Evolution of Cationic Vacancy Defects: A Motif for Surface Restructuration of OER Precatalyst.

Defects have been found to enhance the electrocatalytic performance of NiFe-LDH for oxygen evolution reaction (OER). Nevertheless, their specific configuration and the role played in regulating the surface reconstruction of electrocatalysts remain ambiguous. Herein, cationic vacancy defects are generated via aprotic-solvent-solvation-induced leaking of metal cations from NiFe-LDH nanosheets. DFT calculation and in situ Raman spectroscopic observation both reveal that the as-generated cationic vacancy defects tend to exist as VM (M=Ni/Fe); under increasing applied voltage, they tend to assume the configuration VMOH , and eventually transform into VMOH-H which is the most active yet most difficult to form thermodynamically. Meanwhile, with increasing voltage the surface crystalline Ni(OH)x in the NiFe-LDH is gradually converted into disordered status; under sufficiently high voltage when oxygen bubbles start to evolve, local NiOOH species become appearing, which is the residual product from the formation of vacancy VMOH-H . Thus, we demonstrate that the cationic defects evolve along with increasing applied voltage (VM → VMOH → VMOH-H ), and reveal the essential motif for the surface restructuration process of NiFe-LDH (crystalline Ni(OH)x → disordered Ni(OH)x → NiOOH). Our work provides insight into defect-induced surface restructuration behaviors of NiFe-LDH as a typical precatalyst for efficient OER electrocatalysis.

Relationship between plankton-based ß-carotene and biodegradable adaptablity to petroleum-derived hydrocarbon.

Coastal environment are often stress from petroleum-derived hydrocarbon pollution. However, petroleum-derived hydrocarbon is persistent organic pollutants and their biodegradation by phytoplankton is little known. Five species of marine phytoplankton, including Dunaliella salina, Chlorella sp., Conticribra weissflogii, Phaeodactylum tricornutum Bohlin, and Prorocentrum donghaiense, have been used to test their tolerance to petroleum hydrocarbon contamination. D.salina and Chlorella sp can survive in high levels of No. 0 diesel oils water-soluble fractions (WSFs, 5.0 mg L-1), furthermore, petroleum hydrocarbon could be biodegraded effectively by them (Fig. 2). The content of ß-carotene in these two species of phytoplankton has significant correlation with degradation rate of WSFs concentrations (Fig. 4), petroleum hydrocarbons could be biodegraded effectively by algae. Meanwhile, the ·OH in seawater can be removed by ß-carotene effectively so that algal cells could be protected by the ß-carotene for its strong antioxidant capacity. Therefore, ß-carotene as a coin has two sides on the degradation of WSFs. Here we explore the relationship between plankton-based ß-carotene and biodegradable adaptabllity to petroleum-derived hydrocarbon, which offers a green technology for petroleum-derived hydrocarbon treatment.

Influence of acidification and eutrophication on physiological functions of Conticribra weissflogii and Prorocentrum donghaiense.

Eutrophication and acidification have been the most concerned environmental problems in coastal ecosystem. However, their combined effect on coastal ecosystem function was unknown. Both diatom (Conticribra weissflogii) and dinoflagellate (Prorocentrum donghaiense) are used as coastal algal model. Seven parameters were determined for physiological function assessment, including cell density, chlorophyll a (Chl a), protein, malonaldehyde (MDA), superoxide dismutase, carbonic anhydrase (CA), and nitrate reductase (NR). The influence of nitrate (N) and phosphate (P) on MDA and CA in C. weissflogii was significant, and that on Chl a and protein in P. donghaiense were also significant. However, the influence of acidification on physiological functions was not significant. The effect of acidification could be intensified by coastal eutrophication. More importantly, the coexist influence of acidification and eutrophication on CA, NR and protein in C. weissflogii and MDA in P. donghaiense was significant. Both NR activity and Chl a content in P. donghaiense were positively correlated to N and P concentration when pH were 7.9 and 7.8, respectively. With simultaneous worsening of acidification and eutrophication, the cell growth of P. Donghaiense was accelerated more obviously than C. weissflogii, i.e., dinoflagellate was more adaptable than diatom, thus algal species distribution and abundance could be changed.

Effect of coastal eutrophication on heavy metal bioaccumulation and oral bioavailability in the razor clam, Sinonovacula constricta.

As traditional seafoods, the razor clams are widely distributed from tropical to temperate areas. Coastal razor clams are often exposed to eutrophication. Heavy metal contamination is critical for seafood safety. However, how eutrophication affects bioaccumulation and oral bioavailability of heavy metals in the razor clams is unknown. After a four-month field experimental cultivation, heavy metals (Fe, Cu, Ni, V, As, and Pb) could be bioaccumulated by the razor clams (Sinonovacula constricta) through exposure to metals present in water and sediments or in the food chain, and then transferred to human via consumption of razor clams. Bionic gastrointestinal digestion and monolayer liposome extraction are used for metal oral bioavailability (OBA) assessment. The influence of eutrophication on OBA is decreased for Fe and Pb and increased for V. A significant positive linear correlation was observed between the bioaccumulation factors of Fe, Ni, V, and As in razor clams and the coastal eutrophication. These results may be due to the effect of eutrophication on metal species transformation in coastal seawater and subcellular distribution in razor clams. The maximum allowable daily intakes of razor clams are controlled by eutrophication status and the concentration of affinity-liposome As in razor clams.