Co-Exsolution of Ni-Based Alloy Catalysts for the Valorization of Carbon Dioxide and Methane

ConspectusThe reversible coexsolution mechanism of perovskite oxides is emerging as an alternative method for synthesizing alloy catalyst nanoparticles. Co-exsolution is a partial decomposition process where multiple B cations diffuse from the bulk of a solid precursor and nucleate on the surface. The unique properties of exsolved alloy catalysts, including improved dispersion, thermal stability, and compositional malleability, make them particularly useful for converting CO₂ into chemical commodities and fuels. However, the coexsolution of alloys is still in development, and fundamental insights into the alloying mechanism, formation of nanoparticles, and defect chemistry are needed.This Account examines the solid-state chemistry of perovskite oxide precursors and reaction parameters that can be altered to control the assembly or exsolution of Ni-based alloys. The characteristics of bulk perovskite oxide precursors heavily influence the exsolved alloy catalyst nanoparticle assembly, growth, and composition. Inherent defects, such as oxygen vacancies and grain boundaries, primarily facilitate the transport of catalytic B-cation dopants from the bulk to the surface. An example of how bulk defects can affect the properties of Ni-based alloy catalysts is demonstrated through the formation of NiFe from La(Fe, Ni)O₃. The A/B cation ratio plays a significant role in determining the size and composition of NiFe nanoparticles, which directly impacts their catalytic performance. Using in situ X-ray absorption spectroscopy (in situ XAS), the dynamic behavior of exsolved NiFe nanoparticles can be observed in different reaction environments (oxidation, reduction, and dry reforming of methane) by tracking the oxidation state and local environment of the Ni K-edge and Fe K-edge using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), respectively. Time-resolved experiments with in situ XAS showed that NiFe nanoparticle growth starts at ∼280 °C and transforms from predominantly Ni to NiFe at higher reduction times and temperatures.The challenges of exsolution of higher-order Ni-based alloys, such as 3(NiFeCo), 4(NiCoCuPd), and 5(NiFeCoCuPd) element nanoparticles, to improve the catalyst properties are discussed. The size, concentration, and reducibility of the dopant cation can alter the exsolution kinetics, alloy nanoparticle growth dynamics, and catalyst performance. The size and composition of exsolved Ni-based alloys affect the effectiveness of catalysts in the dry reforming of methane. Large NiFeCo nanoparticles separated from Pd and Cu can lead to catalyst deactivation, but using a complex alloy with smaller NiFeCoPdCu nanoparticles results in a stable performance. The use of in situ XANES reveals how the dry reforming of methane reaction conditions can induce changes in the NiFe with the rapid redissolution of Fe back into the lattice.The dynamicity of the exsolved Ni-based alloy nanoparticles and implications for their regeneration after aging or exposure to waste gas contaminants are discussed. Finally, we summarize the Account and provide promising future directions.