ABSTRACT
The hydrogen evolution reaction (HER) activity of defect-stabilized low-Pt-loading catalysts is closely related with defect type in support materials, while the knowledge about the effect of higher-dimensional defects on the property and activity of trapped Pt atomic species is scarce. Herein, small size (5-10 nm) TiO2 nanoparticles with abundant surface step defects (one kind of line defect) are used to direct the uniform anchoring of Pt atomic clusters (Pt-ACs) via PtâOâTi linkage. The as-made low-Pt catalysts (Pt-ACs/S-TiO2 -NP) exhibit exceptional HER intrinsic activity due to the unique step-site Pi-O-Ti species, in which the mass activity and turnover frequency are as high as 21.46 A mg Pt -1 and 21.69 s-1 at the overpotential of 50 mV, both far beyond those of benchmark Pt/C catalysts and other Pt-ACs/TiO2 samples with less step sites. Spectroscopic measurements and theoretical calculations reveal that the step-defect-located PtâOâTi sites can simultaneously induce the charge transfer from TiO2 substrate to the trapped Pt-ACs and the downshift of d-band center, which helps the proton reduction to H* intermediates and the following hydrogen desorption process, thus improving the HER. The work provides a deep insight on the interactions between high-dimensional defect and well-dispersed atomic metal motifs for superior HER catalysis.
ABSTRACT
The bottleneck of large-scale implementation of electrocatalytic water-splitting technology lies in lacking inexpensive, efficient, and durable catalysts to accelerate the sluggish oxygen evolution reaction kinetics. Owing to more metallic features, transition metal telluride (TMT) with good electronic conductivity holds promising potential as an ideal type of electrocatalysts for oxygen evolution reaction (OER), whereas most TMTs reported up to now still show unsatisfactory OER performance that is far below corresponding sulfide and selenide counterparts. Here, the activation and stabilization of cobalt telluride (CoTe) nanoarrays toward OER through dual integration of sulfur (S) doping and surface oxidization is reported. The as-synthesized CoO@S-CoTe catalyst exhibits a low overpotential of only 246 mV at 10 mA cm-2 and a long-term stability of more than 36 h, outperforming commercial RuO2 and other reported telluride-based OER catalysts. The combined experimental and theoretical results reveal that the enhanced OER performance stems from increased active sites exposure, improved charge transfer ability, and optimized electronic state. This work will provide a valuable guidance to release the catalytic potential of telluride-based OER catalysts via interface modulating engineering.
ABSTRACT
The low fire safety performance (flame retardant and antistatic properties) of poly(methyl methacrylate) (PMMA) has severely limited practical applications. Here, a phosphorylated Zn-based metal-organic framework (ZIF-8-P) is employed as an effective flame retardant and antistatic agent to reduce the fire risk of PMMA. Encouragingly, the as-prepared PMMA/ZIF-8-P composite demonstrated not merely better mechanical properties (e.g., a rise of ca. 136.9% and 175.0% in the reduced modulus and hardness; a higher storage modulus), but also efficient fire safety properties (e.g., lower surface resistance; a decrease of ca. 73.1% in the peak heat release rate; a lower amount of total pyrolysis products), surpassing those of pure PMMA and a PMMA/ZIF-8 composite without phytic acid modification. Mechanism analysis is conducted to reveal the critical role of catalytic charring, char reinforcing, and the dilution of nonflammable gases from ZIF-8 additives during the combustion and pyrolysis process. Our study paves a promising way to achieve high performance PMMA composites.
