Amorphous copper(II)-cyanoimidazole frameworks as peroxidase mimics for hydrogen sulfide assay.

Metal-organic frameworks with hierarchical porosities and exposed active sites are promising for ideal enzyme mimics. In this work, we developed a simple and feasible air oxidation strategy to prepare amorphous Cu(II)-cyanoimidazole frameworks (aCu(II)-CIFs) using CuI as the metal source in dimethylsulfoxide. Benefiting from coordination unsaturation and hierarchical porosities, aCu(II)-CIFs exhibit inherent peroxidase-mimic activity for rapid colorimetric reaction of 3,3',5,5'-tetramethylbenzidine (TMB). aCu(II)-CIFs were utilized to develop a colorimetric platform for specific H2S assay in the range of 0.6-30 µM, achieving a limit of detection (LOD) of 0.071 µM. Structural collapse of aCu(II)-CIFs and subsequent generation of stable CuS particles, along with reducibility of H2S, are likely responsible for suppressing TMBox conversion. The proposed method successfully detected H2S in real water samples, with a relative standard deviation (RSD) lower than 8.4%. This contribution is expected to offer unique insights into the amorphization mechanisms of MOFs and their potential applications.

Self-Powered Infrared Photodetectors with Ultra-High Speed and Detectivity Based on Amorphous Cu-Based MOF Films.

Amorphous metal-organic frameworks (aMOFs) start to challenge their crystalline equivalents due to their unique advantages, like lack of grain boundaries, isotropy, flexibility, numerous defects-induced active sites, etc. However, aMOFs are typically synthesized under rigorous conditions, and their properties and applications need to be further explored. In this work, highly transparent p-type amorphous Cu-HHTP films consisting of Cu2+ and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) were synthesized using a simple electrostatic spinning method and identified as p-a-Cu-HHTP. Besides, a p-a-Cu-HHTP/n-Si infrared photodetector (PD) operating on a self-powered basis with ultra-high speed (response time of 40 µs) and detectivity (1.2 × 1012 Jones) has been developed, with a response time and detectivity that are record values for a MOF-based photodetector. In particular, the p-a-Cu-HHTP/n-Si PD can withstand high temperatures up to 180 °C without property change. Moreover, a flexible metal-semiconductor-metal photodetector based on p-a-Cu-HHTP is constructed, which shows excellent mechanical stability and photoresponse that remain unchanged after bending 120 times, implying its suitability for wearable optoelectronics. The new method to fabricate aMOFs, the unique p-a-Cu-HHTP, and its PDs initiated in this work opens up a new avenue in organic-inorganic hybrid optoelectronics.

Amorphizing of Cu Nanoparticles toward Highly Efficient and Robust Electrocatalyst for CO2 Reduction to Liquid Fuels with High Faradaic Efficiencies.

Conversion of carbon dioxide (CO2 ) into valuable chemicals, especially liquid fuels, through electrochemical reduction driven by sustainable energy sources, is a promising way to get rid of dependence on fossil fuels, wherein developing of highly efficient catalyst is still of paramount importance. In this study, as a proof-of-concept experiment, first a facile while very effective protocol is proposed to synthesize amorphous Cu NPs. Unexpectedly, superior electrochemical performances, including high catalytic activity and selectivity of CO2 reduction to liquid fuels are achieved, that is, a total Faradaic efficiency of liquid fuels can sum up to the maximum value of 59% at -1.4 V, with formic acid (HCOOH) and ethanol (C2 H6 O) account for 37% and 22%, respectively, as well as a desirable long-term stability even up to 12 h. More importantly, this work opens a new avenue for improved electroreduction of CO2 based on amorphous metal catalysts.