Tweaking Photo CO₂ Reduction by Altering Lewis Acidic Sites in Metalated‐Porous Organic Polymer for Adjustable H₂/CO Ratio in Syngas Production

This is the authors' abstract. We don't add key points for this paper.

Herein, we have specifically designed two metalated porous organic polymers ( Zn‐POP and Co‐POP ) for syngas (CO+H 2 ) production from gaseous CO 2 . The variable H 2 /CO ratio of syngas with the highest efficiency was produced in water medium (without an organic hole scavenger and photosensitizer) by utilizing the basic principle of Lewis acid/base chemistry. Also, we observed the formation of entirely different major products during photocatalytic CO 2 reduction and water splitting with the help of the two catalysts, where CO (145.65 μmol g −1 h −1 ) and H 2 (434.7 μmol g −1 h −1 ) production were preferentially obtained over Co‐POP & Zn‐POP , respectively. The higher electron density/better Lewis basic nature of Co‐POP was investigated further using XPS, XANES, and NH 3 ‐TPD studies, which considerably improve CO 2 activation capacity. Moreover, the structure–activity relationship was confirmed via in situ DRIFTS and DFT studies, which demonstrated the formation of COOH* intermediate along with the thermodynamic feasibility of CO 2 reduction over Co‐POP while water splitting occurred preferentially over Zn‐POP .