“…The presence of absorption peaks of monodentate carbonate (m-CO 3 2– , 1507, 1484, and 1310 cm –1 ), bidentate carbonate (b-CO 3 2– , 1587 cm –1 ), bicarbonate (HCO 3 – , 1422 and 1354 cm –1 ), and CO 2 – (1612 and 1244 cm –1 ) suggests the chemisorption of CO 2 on the COF/QDs heterojunction (Figure S20). − Under light irradiation, new adsorption signals corresponding to *COOH (1705 cm –1 ), *CO (2078 cm –1 ), *CHO (1008 cm –1 ), *CH 2 O (967 cm –1 ), and *CH 3 O (1103 and 1187 cm –1 ) are observed, which are critical intermediates in the formation of CO and CH 4 . − During CO 2 photoreduction, the *CO*H intermediate on the catalyst can undergo three processes: the desorption of CO (Pathway I), the release of H from the interface (Pathway II), and continuous protonation to form the *CHO species and generate CH 4 (Pathway III). DFT calculations reveal that the Δ G values for the three pathways are −0.21, – 0.22, and −0.91 eV, respectively (Figure d), providing a reasonable explanation for the production of CO and CH 4 over the COF/QDs heterojunctions.…”