The aim of the present work was to investigate the toxic effects of zinc oxide nanoparticles (ZnO NPs, particle size < 50 nm) on the physiological and anatomical indices of spring barley (Hordeum sativum L.). The results show that ZnO NPs inhibited H. sativum growth by affecting the chlorophyll fluorescence emissions and causing deformations of the stomatal and trichome morphology, alterations to the cellular organizations, including irregularities of the chloroplasts, and disruptions to the grana and thylakoid organizations. There was a lower number of chloroplasts per cell observed in the H. sativum leaf cells treated with ZnO NPs as compared to the non-treated plants. Cytomorphometric quantification revealed that ZnO NPs decreased the size of the chloroplast by 1.5 and 4 times in 300 and 2000 mg/L ZnO NP-treated plants, respectively. The elemental analysis showed higher Zn accumulation in the treated leaf tissues (3.8 and 10.18-fold with 300 and 2000 mg/L ZnO NPs, respectively) than the untreated. High contents of Zn were observed in several spots in ZnO NP-treated leaf tissues using X-ray fluorescence. Deviations in the anatomical indices were significantly correlated with physiological observations. The accumulation of Zn content in plant tissues that originated from ZnO NPs was shown to cause damage to the structural organization of the photosynthetic apparatus and reduced the photosynthetic activities.
The oxygen reduction reaction (ORR) catalyzed by efficient and economical catalysts is critical for sustainable energy devices. Although the newly-emerging atomically dispersed platinum catalysts are highly attractive for maximizing atomic utilization, their catalytic selectivity and durability are severely limited by the inflexible valence transformation between Pt and supports. Here, we present a structure by anchoring Pt atoms onto valence-adjustable CuOx/Cu hybrid nanoparticle supports (Pt1-CuOx/Cu), in which the high-valence Cu (+2) in CuOx combined with zero-valent Cu (0) serves as a wide-range valence electron reservoir (0‒2e) to dynamically adjust the Pt 5d valence states during the ORR. In situ spectroscopic characterizations demonstrate that the dynamic evolution of the Pt 5d valence electron configurations could optimize the adsorption strength of *OOH intermediate and further accelerate the dissociation of O = O bonds for the four-electron ORR. As a result, the Pt1-CuOx/Cu catalysts deliver superior ORR performance with a significantly enhanced four-electron selectivity of over 97% and long-term durability.