Nickel Metal–Organic Framework Monolayers for Photoreduction of Diluted CO2: Metal‐Node‐Dependent Activity and Selectivity

• Published in: Angewandte Chemie Vol. 130; no. 51; pp. 17053 - 17057
• Main Authors: Han, Bin, Ou, Xinwen, Deng, Ziqi, Song, Yao, Tian, Chen, Deng, Hong, Xu, Yi‐Jun, Lin, Zhang
• Format: Journal Article
• Language: English; Japanese
• Published: Weinheim Wiley Subscription Services, Inc 17-12-2018
• Subjects: Adducts; Carbon dioxide; Carbon monoxide; Catalysts; Chemistry; Conversion; Dilution; Metal-organic frameworks; Metall-organische Gerüststrukturen; Metals; Monolayers; Monoschichten; Nickel; Photochemische CO2-Reduktion; Photochemistry; Photoreduction; Selectivity; Selektivität
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201811545

Photocatalytic conversion of diluted CO2 into solar fuel is highly appealing yet still in its infancy. Herein, we demonstrate the metal‐node‐dependent performance for photoreduction of diluted CO2 by constructing Ni metal–organic framework (MOF) monolayers (Ni MOLs). In diluted CO2 (10 %), Ni MOLs exhibit a highest apparent quantum yield of 1.96 % with a CO selectivity of 96.8 %, which not only exceeds reported systems in diluted CO2 but also is superior to most catalysts in pure CO2. Whereas isostructural Co MOLs is almost inactive in diluted CO2, indicating the performance is dependent on the metal nodes. Experimental and theoretical investigations show that strong CO2 binding affinity of Ni MOLs is the crucial factor, which stabilizes the Ni‐CO2 adducts and facilitates CO2‐to‐CO conversion.
Die photokatalytische Umwandlung von verdünntem CO2 gelingt hoch effizient und selektiv an Monoschichten einer Nickel‐organischen Gerüstverbindung. Die anfängliche CO2‐Adsorption ist der entscheidende Schritt; sie hängt von der Natur der Metall‐Baugruppe ab.