Selective photocatalytic CO2 reduction in aerobic environment by microporous Pd-porphyrin-based polymers coated hollow TiO2

• Published in: Nature communications Vol. 13; no. 1; pp. 1400 - 10
• Main Authors: Ma, Yajuan, Yi, Xiaoxuan, Wang, Shaolei, Li, Tao, Tan, Bien, Chen, Chuncheng, Majima, Tetsuro, Waclawik, Eric R., Zhu, Huaiyong, Wang, Jingyu
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 17.03.2022; Nature Publishing Group; Nature Portfolio
• Subjects: 147/143; 639/301/299/890; 639/638/675; 639/925/357; Adsorptivity; Carbon dioxide; Coordination polymers; Crosslinking; Flue gas; High resistance; Humanities and Social Sciences; Irradiation; Light irradiation; multidisciplinary; Oxidation; Photocatalysis; Photoreduction; Polymers; Porphyrins; Reduction; Science; Science (multidisciplinary); Selectivity; Surface chemistry; Titanium dioxide
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-29102-0

Direct photocatalytic CO 2 reduction from primary sources, such as flue gas and air, into fuels, is highly desired, but the thermodynamically favored O 2 reduction almost completely impedes this process. Herein, we report on the efficacy of a composite photocatalyst prepared by hyper-crosslinking porphyrin-based polymers on hollow TiO 2 surface and subsequent coordinating with Pd(II). Such composite exhibits high resistance against O 2 inhibition, leading to 12% conversion yield of CO 2 from air after 2-h UV-visible light irradiation. In contrast, the CO 2 reduction over Pd/TiO 2 without the polymer is severely inhibited by the presence of O 2 ( ≥ 0.2 %). This study presents a feasible strategy, building Pd(II) sites into CO 2 -adsorptive polymers on hollow TiO 2 surface, for realizing CO 2 reduction with H 2 O in an aerobic environment by the high CO 2 /O 2 adsorption selectivity of polymers and efficient charge separation for CO 2 reduction and H 2 O oxidation on Pd(II) sites and hollow TiO 2 , respectively. While selective CO 2 reduction is crucial for its removal from the environment, the presence of O 2 hinders this process. Here authors show CO 2 photoreduction in the presence of O 2 by incorporating Pd(II) sites into a coordination polymer on TiO 2 to selectively adsorb CO 2 .