The successful application of electrochemiluminescence (ECL) in various fields required continuous exploration of novel ECL signal emitters. In this work, we have proposed a pristine ECL luminophor named NiRu MOFs, which owned extremely high and stable ECL transmission efficiency and was synthesized via a straightforward two-step hydrothermal pathway. The foundation framework of pure Ni-MOFs with the initial structure was layered-pillared constructed by the coordinated octahedrally divalent between nickel and terephthalic acid (BDC). The terephthalates were coordinated and pillared directly to the nickel hydroxide layers and the three-dimensional framework was formed, which had a weak ECL response strength. Then, the ruthenium pyridine complex was recombined with pure Ni-MOFs to produce NiRu MOFs and part of the introduced ruthenium was atomically dispersed in the layered-pillared structure through an ion-exchange method, which led to the ECL luminous efficiency being significantly boosted more than pure Ni-MOFs. In order to verify the superiority of this newly synthesized illuminant, an ECL immunoassay model has been designed, and the results demonstrated that it had extremely strong and steady signal output in practical application. This study realized an efficient platform in ECL immunoassay application with the limit of detection of 0.32 pg mL–1 for neuron-specific enolase (NSE). Therefore, the approach which combined the pristine pure Ni-MOFs and the star-illuminant ruthenium pyridine complex would provide a convenient and meaningful solution for exploring the next-generation ECL emitters.
Although Metal-organic frameworks (MOFs) have attracted extensive attention in energy-related fields, the direct application of MOF as bifunctional electrocatalysts for overall water electrolysis still remains a challenging topic. Herein, nickel foam (NF) self-supported hydrangea shaped NiRu bimetallic MOFs (NiRu-PTA/NF) prepared by a simple one-step hydrothermal method was directly used as bifunctional electrocatalyst, and exhibited highly-efficient hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic performances for alkaline freshwater/seawater overall splitting owing to the large active surface area, abundant active sites and high intrinsic activity attributed to the unique morphology, enriched oxygen vacancies and modulated electronic structure of the catalyst. Specifically, NiRu-PTA/NF needed only 16 mV overpotential to drive a HER current density of 10 mA cm −2 and 298 mV overpotential to drive a OER current density of 20 mA cm −2 in alkaline freshwater, much lower than those of Ni-PTA/NF ( η 10,HER = 162 mV, η 20,OER = 372 mV) and Ru-PTA/NF ( η 10,HER = 36 mV, η 20,OER = 335 mV). Furthermore, a two-electrode configured water electrolysis cell assembled with NiRu-PTA/NF as both cathode and anode required a very low cell voltage of 1.54 V to achieve an electrolytic current density of 10 mA cm −2 and were operated continuously for 200 h at various current densities including 10, 100 and 200 mA cm −2 . Additionally, the NiRu-PTA/NF-assembled electrolysis cell also displayed excellent seawater electrolysis performance. This study proposes an available strategy to design highly-efficient bifunctional catalysts for overall freshwater/seawater electrolysis based on electronic structure and oxygen vacancy modulation between bimetallic centers of MOFs, and extends their promising application prospects for industrially clean hydrogen production.
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