Abstract
ABSTRACT Photocatalytic conversion of CO2 into valuable hydrocarbon products offers a potential pathway to mitigate excessive CO2 emissions and support carbon neutrality goals. Carbon nanofibers (CNFs)‐based composites have emerged as promising platforms owing to their interconnected network, high specific surface area, electronic conductivity, and photothermal properties. This review focuses on controllable preparation strategies, including sol‑gel, chemical vapor deposition, vapor‐phase flow catalysis, and electrospinning, and discusses how different synthesis processes and precursor choices influence the pore structure, graphitization degree, defects, and surface functional groups of CNFs. From kinetic and thermodynamic perspectives, rational design strategies such as heteroatom doping, heterostructure construction, single‑atom loading, and interface engineering are explored to optimize band structures and lower activation barriers. Recent breakthroughs in solar‑driven hydrogen production, CO2 reduction, nitrogen fixation, organic pollutant degradation, heavy metal removal, antibacterial, and photothermal treatment are highlighted. Photo‐generated charge separation pathways and surface reaction enhancement mechanisms under light‐thermal‐electric multifield synergy are systematically analyzed. Finally, the main challenges are summarized, including the need for in‑depth structure‐activity relationship analysis and scalable preparation. Promising future directions involving machine learning‑assisted screening, multi‑scale structural design, and in‑situ characterization may contribute to advancing CNFs‐based photocatalysts toward efficient, stable, and scalable solar conversion systems.