Electrocatalysts for oxygen-reduction and oxygen-evolution reactions (ORR and OER) are crucial for metal-air batteries, where more costly Pt- and Ir/Ru-based materials are the benchmark catalysts for ORR and OER, respectively. Herein, for the first time Ni is combined with MnO species, and a 3D porous graphene aerogel-supported Ni/MnO (Ni-MnO/rGO aerogel) bifunctional catalyst is prepared via a facile and scalable hydrogel route. The synthetic strategy depends on the formation of a graphene oxide (GO) crosslinked poly(vinyl alcohol) hydrogel that allows for the efficient capture of highly active Ni/MnO particles after pyrolysis. Remarkably, the resulting Ni-MnO/rGO aerogels exhibit superior bifunctional catalytic performance for both ORR and OER in an alkaline electrolyte, which can compete with the previously reported bifunctional electrocatalysts. The MnO mainly contributes to the high activity for the ORR, while metallic Ni is responsible for the excellent OER activity. Moreover, such bifunctional catalyst can endow the homemade Zn-air battery with better power density, specific capacity, and cycling stability than mixed Pt/C + RuO catalysts, demonstrating its potential feasibility in practical application of rechargeable metal-air batteries.
Exploration of high‐efficiency, economical, and ultrastable electrocatalysts for the oxygen reduction reaction (ORR) to substitute precious Pt is of great significance in electrochemical energy conversion devices. Single‐atom catalysts (SACs) have sparked tremendous interest for their maximum atom‐utilization efficiency and fascinating properties. Therefore, the development of effective synthetic methodology toward SACs becomes highly imperative yet still remains greatly challenging. Herein, a reliable SiO2‐templated strategy is elaborately designed to synthesize atomically dispersed Fe atoms anchored on N‐doped carbon nanospheres (denoted as Fe–N–C HNSs) using the cheap and sustainable biomaterial of histidine (His) as the N and C precursor. By virtue of the numerous atomically dispersed Fe–N4 moieties and unique spherical hollow architecture, the as‐fabricated Fe–N–C HNSs exhibit excellent ORR performance in alkaline medium with outstanding activity, high long‐term stability, and superior tolerance to methanol crossover, exceeding the commercial Pt/C catalyst and most previously reported non‐precious‐metal catalysts. This present synthetic strategy will provide new inspiration to the fabrication of various high‐efficiency single‐atom catalysts for diverse applications.
The development of functional copper nanoclusters (Cu NCs) is becoming increasingly widespread in consumer technologies due to their applications in cellular imaging and catalysis. Herein, we report a simple protein-directed synthesis of stable, water-soluble and fluorescent Cu NCs, using BSA as the stabilising agent. Meanwhile, in this study, hydrazine hydrate (N₂H₄·2H₂O) was used as the reducing agent. N₂H₄·2H₂O was a mild reducing agent suggesting that all processes could be operated at room temperature. The as-prepared Cu NCs showed red fluorescence with a peaking center at 620 nm (quantum yield 4.1%). The fluorescence of the as-prepared BSA-Cu NCs was responsive to pH in that the intensity of fluorescence increased rapidly by decreasing the pH from 12 to 6. Besides, with an arresting set of features including water-dispersibility, red fluorescence, good biocompatibility, surface-bioactivity and small size, the resultant BSA-Cu NCs could be used as probes for cellular imaging and catalysis. In this study, CAL-27 cells and the reaction of oxidation of styrene are used as models to achieve fluorescence imaging and elucidate the catalytic activity of the as-prepared BSA-Cu NCs.
Low toxicity and fluorescent nanomaterials have many advantages in biological imaging. Herein, a novel and facile aqueous-phase approach to prepare biocompatible and fluorescent Ag(2)S nanoclusters (NCs) is designed and investigated. The resultant Ag(2)S NCs show tunable luminescence from the visible red (624 nm) to the near infrared (NIR; 724 nm) corresponding to the increasing size of the NCs. The key for preparing tunable fluorescent Ag(2)S NCs is the proper choice of capping reagent, glutathione (GSH), and the novel sulfur-hydrazine hydrate complex as the S(2-) source. As a naturally occurring and readily available tripeptide, GSH functions as an important scaffold to prevent NCs from growing large nanoparticles. Additionally, GSH is a small biomolecule with several functional groups, including carboxyl and amino groups, which suggests the resultant Ag(2)S NCs are well-dispersed in aqueous solution. These advantages make the as-prepared Ag(2)S NCs potentially applicable to biological labeling as well. For example, the resultant Ag(2)S NCs are used as a probe for MC3T3-EI cellular imaging.
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