Highly porous holey inorganic nanosheets have received growing attention as emerging 2D nanostructures because of their excellent functionalities as active materials and hybridization matrices. Here we report the composition-controlled synthesis of ultrathin holey metal oxynitride nanosheets with subnanometer-level thickness of ∼0.8 nm and tunable defect/surface structures. The application of the obtained holey TiO1−xNx nanosheets as immobilization substrates allowed to maximize mass electrocatalytic activity of hybridized Pt nanoclusters via enhanced interfacial interaction at defective sites. The strong electronic coupling between positively-charged Pt nanoclusters and holey TiO1−xNx nanosheets with interfacial oxygen linkers enabled to achieve a superior electrocatalytic performance for hydrogen evolution reaction with an unusually high gravimetric efficiency (20.8 AmgPt−1), i.e., one of the most efficient values for Pt nanostructures. Density functional theory calculations and in-situ Raman analysis emphasize the significant contributions of interfacial oxygen linker in holey TiO1−xNx substrates and positive charge of Pt nanocluster to optimizing the electrocatalytic activity. The present study underscores that employing composition-controlled holey TiO1−xNx nanosheets as immobilization substrates provides a novel efficient methodology to explore high-performance electrocatalysts via the improvement of charge/mass transport and electrocatalytic kinetics, and the optimization of d-band center upon hybridization.
Bibliographical noteFunding Information:
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. NRF‐2020R1A2C3008671, No. NRF‐2017R1A5A1015365). This work was also supported by National R&D Program through the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT (No. 2021M3H4A1A03049662). T. Lee and A. Soon gratefully acknowledge support from the Basic Science Research Program (2020R1F1A1063070) through the NRF. Computational resources are provided by the Korean Institute of Science and Technology Information (KISTI) supercomputing center through the strategic support program for supercomputing application research (KSC-2020-CRE-0130) and the Australian National Computational Infrastructure (NCI). The experiments at PAL were supported in part by MOST and POSTECH.
© 2022 Elsevier B.V.
All Science Journal Classification (ASJC) codes
- Environmental Chemistry
- Chemical Engineering(all)
- Industrial and Manufacturing Engineering