Barium-Promoted Yttria-Zirconia-Supported Ni Catalyst for Hydrogen Production via the Dry Reforming of Methane: Role of Barium in the Phase Stabilization of Cubic ZrO2

Ahmed Sadeq Al-Fatesh; Rutu Patel; Vijay Kumar Srivastava; Ahmed Aidid Ibrahim; Muhammad Awais Naeem; Anis Hamza Fakeeha; Ahmed Elhag Abasaeed; Abdullah Ali Alquraini; Rawesh Kumar

doi:10.1021/acsomega.2c00471

Barium-Promoted Yttria-Zirconia-Supported Ni Catalyst for Hydrogen Production via the Dry Reforming of Methane: Role of Barium in the Phase Stabilization of Cubic ZrO₂

ACS Omega. 2022 May 3;7(19):16468-16483. doi: 10.1021/acsomega.2c00471. eCollection 2022 May 17.

Authors

Ahmed Sadeq Al-Fatesh¹, Rutu Patel², Vijay Kumar Srivastava³, Ahmed Aidid Ibrahim¹, Muhammad Awais Naeem⁴, Anis Hamza Fakeeha¹, Ahmed Elhag Abasaeed¹, Abdullah Ali Alquraini¹, Rawesh Kumar³

Affiliations

¹ Chemical Engineering Department, College of Engineering, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia.
² Department of Chemistry, Sankalchand Patel University, Visnagar, Gujarat, India 384315.
³ Department of Chemistry, Indus University, Ahmedabad, Gujarat, India 382115.
⁴ ETH Zürich, Department of Mechanical and Process Engineering, CH 8092 Zürich, Switzerland.

Abstract

Developing cost-effective nonprecious active metal-based catalysts for syngas (H₂/CO) production via the dry reforming of methane (DRM) for industrial applications has remained a challenge. Herein, we utilized a facile and scalable mechanochemical method to develop Ba-promoted (1-5 wt %) zirconia and yttria-zirconia-supported Ni-based DRM catalysts. BET surface area and porosity measurements, infrared, ultraviolet-visible, and Raman spectroscopy, transmission electron microscopy, and temperature-programmed cyclic (reduction-oxidation-reduction) experiments were performed to characterize and elucidate the catalytic performance of the synthesized materials. Among different catalysts tested, the inferior catalytic performance of 5Ni/Zr was attributed to the unstable monoclinic ZrO₂ support and weakly interacting NiO species whereas the 5Ni/YZr system performed better because of the stable cubic ZrO₂ phase and stronger metal-support interaction. It is established that the addition of Ba to the catalysts improves the oxygen-endowing capacity and stabilization of the cubic ZrO₂ and BaZrO₃ phases. Among the Ba-promoted catalysts, owing to the optimal active metal particle size and excess ionic CO₃ ^2- species, the 5Ni4Ba/YZr catalyst demonstrated a high, stable H₂ yield (i.e., 79% with a 0.94 H₂/CO ratio) for up to 7 h of time on stream. The 5Ni4Ba/YZr catalyst had the highest H₂ formation rate, 1.14 mol g^-1 h^-1 and lowest apparent activation energy, 20.07 kJ/mol, among all zirconia-supported Ni catalyst systems.