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论文类型：期刊论文

发表时间：2021-02-02

发表刊物：ACS OMEGA

卷号：4

期号：2

页面范围：4113-4128

ISSN号：2470-1343

摘要：It has been known that dedicated photoinduced catalysis over artificial functional nanostructures and/or combined with effective peroxymonosulfate (PMS) activations toward highly effective greener synthesis and/or environmental remediation have been well recognized to be one of the best options for efficiently exploiting solar light to convert into chemical fuel and energy. Novel ZnxCu1-xFe2O4 (0 <= x <= 1) hierarchical yolk-shell hollow nano-microspheres/PMS/Vis (ZCF/PMS/Vis) tandem systems with remarkable light harvesting capability and superior environmental catalytic activity toward elimination of antibiotic enrofloxacin up to 90.5% removal efficiency have been successfully designed and fabricated via combined solvothermal strategy and morphologically conserved sintering in this current work. The physicochemical characteristics, diverse structures including the spinel crystal structures, hierarchical nano-microstructure, and internal correlations of structure-dependent properties, and the catalytic reaction mechanism in terms of the synergetic effect between instant PMS activation and dedicated photoinitiated catalysis have been methodically inspected and thoroughly illustrated by a variety of in/ex situ physicochemical ways, and the diverse microstructures including solid microspheres with villiform surfaces, YSHMs composed of exquisite particles, and YSHM alternative formation of diverse microstructures could be ultimately tailored and formed. ZCF YSHMs exhibit higher efficiency of both dedicated catalysis and spatial charge separations owing to their physicochemical characteristics and surface structures, namely, more surface oxygen vacancies, highest specific surface area, and interior structures. Specifically, as confirmed by primary combined characterizations, namely, room-temperature Mossbauer, in situ spin-trap EPR, SPV, ns-TAS, and in situ Raman and sequential investigations, the primary reactive oxygen species were deemed to be SO4 center dot- and (OH)-O-center dot radicals, which generated instantly and simultaneously through surface covalent Cu2+ ions. Sequential-derived Cu(II)/Cu(III)/Cu(II) redox cycling initiated PMS activations and photoinitiated catalysis, and the superior catalytic performance as derived from ZCF HYSHM hierarchical-structured spinels could be primarily attributed to the diverse bulk and surface structures, highly efficient photonic energy harvesting, spatial charge separations and surface-interfacial transfers, more surface oxygen vacancies, and crucial reactive species including SO4 center dot- and (OH)-O-center dot generations with long radical lifetimes up to 14.57 mu s. The work could bring a brand new and deep insight into further understanding of both the intrinsic spinel structural influence factors governing the catalytic properties and the synergetic effect between instant PMS activation and simultaneous photoinitiated catalysis at the molecular level, which would be very beneficial for mimicking the natural photosynthetic solar energy harness system with marvelous featured properties in both environmental elimination and solar energy conversions.