Ionothermal synthesis of activated carbon from waste PET bottles as anode materials for lithium-ion batteries

Waste polyethylene terephthalate (PET) bottles have become a significant post-consumer plastic waste with attendant environmental problems. Hence, ionothermal synthesis has been used to prepare activated carbon (AC) anode materials from waste PET for both high performance and sustainable lithium-ion batteries (LIB). Particularly, using choline chloride deep eutectic salts (CU-DES) does not require post-synthesis washing and thereby reduces the complexity of the process and produces materials with unique low-surface area, higher levels of graphitization/ordering, and high nitrogen doping in the obtained ACs. The results show that the AC produced using CU-DES (PET-CU-A-ITP2) gave good electrochemical performance. Even though the material possesses a low surface area (∼23 m2 g−1), it displays a gravimetric capacity (GC) of ∼460 mA h g−1 and a coulombic efficiency (CE) of ∼53% in the 1st cycle and very good cycling performance with a capacity retention of 98% from the 2nd to the 100th cycle. The superior electrochemical performance of the PET-CU-A-ITP2 anode was found to be due to its better graphitization/ordering and dense structure which results in higher capacity, formation of less solid electrolyte interphase, and higher CE. These results show that dense carbons can be exploited as high-performance anodes in LIBs. Also, this research presents both a pathway for waste PET management and a waste-energy approach that could offer cheaper and greener LIBs to meet the sustainable development goals

Bright triplet excitons in lead halide perovskites

Nanostructured semiconductors emit light from electronic states known as excitons[1]. According to Hund's rules[2], the lowest energy exciton in organic materials should be a poorly emitting triplet state. Analogously, the lowest exciton level in all known inorganic semiconductors is believed to be optically inactive. These 'dark' excitons (into which the system can relax) hinder light-emitting devices based on semiconductor nanostructures. While strategies to diminish their influence have been developed[3-5], no materials have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in quasi-cubic lead halide perovskites is optically active. We first use the effective-mass model and group theory to explore this possibility, which can occur when the strong spin-orbit coupling in the perovskite conduction band is combined with the Rashba effect [6-10]. We then apply our model to CsPbX3 (X=Cl,Br,I) nanocrystals[11], for which we measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright character of the lowest exciton immediately explains the anomalous photon-emission rates of these materials, which emit 20 and 1,000 times faster[12] than any other semiconductor nanocrystal at room[13-16] and cryogenic[17] temperatures, respectively. The bright exciton is further confirmed by detailed analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals[18], which are already used in lighting[19,20], lasers[21,22], and displays[23], these optically active excitons can lead to materials with brighter emission and enhanced absorption. More generally, our results provide criteria for identifying other semiconductors exhibiting bright excitons with potentially broad implications for optoelectronic devices.Comment: 14 pages and 3 figures in the main text, Methods and extended data 16 pages which include 11 figures, and supporting information 28 page

Bright triplet excitons in caesium lead halide perovskites

Nanostructured semiconductors emit light from electronic states known as excitons. For organic materials, Hund’s rules state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules predict an analogue of this triplet state known as the ‘dark exciton’. Because dark excitons release photons slowly, hindering emission from inorganic nanostructures, materials that disobey these rules have been sought. However, despite considerable experimental and theoretical efforts, no inorganic semiconductors have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in caesium lead halide perovskites (CsPbX_3, with X = Cl, Br or I) involves a highly emissive triplet state. We first use an effective-mass model and group theory to demonstrate the possibility of such a state existing, which can occur when the strong spin–orbit coupling in the conduction band of a perovskite is combined with the Rashba effect. We then apply our model to CsPbX_3 nanocrystals, and measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright triplet character of the lowest exciton explains the anomalous photon-emission rates of these materials, which emit about 20 and 1,000 times faster than any other semiconductor nanocrystal at room and cryogenic temperatures, respectively. The existence of this bright triplet exciton is further confirmed by analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals, which are already used in lighting, lasers and displays, these excitons could lead to materials with brighter emission. More generally, our results provide criteria for identifying other semiconductors that exhibit bright excitons, with potential implications for optoelectronic devices

Seawater carbon chemistry and calcification,carbonic anhydrase activity of cold-water coral Lophelia pertusa

Ocean acidification, the decrease in seawater pH due to the absorption of atmospheric CO2, profoundly threatens the survival of a large number of marine species. Cold-water corals are considered to be among the most vulnerable organisms to ocean acidification because they are already exposed to relatively low pH and corresponding low calcium carbonate saturation states (Omega). Lophelia pertusa is a globally distributed cold-water scleractinian coral that provides critical three-dimensional habitat for many ecologically and economically significant species. In this study, four different genotypes of L. pertusa were exposed to three pH treatments (pH=7.60, 7.75, and 7.90) over a short (two-week) experimental period, and six genotypes were exposed to two pH treatments (pH=7.60, and 7.90) over a long (six-month) experimental period. Their physiological response was measured as net calcification rate and the activity of carbonic anhydrase, a key enzyme in the calcification pathway. In the short-term experiment, net calcification rates did not significantly change with pH, although they were highly variable in the low pH treatment, including some genotypes that maintained positive net calcification in undersaturated conditions. In the six-month experiment, average net calcification was significantly reduced at low pH, with corals exhibiting net dissolution of skeleton. However, one of the same genotypes that maintained positive net calcification (+0.04% day-1) under the low pH treatment in the short-term experiment also maintained positive net calcification longer than the other genotypes in the long-term experiment, although none of the corals maintained positive calcification for the entire 6 months. Average carbonic anhydrase activity was not affected by pH, although some genotypes exhibited small, insignificant, increases in activity after the sixth month. Our results suggest that while net calcification in L. pertusa is adversely affected by ocean acidification in the long term, it is possible that some genotypes may prove to be more resilient than others, particularly to short perturbations of the carbonate system. These results provide evidence that populations of L. pertusa in the Gulf of Mexico may contain the genetic variability necessary to support an adaptive response to future ocean acidification

Intra-Specific Variation Reveals Potential for Adaptation to Ocean Acidification in a Cold-Water Coral from the Gulf of Mexico

Ocean acidification, the decrease in seawater pH due to the absorption of atmospheric CO2, profoundly threatens the survival of a large number of marine species. Cold-water corals are considered to be among the most vulnerable organisms to ocean acidification because they are already exposed to relatively low pH and corresponding low calcium carbonate saturation states (Ω). Lophelia pertusa is a globally distributed cold-water scleractinian coral that provides critical three-dimensional habitat for many ecologically and economically significant species. In this study, four different genotypes of L. pertusa were exposed to three pH treatments (pH = 7.60, 7.75, and 7.90) over a short (2-week) experimental period, and six genotypes were exposed to two pH treatments (pH = 7.60 and 7.90) over a long (6-month) experimental period. Their physiological response was measured as net calcification rate and the activity of carbonic anhydrase, a key enzyme in the calcification pathway. In the short-term experiment, net calcification rates did not significantly change with pH, although they were highly variable in the low pH treatment, including some genotypes that maintained positive net calcification in undersaturated conditions. In the 6-month experiment, average net calcification was significantly reduced at low pH, with corals exhibiting net dissolution of skeleton. However, one of the same genotypes that maintained positive net calcification (+0.04% day−1) under the low pH treatment in the short-term experiment also maintained positive net calcification longer than the other genotypes in the long-term experiment, although none of the corals maintained positive calcification for the entire 6 months. Average carbonic anhydrase activity was not affected by pH, although some genotypes exhibited small, insignificant, increases in activity after the sixth month. Our results suggest that while net calcification in L. pertusa is adversely affected by ocean acidification in the long term, it is possible that some genotypes may prove to be more resilient than others, particularly to short perturbations of the carbonate system. These results provide evidence that populations of L. pertusa in the Gulf of Mexico may contain the genetic variability necessary to support an adaptive response to future ocean acidification

Data from: Niche divergence by deep-sea octocorals in the genus Callogorgia across the continental slope of the Gulf of Mexico

Environmental variables that are correlated with depth have been suggested to be among the major forces underlying speciation in the deep sea. This study incorporated phylogenetics and ecological niche models (ENM) to examine whether congeneric species of Callogorgia (Octocorallia: Primnoidae) occupy different ecological niches across the continental slope of the Gulf of Mexico (GoM), and whether this niche divergence could be important in the evolution of these closely related species. Callogorgia americana americana, C. americana delta, and C. gracilis were documented at 13 sites in the GoM (250-1000 m) from specimen collections and extensive video observations. On a first order, these species were separated by depth, with C. gracilis occurring at the shallowest sites, C. a. americana at mid-depths, and C. a. delta at the deepest sites. Callogorgia a. delta was associated with areas of increased seep activity whereas C. gracilis and C. a. americana were associated with narrow, yet warmer, temperature ranges and did not occur near cold seeps. ENM background and identity tests revealed little to no overlap in ecological niches between species. Temporal calibration of the phylogeny revealed the formation of the Isthmus of Panama was a vicariance event that may explain some of the patterns of speciation within this genus. These results elucidate the potential mechanisms for speciation in the deep sea, emphasizing both bathymetric speciation and vicariance events in the evolution of a genus across multiple regions

Scientists\u27 Warning of an Imperiled Ocean

In 2017, more than 15,000 scientists from 184 countries signed a second warning letter to humanity to caution against our continued wholesale destruction of global ecosystems (Ripple et al., 2017). Here, we reaffirm their message with a similar warning specifically focused on the ocean: humanity must immediately and significantly alter our harmful trajectory in order to avoid irrevocably damaging our oceans in multiple ways that will further affect ocean health for both us and future generations. The ocean is the world\u27s largest realm, housing an astonishing array of biodiversity that provides critical ecological functions that ultimately support life on Earth. In this paper, we outline some of the significant ongoing and imminent activities that degrade ocean health, including destructive fishing practices, oil and natural gas extraction, seabed mining, coastal development, shipping, pollution, and greenhouse-gas emissions. We end by offering potential avenues to mitigate these impacts, including the cessation of particularly harmful activities, restoration of damaged habitats, strong protection of key and representative ecosystems, reduction in waste and emissions, and global policy shifts that prioritize ecosystem health

Biogeographic variability in the physiological response of the cold-water coral Lophelia pertusa to ocean acidification

While ocean acidification is a global issue, the severity of ecosystem effects is likely to vary considerably at regional scales. The lack of understanding of how biogeographically separated populations will respond to acidification hampers our ability to predict the future of vital ecosystems. Cold-water corals are important drivers of biodiversity in ocean basins across the world and are considered one of the most vulnerable ecosystems to ocean acidification. We tested the short-term physiological response of the cold-water coral Lophelia pertusa to three pH treatments (pH = 7.9, 7.75 and 7.6) for Gulf of Mexico (USA) and Tisler Reef (Norway) populations, and found that reductions in seawater pH elicited contrasting responses. Gulf of Mexico corals exhibited reductions in net calcification, respiration and prey capture rates with decreasing pH. In contrast, Tisler Reef corals showed only slight reductions in net calcification rates under decreased pH conditions while significantly elevating respiration and capture rates. These differences are likely the result of environmental differences (depth, pH, food supply) between the two regions, invoking the potential for local adaptation or acclimatization to alter their response to global change. However, it is also possible that variations in the methodology used in the experiments contributed to the observed differences. Regardless, these results provide insights into the resilience of L. pertusa to ocean acidification as well as the potential influence of regional differences on the viability of species in future oceans

High-Resolution Habitat Suitability Models for the Conservation and Management of Vulnerable Marine Ecosystems on the Louisville Seamount Chain, South Pacific Ocean

Vulnerable marine ecosystems (VMEs) are ecosystems at risk from the effects of fishing or other kinds of disturbance, as determined by the vulnerability of their components (e.g., habitats, communities, or species). Habitat suitability modeling is being used increasingly to predict distribution patterns of VME indicator taxa in the deep sea, where data are particularly sparse, and the models are considered useful for marine ecosystem management. The Louisville Seamount Chain is located within the South Pacific Regional Fishery Management Organization (SPRFMO) Convention Area, and some seamounts are the subject of bottom trawling for orange roughy by the New Zealand fishery. The aim of the present study was to produce high-resolution habitat suitability maps for VME indicator taxa and VME habitat on these seamounts, in order to evaluate the feasibility of designing within-seamount spatial closures to protect VMEs. We used a multi-model habitat suitability mapping approach, based on bathymetric and backscatter data collected by multibeam echo sounder survey, and data collected by towed underwater camera for the stony coral and habitat-forming VME indicator species Solenosmilia variabilis, as well as two taxa indicative of stony coral habitat (Brisingida, Crinoidea). Model performance varied among the different model types used (Boosted Regression Tree, Random Forest, Generalized Additive Models), but abundance-based models consistently out-performed models based on presence-absence data. Uncertainty for ensemble models (combination of all models) was lower overall compared to the other models. Maps resulting from our models showed that suitable habitat for S. variabilis is distributed around the summit-slope break of seamounts, and along ridges that extend down the seamount flanks. Only the flat, soft sediment summits are predicted to be unsuitable habitat for this stony coral species. We translated a definition for stony coral-reef habitat into a S. variabilis abundance-based threshold in order to use our models to map this VME habitat. These maps showed that coral-reef occurred in small and isolated patches, and that most of the seabed on these seamounts is predicted to be unsuitable habitat for this VME. We discuss the implications of these results for spatial management closures on the Louisville Seamount Chain seamounts and the wider SPRFMO area, and future modeling improvements that could aid efforts to use habitat suitability maps for managing the impact of fishing on VMEs

Quattrini_Callogorgia_ENVABUNDATA

Abundances and densities for Callogorgia spp. collected in the Gulf of Mexico, with corresponding site, location, and environmental data