Phase transition Ni-Co-Ca-O bifunctional catalysts for high and stable hydrogen production from sorption enhanced steam methane reforming

Sorption enhanced steam methane reforming (SESMR) is an effective method to improve the efficiency of hydrogen production from methane reforming while fixing CO2 to reduce carbon emissions. However, the deactivation of adsorbents during high temperature recycling limits the utilization of SESMR. In this paper, by combining the phase transition process of Ca-Co-O species and Ni-Co alloy, we prepared a series of Ni-Co-Ca-O bifunctional catalysts for SESMR hydrogen production. The 1Ni4.5Co4.5CaO catalyst exhibited high catalytic activity in the SESMR reaction with hydrogen concentration exceeding 99.6 % and complete methane conversion. The catalyst also showed high stability in 50 cycle experiments with no significant reduction in hydrogen production and CO2 uptake performance. The Ni-Co-Ca-O bifunctional catalysts consisted of NiO and Co-Ca-O species, by analyzing the fresh and reacted catalysts, the mechanism of the catalyst with high catalytic activity and stability was revealed. Firstly, the catalyst formed Ni-Co alloy and CaO adsorbent by a reduction reaction, and then the SESMR hydrogen production reaction was carried out. After the complete conversion of CaO to CaCO3, the catalyst was re-formed into NiO and Co-Ca-O species by introducing O2 in the regeneration reaction to carry out a new cycle of reduction -> hydrogen production. The synergistic interaction between the Ni-Co alloy enhanced the methane reforming and water gas shift reaction, leading to an increase in hydrogen production and methane conversion. The phase transition of Co from Co-Ca-O species to Ni-Co alloy and back to Co-Ca-O species inhibited the sintering of CaO, which significantly enhanced the cyclic stability of the catalyst. The results of this study are expected to provide a new pathway for the design of SESMR bifunctional catalysts.