Methanol synthesis from greenhouse gas CO₂ and green H₂ is envisioned to be a promising approach for achieving carbon neutrality and sustainability. Although this process is traditionally carried out by thermal heterogeneous catalysis, the methanol production rate and selectivity, however, are limited by thermodynamic constraints. To circumvent this challenge, we discovered that photons could break the limitations of traditional methanol synthesis by shifting the thermodynamic equilibrium to a photo-thermodynamic state. Under light irradiation, about 80% of the photogenerated charge carriers were found to be directed to the methanol synthesis pathway, leading to a 17.5-fold increase in the methanol production rate to 1,757.1 μmol g⁻¹ h⁻¹ and a concomitant boost in selectivity. Overall, this advance emphasizes the advantages provided by light in the synthesis of green methanol and provides new insights into reaction pathway regulation through light intensity and wavelength, know-how which can be expanded to other solar-powered heterogeneous catalytic processes.

从温室气体 CO ₂和绿色 H _{2合成甲醇}被认为是实现碳中和和可持续性的有前途的方法。尽管这一过程传统上是通过热多相催化进行的，但是甲醇的生产率和选择性受到热力学约束的限制。为了规避这一挑战，我们发现光子可以通过将热力学平衡转变为光热力学状态来打破传统甲醇合成的局限性。在光照射下，发现大约 80% 的光生载流子被定向到甲醇合成途径，导致甲醇生产率增加 17.5 倍，达到 1,757.1 μmol g ^-1 h^-1和伴随的选择性提升。总的来说，这一进展强调了光在绿色甲醇合成中的优势，并通过光强度和波长提供了对反应途径调节的新见解，这些知识可以扩展到其他太阳能多相催化过程。