Perovskite-Type LaCoO3-Based Catalysts for Higher Alcohol Synthesis from Syngas: Advances in Synthesis, Characterization, and Mechanism over the Past Decade

The selective conversion of syngas (CO + H₂) to higher alcohols (C₂₊OH) via Fischer–Tropsch synthesis (FTS) is a strategically important but challenging process, requiring catalysts that can simultaneously sustain C–C chain growth and preserve C–O bonds in reactive intermediates. Over the past decade (2015–2025), perovskite-type complex oxides with the formula ABO₃ have emerged as powerful precatalysts for this application, with LaCoO₃ attracting particular attention due to its structural flexibility, controllable reducibility, and the unique catalytic role of the La₂O₃ phase formed upon reduction. This review systematically covers recent advances in synthesis strategies for LaCoO₃ and substituted perovskites, including sol–gel, co-precipitation, mechanochemical, and template-assisted (KIT-6, SBA-15) methods; effects of A-site (Sr) and B-site (Cu, Ga, Ni, Mn) substitution on reducibility, active phase dispersion, and product selectivity; alkali promotion and its interaction with the perovskite-derived active phase; mechanistic understanding of the alcohol-forming pathway, including the Co⁰/Co³⁺ bifunctional site concept, CO insertion mechanism, and the role of La₂O₃ in suppressing the Boudouard reaction; and catalyst stability and deactivation pathways under FTS conditions. Original data from LaCoO₃ catalysts prepared by co-precipitation with ethylene glycol (LCO-1: S_KOH = 90%, Y_KOH = 57 mg·g⁻¹·h⁻¹) and via citrate/KIT-6 template synthesis (LCO/KIT-6: Y_KOH = 80 mg·g⁻¹·h⁻¹, S_BET = 220 m²/g) at 240 °C and 2 MPa serve as the primary experimental reference throughout. Key challenges, including the surface area–selectivity trade-off, long-term stability under industrial conditions, and opportunities in CO₂ hydrogenation, are critically discussed.