RESUMEN
NiFe-based oxides are one of the best-known active oxygen evolution electrocatalysts. Unfortunately, they rapidly lost performance in Fe-purified KOH during the reaction. Herein, tetraphenylporphyrin (TPP) was loaded on a catalyst/electrolyte interface to alleviate the destabilization of NiFe (oxy)hydroxide. We propose that the degradation occurs primarily due to the release of thermodynamically unstable Fe. TPP acts as a protective layer and suppresses the dissolution of hydrated metal at the catalyst/electrolyte interface. In the electric double layer, the nonpolar TPP layer on the NiFe surface also invigorates the redeposition of the active site, Fe, which leads to prolonging the lifetime of NiFe. The TPP-coated NiFe was demonstrated in anion exchange membrane water electrolysis, where hydrogen was generated at a rate of 126â L h-1 for 115â h at a 1.41â mV h-1 degradation rate. Consequently, TPP is a promising protective layer that could stabilize oxygen evolution electrocatalysts.
RESUMEN
The unique optical and photoredox properties of heptazine-based polymeric carbon nitride (PCN) materials make them promising semiconductors for driving various productive photocatalytic conversions. However, their typical absorption onset at ca. 430-450â nm is still far from optimum for efficient sunlight harvesting. Despite many reports of successful attempts to extend the light absorption range of PCNs, the determination of the structural features responsible for the red shift of the light absorption edge beyond 450â nm has often been obstructed by the highly disordered structure of PCNs and/or low content of the moieties responsible for changes in optical and electronic properties. In this work, we implement a high-temperature (900 °C) treatment procedure for turning the conventional melamine-derived yellow PCN into a red carbon nitride. This approach preserves the typical PCN structure but incorporates a new functionality that promotes visible light absorption. A detailed characterization of the prepared material reveals that partial heptazine fragmentation accompanied by de-ammonification leads to the formation of azo-groups in the red PCN, a chromophore moiety whose role in shifting the optical absorption edge of PCNs has been overlooked so far. These azo moieties can be activated under visible-light (470â nm) for H2 evolution even without any additional co-catalyst, but are also responsible for enhanced charge-trapping and radiative recombination, as shown by spectroscopic studies.
RESUMEN
Heptazine-based polymeric carbon nitrides (PCN) are promising photocatalysts for light-driven redox transformations. However, their activity is hampered by low surface area resulting in low concentration of accessible active sites. Herein, we report a bottom-up preparation of PCN nanoparticles with a narrow size distribution (ca. 10±3â nm), which are fully soluble in water showing no gelation or precipitation over several months. They allow photocatalysis to be carried out under quasi-homogeneous conditions. The superior performance of water-soluble PCN, compared to conventional solid PCN, is shown in photocatalytic H2 O2 production via reduction of oxygen accompanied by highly selective photooxidation of 4-methoxybenzyl alcohol and benzyl alcohol or lignocellulose-derived feedstock (ethanol, glycerol, glucose). The dissolved photocatalyst can be easily recovered and re-dissolved by simple modulation of the ionic strength of the medium, without any loss of activity and selectivity.
RESUMEN
Ternary composites of amorphous carbon nanotube/MnO2/graphene oxide (a-CNT/MnO2/GO) were synthesized by a facile direct redox reaction between potassium permanganate and a-CNT, which was prepared by anodic aluminum oxide template method following co-filtration with GO. Needle-like, 100-nm-thick, MnO2 crystals were homogeneously coated on the a-CNT surface, which was then covered with GO. The electrochemical performance of the resulting MnO2-coated a-CNTs exhibited a specific capacitance of 473 F/g at a scan rate of 5 mV/s, and excellent charge/discharge stability after 500 cycles.
RESUMEN
Ultrafine metal nanoparticles (NPs) hold promise for applications in many fields, including catalysis. However, ultrasmall NPs are typically prone to aggregation, which often leads to performance losses, such as severe deactivation in catalysis. Conventional stabilization strategies (e.g., immobilization, embedding, or surface modification by capping agents) are typically only partly effective and often lead to loss of catalytic activity. Herein, a novel type of stabilizers based on water-soluble ionic (K+ and Na+ containing) polymeric carbon nitride (i.e., K,Na-poly(heptazine imide) = K,Na-PHI) is reported that enables effective stabilization of highly catalytically active ultrafine (size of â¼2-3 nm) gold NPs. Experimental and theoretical comparative studies using different structural units of K,Na-PHI (i.e., cyanurate, melonate, cyamelurate) indicate that the presence of functionalized heptazine moieties is crucial for the synthesis and stabilization of small Au NPs. The K,Na-PHI-stabilized Au NPs exhibit remarkable dispersibility and outstanding stability even in solutions of high ionic strength, which is ascribed to more effective charge delocalization in the large heptazine units, resulting in more effective electrostatic stabilization of Au NPs. The outstanding catalytic performance of Au NPs stabilized by K,Na-PHI is demonstrated using the selective reduction of 4-nitrophenol to 4-aminophenol by NaBH4 as a model reaction, in which they outperform even the benchmark "naked" Au NPs electrostatically stabilized by excess NaBH4. This work thus establishes ionic carbon nitrides (PHI) as alternative capping agents enabling effective stabilization without compromising surface catalysis, and opens up a route for further developments in utilizing PHI-based stabilizers for the synthesis of high-performance nanocatalysts.