RESUMO
While the ambient N2 reduction to ammonia (NH3) using H2O as hydrogen source (2N2+6H2O=4NH3+3O2) is known as a promising alternative to the Haber-Bosch process, the high bond energy of N≡N bond leads to the extremely low NH3 yield. Herein, we report a highly efficient catalytic system for ammonia synthesis using the low-temperature dielectric barrier discharge plasma to activate inert N2 molecules into the activated nitrogen species, which can efficiently react with the confined and concentrated H2O molecules in porous metal-organic framework (MOF) reactors with V3+, Cr3+, Mn3+, Fe3+, Co2+, Ni2+ and Cu2+ ions. Specially, the Fe-based catalyst MIL-100(Fe) causes a superhigh NH3 yield of 22.4 mmol g-1 h-1. The investigation of catalytic performance and systematic characterizations of MIL-100(Fe) during the plasma-driven catalytic reaction unveils that the in situ generated defective Fe-O clusters are the highly active sites and NH3 molecules indeed form inside the MIL-100(Fe) reactor. The theoretical calculation reveals that the porous MOF catalysts have different adsorption capacity for nitrogen species on different catalytic metal sites, where the optimal MIL-100(Fe) has the lowest energy barrier for the rate-limiting *NNH formation step, significantly enhancing efficiency of nitrogen fixation.
RESUMO
Visible light catalysis has been widely coupled with persulfate activation for refractory pollutants removal, while the exact role of persulfate played in such composite system is still questionable. In this work, the relation between peroxymonosulfate (PMS) induced structure change and visible light responsive activity of inverse spinel: i.e., Zn2SnO4, was deciphered. Under the visible light illumination (λ> 420nm) PMS addition would endow the composite system with pollutant removal performance. Batch test revealed that 60% of bisphenol-A (5 mg L-1) was mineralized within 3 h reaction time, by dosing 0.81 mM PMS and 0.1 g L-1 catalyst. The above oxidative system was also effective for other refractory pollutants elimination. Further analysis indicated that PMS could reduce the band gap of spinel from 2.75 to 2.52 eV and thereby enabling its visible light activity. Photogenerated h+ induced â¢OH and e- mediated â¢O2- contributed to the pollutant removal while h+ played a leading role. Density functional theory revealed that PMS would capture oxygen atom of spinel and induce surface oxygen vacancy defect structure formation. Also, three-oxygen atom coordinated Zn was identified as the possible catalyze site. This work is valuable for deep understanding the exact role of persulfate in photocatalytic system.
RESUMO
Bioceramics have been developed from bioinert to bioactive or biodegradable materials in the past few decades. However, at present, traditional bioceramics are still mainly used in bone tissue regeneration and dental restoration. In this work, a new generation of "black bioceramics," extending the applications from tissue regeneration to disease therapy, is presented. Black bioceramics, through magnesium thermal reduction of traditional white ceramics, including silicate-based (e.g., CaSiO3 , MgSiO3 ) and phosphate-based (e.g., Ca3 (PO4 )2 , Ca5 (PO4 )3 (OH)), are successfully synthesized. Due to the presence of oxygen vacancies and structural defects, the black bioceramics possess photothermal functionality while maintaining their initial high bioactivity and regenerative capacity. These black bioceramics show excellent photothermal antitumor effects for both skin and bone tumors. At the same time, they have significantly improved bioactivity for skin/bone tissue repair in vitro and in vivo. These fascinating properties award the black bioceramics with profound applications in both tumor therapy and tissue regeneration, which should greatly promote the scientific relevance and clinical application of bioceramics, representing a promising new direction of cell-instructive biomaterials.