RESUMEN
Development of nonprecious metal-based single-atom catalysts (SACs) has provided opportunities to substitute Pt group metals and offer maximum atom utilization and unique coordination environments. Among these catalysts, Fe-N-C catalysts with atomically dispersed Fe-N4 active sites have emerged as some of the most promising oxygen reduction reaction (ORR) catalysts. However, furnace synthesis of Fe-N-C catalysts with carbon substrate derived from metal-organic framework (MOF) involves a high-temperature procedure, in which nitrogen from the carbonized MOF tends to be removed, subsequently leading to a low density of active sites. In this work, we developed a rapid and simple solid-state route to fabricate SACs through laser-induced thermal activation (LITA) of carbonized zeolitic imidazolate framework-8 (ZIF-8) adsorbed with Fe precursors. The results demonstrate that the laser process effectively avoids the loss of nitrogen in the nitrogen-doped carbon substrate and achieves a loading of Fe single atoms of 2.3 wt %, in comparison with that of 1.2 wt % from the conventional furnace treatment. The Fe-N-C catalyst synthesized in the study presents a half-wave potential of 0.91 V for ORR in alkaline media, which is higher than that of commercial Pt/C (0.87 V). When used as a cathode catalyst in zinc-air batteries (ZABs), the battery exhibits excellent electrochemical performance. This work also demonstrates the versatility of the technique through the successful synthesis of Co-N-C and Ni-N-C single atoms on nitrogen-doped carbon substrates.
RESUMEN
Rapid, simple, accurate and highly sensitive detection of enzymes is essential for early screening and clinical diagnosis of many diseases. In this study, we report the fabrication of a turn-on ratiometric electrochemical sensor for the in situ determination of ß-Galactosidase (ß-Gal) based on surface engineering and the design of a molecular probe (Pygal) specific for ß-Gal recognition. First, Pygal probe was synthesized and characterized, and then co-assembled with the methylene blue (MB) internal reference probe on the surface of single-wall carbon nanotubes (SWCNT)-modified carbon fiber microelectrode (CFME). The resulting CFME/SWCNT/MB + Pygal sensor is activated in the presence of ß-Gal giving one peak at 0.33 V originating from the oxidation of the product of Pygal enzymatic hydrolysis (PyOH). Another oxidation peak attributed to MB appears simultaneously at -0.28 V allowing the construction of a ratiometric electrochemical sensor for ß-Gal detection with improved sensitivity and accuracy. The sensor showed a linear response to ß-Gal in a wide concentration range from 1.5 to 30 U L-1 and a low detection limit of 0.1 U L-1. Moreover, the sensor demonstrated excellent selectivity against several biologically relevant hydrolases and redox-active molecules. Finally, the combination of excellent electrochemical performance and favorable physicochemical properties of CFME allowed the determination of ß-Gal in the whole blood of Parkinson's Disease (PD) model mice. The workflow reported in this study provides a strategy for the design and development of sensors for the in vivo monitoring of other enzymes important for the early diagnosis of different health issues.