RESUMEN

Here, we report the fabrication of the unique intertwined Ni9 S8 /Ag2 S composite structure with hexagonal shape from their molecular precursors by one-pot thermal decomposition. Various spectroscopic and microscopic techniques were utilized to confirm the Ni9 S8 /Ag2 S intertwined structure. Powder X-ray Powder Diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis suggest that there is an enrichment of Ni9 S8 phase in Ni9 S8 /Ag2 S. The presence of Ag2 S in Ni9 S8 /Ag2 S improves the conductivity by reducing the interfacial energy and charge transfer resistance. When Ni9 S8 /Ag2 S is employed as an electrocatalyst for electrochemical oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) activity, it requires a low overpotential of 152 mV for HER and 277 mV for OER to obtain the geometrical current density of 10 mA cm-2 , which is definitely superior to that of its components Ni9 S8 and Ag2 S. This work provides a simple design route to develop an efficient and durable electrocatalyst with outstanding OER and HER performance and the present catalyst (Ni9 S8 /Ag2 S) deserves as a potential candidate in the field of energy conversion systems.

Asunto(s)

RESUMEN

A new zinc-based two-dimensional coordination polymer, [Zn(5-AIP)(Ald-4)]·H2O (5-AIP = 5-amino isophthalate, Ald-4 = aldrithiol-4), 1, has been synthesized at room temperature by the layer diffusion technique. Single-crystal X-ray diffraction analysis of 1 showed a two-dimensional bilayer structure. An aqueous suspension of 1 upon excitation at 300 nm displayed an intense blue emission at 403 nm. The luminescence spectra were interestingly responsive and selective to Al3+, Cr3+ and Fe3+ ions even in the presence of other interfering ions. The calculated detection limits for Al3+, Cr3+ and Fe3+ were 0.35 µM ([triple bond, length as m-dash]8.43 ppb), 0.46 µM ([triple bond, length as m-dash]22.6 ppb) and 0.30 µM ([triple bond, length as m-dash]15.85 ppb), respectively. Notably, with the cumulative addition of Al3+ ions, the luminescence intensity at 403 nm decreased steadily with a gradual red shift up to 427 nm. Afterward, this red shifted peak showed a turn-on effect upon further addition of Al3+ ions. On the other hand, for Cr3+ and Fe3+ ions, there was only drastic luminescence quenching and a large red shift up to 434 nm. This indicated the formation of a complex between 1 and these metal ions, which was also supported by the UV-Visible absorption spectra of 1 that showed the appearance of a new band at 280 nm in the presence of these three metal ions. The FTIR spectra revealed that these ions interacted with the carboxylate oxygen atom of 5-AIP and the nitrogen atom of the Ald-4 ligand in the structure. The luminescence lifetime decay analysis manifested that a charge-transfer type complex was formed between 1 and Cr3+ and Fe3+ ions that resulted in huge luminescence quenching due to the efficient charge transfer involving the vacant d-orbitals, whereas for Al3+ ions having no vacant d-orbital, turn-on of luminescence occurred because of the increased rigidity of 1 upon complexation.