RESUMO
The low-temperature molecular precursor approach can be beneficial to conventional solid-state methods, which require high temperatures and lead to relatively large crystalline particles. Herein, a novel, single-step, room-temperature preparation of amorphous nickel pnictide (NiE; EP, As) nanomaterials is reported, starting from NaOCE(dioxane)n and NiBr2 (thf)1.5 . During application for the oxygen evolution reaction (OER), the pnictide anions leach, and both materials fully reconstruct into nickel(III/IV) oxide phases (similar to γ-NiOOH) comprising edge-sharing (NiO6 ) layers with intercalated potassium ions and a d-spacing of 7.27 Å. Remarkably, the intercalated γ-NiOOHx phases are nanocrystalline, unlike the amorphous nickel pnictide precatalysts. This unconventional reconstruction is fast and complete, which is ascribed to the amorphous nature of the nanostructured NiE precatalysts. The obtained γ-NiOOHx can effectively catalyse the OER for 100 h at a high current density (400 mA cm-2 ) and achieves outstandingly high current densities (>600 mA cm-2 ) for the selective, value-added oxidation of 5-hydroxymethylfurfural (HMF). The NiP-derived γ-NiOOHx shows a higher activity for both processes due to more available active sites. It is anticipated that the herein developed, effective, room-temperature molecular synthesis of amorphous nickel pnictide nanomaterials can be applied to other functional transition-metal pnictides.
RESUMO
The development of a competent (pre)catalyst for the oxygen evolution reaction (OER) to produce green hydrogen is critical for a carbon-neutral economy. In this aspect, the low-temperature, single-source precursor (SSP) method allows the formation of highly efficient OER electrocatalysts, with better control over their structural and electronic properties. Herein, a transition metal (TM) based chalcogenide material, nickel sulfide (NiS), is prepared from a novel molecular complex [NiII (PyHS)4 ][OTf]2 (1) and utilized as a (pre)catalyst for OER. The NiS (pre)catalyst requires an overpotential of only 255 mV to reach the benchmark current density of 10 mA cm-2 and shows 63 h of chronopotentiometry (CP) stability along with over 95% Faradaic efficiency in 1 m KOH. Several ex situ measurements and quasi in situ Raman spectroscopy uncover that NiS irreversibly transformed to a carbonate-intercalated γ-NiOOH phase under the alkaline OER conditions, which serves as the actual active structure for the OER. Additionally, this in situ formed active phase successfully catalyzes the selective oxidation of alcohol, aldehyde, and amine-based organic substrates to value-added chemicals, with high efficiencies.
RESUMO
Evolutionarily elderly proteins commonly feature greater catalytic promiscuity. Cytochromeâ c is among the first set of proteins in evolution to have known prospects in electron transport and peroxidative properties. Here, we report that cytâ c is also a proficient proton-transfer catalyst and enhances the Kemp elimination (KE; model reaction to show proton transfer catalytic property) by â¼750-fold on self-organized systems like micelles and vesicles. The self-organized systems mimic the mitochondrial environment inâ vitro for cytâ c. Using an array of biophysical and biochemical mutational assays, both acid-base and redox mechanistic pathways have been explored. The histidine moiety close to hemin group (His18) is mainly responsible for proton abstraction to promote the concerted E2 pathway for KE catalysis when cytâ c is in its oxidized form; this has also been confirmed by a H18A mutant of cytâ c. However, the redox pathway is predominant under reducing conditions in the presence of dithiothreitol over the pH range 6-7.4. Interestingly, we found almost 750-fold enhanced KE catalysis by cytâ c compared to aqueous buffer. Overall, in addition to providing mechanistic insights, the data reveal an unprecedented catalytic property of cytâ c that could be of high importance in an evolutionary perspective considering its role in delineating the phylogenic tree and also towards generating programmable designer biocatalysts.
Assuntos
Citocromos c/metabolismo , Biocatálise , Citocromos c/genética , Ditiotreitol/química , Hemina/química , Histidina/química , Concentração de Íons de Hidrogênio , Mutagênese Sítio-Dirigida , Oxirredução , PrótonsRESUMO
Understanding the fundamental facts behind dynamicity of catalytic processes has been a longstanding quest across disciplines. Herein, we report self-assembly of catalytically active gold nanorods that can be regulated by tuning its reactivity towards a proton transfer reaction at different pH. Unlike substrate-induced templating and co-operativity, the enhanced aggregation rate is due to alteration of catalytic surface charge only during reactivity as negatively charged transition state of reactant (5-nitrobenzisoxazole) is formed on positively charged nanorod while undergoing a concerted E2-pathway. Herein, enhanced diffusivity during catalytic processes might also act as an additional contributing factor. Furthermore, we have also shown that nanosized hydrophobic cavities of clustered nanorods can also efficiently accelerate the rate of an aromatic nucleophilic substitution reaction, which also demonstrates a catalytic phenomenon that can lead to cascading of other reactions where substrates and products of the starting reactions are not directly involved.