Dual-Atom-Site Sn-Cu/C3N4 Photocatalyst Selectively Produces Formaldehyde from CO2 Reduction

The solar-driven catalytic reduction of CO2 to value-added chemicals is under intensive investigation. The reaction pathway via *OCHO intermediate (involving CO2 adsorbed through O-binding) usually leads to the two-electron transfer product of HCOOH. Herein, a single-atom catalyst with dual-atom-sites featuring neighboring Sn(II) and Cu(I) centers embedded in C3N4 framework is developed and characterized, which markedly promotes the production of HCHO via four-electron transfer through the *OCHO pathway. The optimized catalyst achieves a high HCHO productivity of 259.1 mu mol g(-1) and a selectivity of 61% after 24 h irradiation, which is ascribed to the synergic role of the neighboring Sn(II)-Cu(I) dual-atom sites that stabilize the target intermediates for HCHO production. Moreover, adsorbed *HCHO intermediate is detected by in situ Fourier transform infrared spectroscopy (C(sic)O stretches at 1637 cm(-1)). This study provides a unique example that controls the selectivity of the multi-electron transfer mechanisms of CO2 photoconversion using heteronuclear dual-atom-site catalyst to generate an uncommon product (HCHO) of CO2 reduction.

Automated summary

A new single-atom dual-atom-site catalyst has been developed to significantly promote the production of formaldehyde through the four-electron transfer pathway of *OCHO. The neighboring Sn(II)-Cu(I) dual-atom sites stabilize the intermediates for formaldehyde production, and the adsorbed *HCHO intermediate is detected by in situ Fourier transform infrared spectroscopy. This study provides a unique example of controlling the selectivity of multi-electron transfer mechanisms for CO2 photoconversion using a heteronuclear dual-atom-site catalyst to generate an uncommon product (formaldehyde) from CO2 reduction.