MOF- and COF-Based Nanocatalysts for Selective CO₂ Hydrogenation to Methanol under Mild Conditions: Recent Advances (2023–2025) and Industrial Prospects in Iran

Abstract

Carbon dioxide hydrogenation to methanol using green hydrogen is a promising carbon capture and utilization (CCU) route for achieving carbon neutrality. This review focuses on the latest advances (2023–2025) in metal-organic framework (MOF) and covalent organic framework (COF)-based nanocatalysts for selective CO₂-to-methanol conversion under mild conditions (T < 150 °C, P < 20 bar). Single-atom Cu anchored on amino-functionalized UiO-66, defect-engineered TpPa-1 COFs with Cu-N₄ sites, and hierarchical MOF–COF hybrids have achieved methanol yields exceeding 85% and space-time yields up to 2.8 g g_cat⁻¹ h⁻¹ by enhancing CO₂ adsorption, H₂ activation, and water tolerance. Key challenges such as hydrothermal instability and water poisoning are addressed through defect engineering, hydrophobic functionalization, and sorption-enhanced reactors. Iran, with over 12 Mt yr⁻¹ methanol capacity and abundant CO₂ emissions from Assaluyeh and Mahshahr complexes, is uniquely positioned to lead green methanol production. Integration of solar-driven hydrogen (LCOH ≈ $1.5–2 kg⁻¹ in southern Iran) with existing methanol plants could yield 2–5 Mt yr⁻¹ green methanol by 2030 at a levelized cost of $300–450 t⁻¹. Pilot-scale implementation of UiO-66–TpPa-1 catalysts and policy incentives for 20% CCU blending are recommended to accelerate commercialization. These breakthroughs, combined with Iran’s abundant CO₂ point sources and solar potential, pave the way for cost-competitive green methanol production and significant decarbonization of the petrochemical sector by 2030.