RESUMO
Tetrahedral NiS2 /NiSe2 heterocages with rich-phase boundaries are synthesized through a simultaneous sulfuration/selenylation process using Ni-based acetate hydroxide prisms as precursor. Such a nanocage-like NiS2 /NiSe2 heterostructure can expose more active sites, accelerate the mass transport of the ions/gas, and optimize the interfacial electronic structure, which shows a significantly lower overpotential of 290 mV at 20 mA cm-2 than those of NiS/NiS2 and NiSe2 as counterparts. The experimental characterizations and theoretical density functional theory (DFT) calculations unveil that the interfacial electron transfer from NiSe2 to NiS2 at the heterointerface can modulate the electronic structure of NiS2 /NiSe2 , which further cooperates synergistically to change the Gibbs free energy of oxygen-containing intermediates as the rate-determining step (RDS) from 2.16 eV (NiSe2 ) and 2.10 eV (NiS2 ) to 1.86 eV (NiS2 /NiSe2 heterostructures) during the oxygen evolution reaction (OER) process. And as a result, tetrahedral NiS2 /NiSe2 heterocages with dual-phase synergy efficiently trigger the OER process, and accelerate the OER kinetics. This work provides insights into the roles of the interfacial electron transfer in electrocatalysis, and can be an admirable strategy to modulate the electronic structure for developing highly active electrocatalysts.
RESUMO
The acidity/alkalinity and structural properties of NiMgAl trimetallic oxides (MMOs) can be effectively modulated by the alkaline-etching process with various etching times, which are further used as a support to prepare KMoS-based catalysts through the cetyltrimethylammonium bromide-encapsulated Mo-precursor strategy. The enriched surface anion groups in alkaline-etched MMO affect the textural properties, metal-support interaction, and sulfidation degree of the as-synthesized KMoS-based catalysts. As a result, KMoS-based catalysts using alkaline-etched MMO as supports effectively enhance the reducibility and dispersion of Mo species, which exert a positive influence on higher alcohol synthesis (HAS) performance in CO hydrogenation. A proper balance between acidity/alkalinity and structural properties in K, Mo/MMO- x catalysts can significantly enhance the alcohol selectivity in HAS from 55 to 65% (carbon selectivity). The formation of C2+ alcohols can be boosted by adol condensation with optimal acidic/basic properties via suppressing the acidity and increasing the amount of basic sites. The alkaline-etching process also significantly improves the space time yield of C2+ alcohols over unit mass of molybdenum.
RESUMO
Electrochemical water splitting is a promising way for the sustainable production of hydrogen, but the efficiency of the overall water-splitting reaction largely depends on the oxygen evolution reaction (OER) because of its sluggish kinetics. Herein, a series of hierarchical ZnCo2 O4 /Co3 O4 /NC-CNT (NC-CNT=nitrogen-rich carbon nanotube) mesoporous dodecahedrons grafted to carbon nanotubes have been synthesized from ZnCo bimetallic zeolitic imidazolate frameworks (ZnCo-ZIFs) through sequential pyrolysis in nitrogen and mild oxidation in air. The simultaneous modulation of oxygen vacancies, composition, and hierarchical mesoporous architecture remarkably enhanced their electronic conduction and the amount and reactivity of accessible actives; thus boosting their intrinsic activity in the OER. The optimal ZnCo2 O4 /Co3 O4 /NC-CNT-700 sample exhibited a large current density of 50â mA cm-2 at a potential of 1.65â V, a small Tafel slope of 88.5â mV dec-1 , and superior stability in alkaline media. This work should provide a facile strategy for the rational design of advanced OER catalysts by simultaneous engineering of oxygen vacancies and composition.
