Efficient Base-Metal NiMn/TiO₂ Catalyst for CO₂ Methanation

Energy storage solutions are a vital component of the global transition toward renewable energy sources. The power-to-gas (PtG) concept, which stores surplus renewable energy in the form of methane, has therefore become increasingly relevant in recent years. At present, supported Ni nanoparticles are preferred as industrial catalysts for CO₂ methanation due to their low cost and high methane selectivity. However, commercial Ni catalysts are not active enough in CO₂ methanation to reach the high CO₂ conversion (>99%) required by the specifications for injection in the natural gas grid. Herein we demonstrate the promise of promotion of Ni by Mn, another low-cost base metal, for obtaining very active CO₂ methanation catalysts, with results comparable to more expensive precious metal-based catalysts. The origin of this improved performance is revealed by a combined approach of nanoscale characterization, mechanistic study, and density functional theory calculations. Nanoscale characterization with scanning transmission electron microscopy–energy-dispersive X-ray spectroscopy (STEM-EDX) and X-ray absorption spectroscopy shows that NiMn catalysts consist of metallic Ni particles decorated by oxidic Mn²⁺ species. A mechanistic study combining IR spectroscopy of surface adsorbates, transient kinetic analysis with isotopically labeled CO₂, density functional theory calculations, and microkinetics simulations ascertains that the MnO clusters enhance CO₂ adsorption and facilitate CO₂ activation. A macroscale perspective was achieved by simulating the Ni and NiMn catalytic activity in a Sabatier reactor, which revealed that NiMn catalysts have the potential to meet the demanding PtG catalyst performance requirements and can largely replace the need for expensive and scarce noble metal catalysts.