Toward Optimal Photocatalytic Hydrogen Generation from Water Using Pyrene-Based Metal–Organic Frameworks

• Published in: ACS applied materials & interfaces Vol. 13; no. 48; pp. 57118 - 57131
• Main Authors: Kinik, F. Pelin, Ortega-Guerrero, Andres, Ebrahim, Fatmah Mish, Ireland, Christopher P, Kadioglu, Ozge, Mace, Amber, Asgari, Mehrdad, Smit, Berend
• Format: Journal Article
• Language: English
• Published: American Chemical Society 08.12.2021
• Subjects: density functional theory; Energy, Environmental, and Catalysis Applications; hydrogen evolution; metal-organic frameworks; photocatalysis; pyrene; hydrogen evolution; photocatalysis; metal−organic frameworks; pyrene; density functional theory
• ISSN: 1944-8244; 1944-8252; 1944-8252
• DOI: 10.1021/acsami.1c16464

Metal–organic frameworks (MOFs) are promising materials for the photocatalytic H2 evolution reaction (HER) from water. To find the optimal MOF for a photocatalytic HER, one has to consider many different factors. For example, studies have emphasized the importance of light absorption capability, optical band gap, and band alignment. However, most of these studies have been carried out on very different materials. In this work, we present a combined experimental and computation study of the photocatalytic HER performance of a set of isostructural pyrene-based MOFs (M-TBAPy, where M = Sc, Al, Ti, and In). We systematically studied the effects of changing the metal in the node on the different factors that contribute to the HER rate (e.g., optical properties, the band structure, and water adsorption). In addition, for Sc-TBAPy, we also studied the effect of changes in the crystal morphology on the photocatalytic HER rate. We used this understanding to improve the photocatalytic HER efficiency of Sc-TBAPy, to exceed the one reported for Ti-TBAPy, in the presence of a co-catalyst.