Hydrogen production by the water-gas shift reaction: A comprehensive review on catalysts, kinetics, and reaction mechanism

The global push towards a hydrogen economy fuels hydrogen production from various sources. A crucial step in enriching hydrogen and reducing CO in syngas derived from carbon-based hydrogen production is the water-gas shift reaction (WGSR). Given the equilibrium-limited nature of WGSR, low temperatures are necessary to reduce carbon monoxide concentrations to the desired level. Traditionally, iron‑chromium (Fe/Cr) and copper‑zinc (Cu/Zn) catalysts have been widely used at high and low temperatures, respectively. Numerous studies have focused on developing optimal WGS catalysts with the desired characteristics and efficiency. This review extensively discusses various catalysts for different stages of WGSR, including low, medium, high-temperature, and sour WGS catalysts. However, understanding the contrast between the redox and associative mechanisms and the nature of intermediates in the WGS pathway remains unclear. A detailed study of the WGSR pathway is imperative to develop highly active and stable catalysts. Various experimental kinetic values and models have also been reported to elucidate the WGSR mechanism at different temperatures. The primary deactivation sources of WGS catalysts have been discussed to highlight recent advances to improve catalyst performance. The contribution of computational methods such as Density Functional Theory (DFT) to developing WGS catalysts is also explored. Furthermore, the review addresses the challenges encountered in the WGSR, and recommendations and conclusions are drawn to guide future research efforts.