, Mruthunjaya Uddi, Nikolai Tsvetkov, Bilge Yildiz, Ahmed F. Ghoniem

Research output: Contribution to journalArticlepeer-review

32 Scopus citations


Water splitting and chemical fuel production as a promising carbon-neutral energy solution relies critically on an efficient electrochemical process over catalyst surfaces. The fundamentals within the surface redox pathways, including the complex interactions of mobile ions and electrons between the bulk and the surface, along with the role of adsorbates and electrostatic fields remain yet to be understood quantitatively. This work presents a detailed kinetics study and nonstoichiometry characterization of Ce0.5Zr0.5O2−δ (CZO), one of the most recognized catalysts for water splitting. The use of CZO leads to >60% improvement in the kinetic rates as compared with undoped ceria with twice the total yield at 700 °C, resulting from the improved reducibility. The peak H2 production rate is 95 μmol g–1 s–1 at 700 °C, and the total production is 750 μmol g–1. A threshold temperature of 650 °C is required to achieve significant H2 production at fast rates. The redox kinetics is modeled using two-step surface chemistry with bulk-to-surface transport equilibrium. Kinetics and equilibrium parameters are extracted, and the model predictions show good agreement with the measurements. The enthalpy of bulk defect formation for CZO is found to be 262 kJ/mol, >40% lower than that of undoped ceria. As oxygen vacancy is gradually filled up, the surface H2O splitting chemistry undergoes a transition from exothermic to endothermic, with the crossover around δ = 0.04 to 0.05, which constrains the further ion incorporation process. Our kinetics study reveals that the H2O splitting process with CZO is kinetics limited at low temperature and transitions to partial-equilibrium with significantly enhanced backward reaction at high temperature. The charge-transfer step is found to be the rate-limiting step for H2O splitting. The detailed kinetics and nonstoichiometric equilibria should be helpful in guiding the design and optimization of CZO as a catalyst, oxygen storage material, as well as oxygen carrier for water-splitting applications.
Original languageEnglish (US)
Pages (from-to)11055-11068
Number of pages14
JournalThe Journal of Physical Chemistry C
Issue number21
StatePublished - May 11 2017
Externally publishedYes


Dive into the research topics of 'Redox Kinetics and Nonstoichiometry of Ce0.5Zr0.5O2−δ for Water Splitting and Hydrogen Production'. Together they form a unique fingerprint.

Cite this