Hua Lei

Coating materials on the bottoms of reactors/beakers has emerged as an effective method to regulate tribo-catalytic reactions. In this study, silicon single crystals were coated on the bottoms of glass beakers, in which 30 mg/L methyl orange (MO) solutions suspended with alumina nanoparticles were subjected to magnetic stirring using Teflon magnetic rotary disks. With a gentle rotating speed of 400 rpm for the Teflon disks, the MO solutions were changed from yellow to colorless and the characteristic absorption peak of MO at 450 nm in the UV-Vis spectrum disappeared entirely within 120 min. Mass spectrometry tests were further performed to gain insights into the degradation process, which suggested that the degradation was initiated with the cleavage of the nitrogen-nitrogen double bond in ionized MO molecules by the attack of •OH radicals. Through comparison experiments, we established that the observed degradation was related to the friction between alumina and silicon during magnetic stirring, and hydroxyl and superoxide radicals were formed from the friction, according to electron paramagnetic resonance analysis. It is proposed that electron-hole pairs are excited in silicon single crystals through friction with alumina, which diffuse to the surface of the single crystals and result in the degradation.

NiO has been found to be highly outstanding in producing H₂ and O₂ from H₂O through magnetic stirring, while its capability for the reduction of CO₂ through mechanical stimulation has not been investigated. Presently, NiO particles have been employed to promote the conversion of H₂O and CO₂ enclosed in reactors into flammable gases through magnetic stirring. For a 150 mL glass reactor filled with 50 mL water, 1.00 g of NiO particles, and 1 atm of CO₂, 24 h of magnetic stirring using a home-made Teflon magnetic rotary disk resulted in the formation of 33.80 ppm CO, 10.10 ppm CH₄, and 12,868.80 ppm H₂. More importantly, the reduction of CO₂ was found to be substantially enhanced through coating some polymers and metals on the reactor bottoms, including 25.64 ppm CO and 70.97 ppm CH₄ obtained for a PVC-coated reactor and 30.68 ppm CO, 52.78 ppm CH₄, 3.82 ppm C₂H₆, and 2.18 ppm C₂H₄ obtained for a stainless steel-coated reactor. Hydroxyl radicals were detected using fluorescence spectroscopy for NiO particles under magnetic stirring in water. A tribo-catalytic mechanism has been proposed for the conversion of H₂O and CO₂ into flammable gases by NiO particles under magnetic stirring that is based on the excitation of electron-hole pairs in NiO by mechanical energy absorbed through friction. These findings not only reveal a great potential for mechanical energy to be utilized for CO₂ conversion but are also valuable for fundamental studies.

More and more metal oxide nanomaterials are being synthesized and investigated for degradation of organic pollutants through harvesting friction energy, yet the strategy to optimize their performance for this application has not been carefully explored up to date. In this work, three commercially available ZnO powders are selected and compared for tribocatalytic degradation of organic dyes, among which ZnO-1 and ZnO-2 are agglomerates of spherical nanoparticles around 20 nm, and ZnO-3 are particles of high crystallinity with a regular prismatic shape and smooth surfaces, ranging from 50 to 150 nm. Compared with ZnO-1 and ZnO-2, ZnO-3 exhibits a much higher tribocatalytic degradation performance, and a high degradation rate constant of 6.566 × 10⁻² min⁻¹ is achieved for RhB, which is superior compared with previous tribocatalytic reports. The stability and universality of ZnO-3 were demonstrated through cycling tests and degradation of different types of dyes. Furthermore, the mechanism of tribocatalysis revealed that h+ was the main active species in the degradation process by ZnO. This work highlights the great significance of high crystallinity rather than a large specific surface area for the development of high-performance tribocatalysts and demonstrates the great potential of tribocatalysis for water remediation.