Cooperative Brønsted Acid-Single Atom Photocatalysis in Metal–Organic Framework
Yoon Jung, Chan Woo Lee, Byoung‐Hoon Lee, Yunjae Yu, Jaeho Moon, Hyeon Seok Lee, Wonjae Ko, Jinsol Bok, Kangjae Lee, Jae Wook Lee, Megalamane S. Bootharaju, Jaeyune Ryu, Minho Kim, Taeghwan Hyeon
Abstract
Enzymes, composed of earth-abundant elements, outperform conventional heterogeneous photocatalysts in hydrogen production due to the dual-site cooperation between adjacent active metal sites and proton-transferring ligands. However, the realization of such dual-site cooperation in heterogeneous catalytic systems is hindered by the challenges in the precise construction of cooperative active sites. In this study, we present the design of a structurally tuned metal–organic framework (MOF) photocatalyst that incorporates cooperative Brønsted acid-single atom catalytic sites. By grafting Co single-atom sites onto the Ti-oxo clusters and introducing Brønsted acidic P–OH moieties in tandem within the MOF-based catalyst structure, we achieved a visible-light-activated photocatalytic H 2 production rate of 6.6 mmol g –1 h –1, which is 6.6 times higher than that of a Pt nanoparticle-based cocatalyst, emphasizing the significance of incorporating cooperative Brønsted acid-single atom catalytic sites.