Abstract

We report a Ni-MOF (nickel metal-organic framework), Ni-SIP-BPY, synthesized by using two linkers 5-sulfoisophthalic acid (SIP) and 4,4'-bipyridine (BPY) simultaneously. It displays an orthorhombic crystal system with the Ama2 space group: a = 31.425 Å, b = 19.524 Å, c = 11.2074 Å, α = 90°, β = 90°, γ = 90°, and two different types of nickel(II) centers. Interestingly, Ni-SIP-BPY exhibits excellent sensitivity (limit of detection, 87 ppb) and selectivity toward the 2,4,6-trinitrophenol (TNP)-like mutagenic environmental toxin in the pool of its other congeners via "turn-off" fluorescence response by the synergism of resonance energy transfer, photoinduced electron transfer, intermolecular charge transfer, π-π interactions, and competitive absorption processes. Experimental studies along with corroborated theoretical experimentation, vide density functional theory studies, shed light on determining the plausible mechanistic pathway in selective TNP detection, which is highly beneficial in the context of homeland security perspective. Along with the sensing of nitroaromatic explosives, the moderately low band gap and the p-type semiconducting behavior of Ni-SIP-BPY make it suitable as a photoanode material for visible-light-driven water splitting. Highly active surface functionalities and sufficient conduction band minima effectively reduce the water and result in a seven times higher photocurrent density under visible-light illumination.

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