Selective CO₂-to-Formate Conversion Driven by Visible Light over a Precious-Metal-Free Nonporous Coordination Polymer

Yoshinobu Kamakura, Shuhei Yasuda, Naoki Hosokawa, Shunta Nishioka, Sawa Hongo, Toshiyuki Yokoi, Daisuke Tanaka*, Kazuhiko Maeda*

Metal–organic frameworks (MOFs) and coordination polymers (CPs) are potential candidates for high-performance photocatalysts because of their high tunability of electronic and structural properties. For example, MOFs and CPs having a high specific surface area (∼1000 m² g^–1) have been applied as visible-light-driven photocatalysts for CO₂ reduction and water splitting. Herein, we show a unique CP possessing a metal–sulfur bond with Pb²⁺, an earth-abundant metal ion. Different from ordinary high-surface-area MOFs and CPs, this CP is nonporous and has just 0.7 m² g^–1 surface area. Nevertheless, owing to its capability of absorbing visible light up to ∼500 nm, it efficiently photocatalyzes CO₂ reduction to formate (HCOO^–) under visible-light irradiation with >99% selectivity and an apparent quantum yield of 2.6% at 400 nm, even without postmodification treatment such as cocatalyst loading. These values are the highest yet reported for a precious-metal-free single-component photocatalyst for the visible-light-driven reduction of CO₂ to HCOO^–. This work may thus shed light on the great potential of nonporous CPs as building units of photocatalytic CO₂ conversion systems.

ACS Catal. 2022,12, 10172-10178.
https://pubs.acs.org/doi/10.1021/acscatal.2c02177