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Furthermore, density functional theory and experimental evidence are also provided for the hierarchical structure of HHS and PNIPA coating associated with substrates to demonstrate how a substrate could have access or be blocked into the confined active centers (MNPs). Therefore, this work would open a new window to design efficient catalysts for a wide variety of substrate-selective catalyses.The interface of transition-metal dichalcogenides (TMDCs) and high-k dielectric transition-metal oxides (TMOs) had triggered umpteen discourses