Circular economy strategies for mitigating metals shortages in electric vehicle batteries under China's carbon-neutral target.

Concerns over supply risks of critical metals used in electric vehicle (EV) batteries are frequently underscored as impediments to the widespread development of EVs. With the progress to achieve carbon neutrality by 2060 for China, projecting the critical metals demand for EV batteries and formulating strategies, especially circular economy strategies, to mitigate the risks of demand-supply imbalance in response to potential obstacles are necessary. However, the development scale of EVs in the transport sector to achieve China's carbon neutrality is unclear, and it remains uncertain to what extent circular economy strategies might contribute to the reduction of primary raw materials extraction. Consequently, we explore the future quantity of EVs in China required to achieve carbon neutrality and quantify the primary supply security levels of critical metals with the effort of battery cascade utilization, technology substitutions, recycling efficiency improvement, and novel business models, by integrating dynamic material flow analysis and national energy technology model. This study reveals that although 18%-30% of lithium and 20%-41% of cobalt, nickel, and manganese can be supplied to EVs through the reuse and recycling of end-of-life batteries, sustainable circular economy strategies alone are insufficient to obviate critical metals shortages for China's EV development. However, the supplementary capacity offered by second-life EV batteries, which refers to the use of batteries after they have reached the end of their first intended life, may prove adequate for China's prospective novel energy storage applications. The cumulative primary demand for lithium, cobalt, and nickel from 2021 to 2060 would reach 5-7 times, 23-114 times, and 4-19 times the corresponding mineral reserves in China. Substantial reduction of metals supply risks apart from lithium can be achieved by the cobalt-free battery technology developments combined with efficient recycling systems, where secondary supply can satisfy the demand as early as 2054.

Metal-Organic Framework Membrane Constructor: A Tool for High-Throughput Construction of Metal-Organic Framework Membrane Models.

With the rapid development of metal-organic framework (MOF) membranes for separation applications, computational screening of their separation performance has attracted increasing interest in the design and fabrication of such materials. Although bulk crystal models in MOF databases are often used to represent MOF membrane structures, membrane models in slab geometries are still essential for researchers to simulate the separation performance, particularly to understand the effects of the surface/interface structure, pore sieving, and exposed lattice plane on guest permeability. However, to date, no database or method has been established to provide researchers with numerous membrane models, restricting the further development of related theoretical studies. Herein, we propose an algorithm and develop a tool called the "MOF-membrane constructor" to realize the high-throughput construction of membrane models based on the MOF crystal structures. Using this tool, membrane models can be generated with desired sizes, reasonable surface terminations, and assigned exposed crystal planes. The tool can also deduce the most prominent surface in the Bravais-Friedel-Donnay-Harker morphology or identify the pores in MOF crystals and automatically determine an exposed plane for each membrane model. Thus, an MOF-membrane database can be established rapidly according to user simulation requirements. This study can considerably improve the efficiency of building MOF membrane models and may be beneficial for the future development of simulation studies on MOF membranes.

A Heavy-atom-free Molecular Motif Based on Symmetric Bird-like Structured Tetraphenylenes with Room-Temperature Phosphorescence (RTP) Afterglow over 8 s.

In recent years, pure organic room-temperature phosphorescence (RTP) with highly efficient and long-persistent afterglow has drawn substantial awareness. Commonly, spin-orbit coupling can be improved by introducing heavy atoms into pure-organic molecules. However, this strategy will simultaneously increase the radiative and non-radiative transition rate, further resulting in dramatic decreases in the excited state lifetime and afterglow duration. Here in this work, a highly symmetric bird-like structure tetraphenylene (TeP), and its three symmetrical halogenated derivatives (TeP-F, TeP-Cl and TeP-Br) are synthesized, while their RTP properties and mechanisms are systematically investigated by both theoretical and experimental approaches. As the results, the rigid, highly twisted conformation of TeP restricts the non-radiative processes of RTP and gives rise to the enhancement of electron-exchange, which can contribute to the RTP radiation process. Despite the faint RTP of the bromine and chlorine-substituted ones (TeP-Br, TeP-Cl), the fluoro-substituted TeP-F exhibited a long phosphorescent lifetime up to 890 ms, corresponding to an extremely long RTP afterglow over 8 s, which could be incorporated into the best series of non-heavy-atom RTP materials reported in previous literature.

Boosting the Optoelectronic Performance by Regulating Exciton Behaviors in a Porous Semiconductive Metal-Organic Framework.

Exciton behaviors including exciton formation and dissociation dynamics play an essential role in the optoelectronic performance of semiconductive materials but remain unexplored in semiconductive metal-organic frameworks (MOFs). Herein, we reveal that the exciton behaviors in semiconductive MOFs can be regulated by framework-guest interactions, a feature often not achievable in traditional inorganic or organic semiconductors. Incorporation of the electron-deficient molecule within the pores of a terbium-based semiconductive MOF (Tb2L2·4H2O·6DMF, L = TATAB3-, 4,4',4″-s-triazine-1,3,5-triyltri-p-aminobenzoate, DMF = N,N-dimethylformamide) results in efficient energy transfer from the MOF skeleton to molecular acceptors, with a yield of up to 77.4%. This interaction facilitates distinctive exciton type conversion, giving rise to modified conductivity and photoelectric performance. We further fabricated a MOF-based X-ray detection device to demonstrate how the new architecture bolsters the optoelectronic efficiency, which outperforms the properties of parent semiconductive MOFs, with more than 60 times and 40 times enhancement of the photocurrent on-off ratio and detection sensitivity, respectively. With judiciously optimized exciton behaviors, the detection device exhibits a high sensitivity of 51.9 µC Gyair-1 cm-2 and records a charge carrier mobility-lifetime product of 1.12 × 10-3 cm2 V-1 among MOF-based X-ray detectors, which are competitive with values for commercially available detectors. These findings demonstrate a rational synthetic approach to designing exciton arrangements to improve the optoelectronic efficiency of semiconductive MOFs.

Source tracing and chemical weathering implications of strontium in agricultural basin in Thailand during flood season: A combined hydrochemical approach and strontium isotope.

87Sr/86Sr of river water are of great significance in constraining oceanic strontium (Sr) record and terrestrial climate change due to the connection of continental weathering and the adjacent ocean. This work presents the geochemical characteristics of dissolved Sr and hydrochemistry, and estimates chemical weathering rate together with elemental Sr flux during the flood season of the Mun River, the largest tributary of Mekong River. Hydrochemistry analysis indicates the dominance of Cl- and HCO3- for major anions with the average of 34.6 and 43.0 mg/L, respectively, and Na+ and Ca2+ together dominated the cationic composition with the average of 22.9 and 10.5 mg/L, respectively. The ion concentrations during flood season were lower than that in dry season, implying tremendous river runoff due to extreme rainfall. The dissolved Sr ranges 6.1-237.5 µg/L with higher contents in the upper Mun. Sr contents in flood season are lower and less fluctuated than that in dry season, whereas the divergence between up and downstream becomes larger. 87Sr/86Sr ranges 0.7100-0.7597, slightly higher than global average. Elemental molar ratio analysis partly corroborates the inference from correlation analysis, but 87Sr/86Sr does not correlate with Na/Ca, indicating additional influence except for the weathering of evaporites and silicates. Comparing to regional wastewater and rainwater, the lower reaches exhibits superimposed impact of agricultural inputs on weathering to dissolved loads, especially in downstream with more tributary convergence. Extreme rainfall during flood season and extensive agricultural production activities may interfere in altering riverine solutes. Silicate weathering rate and CO2 consumption rate are calculated as well as the yearly 87Sr in excess to the Mekong River and finally to the Pacific Ocean with a Sr flux of 1.98 × 103 tons/year, indicating significant influence on seawater strontium isotope evolution in the long run. Together with tropical climate and high-intensity precipitation, the accelerated chemical weathering process seems inevitable. Therefore, the impact of agricultural interference in the pan-Mekong River basin needs more systematic and multi-angle research to provide a comprehensive insight on better watershed management under tropical climatic conditions.

Environmental implications of agricultural abandonment on Fe cycling: Insight from iron forms and stable isotope composition in karst soil, southwest China.

Land-use change influences the fate of nutrient elements, including iron (Fe), and then threaten soil security. In this study, Fe forms and stable isotope composition (δ56Fe) in soils were investigated to identify the variations in the processes of Fe cycling during agricultural abandonment in a karst region of Southwest China. Soil δ56Fe compositions varied from -0.05‰-0.02‰ in croplands, 0.05‰-0.12‰ in abandoned croplands, to 0.30‰-0.80‰ in the native vegetation lands. In the croplands, Fe oxidation-precipitation process is considered as the main contributor to Fe migration and isotope fractionation, leading to a relatively enrichment of heavier Fe isotope in deeper soil layer. In the abandoned croplands and native vegetation lands, Fe isotope in the organic-rich layer (0-10 cm) was significantly lighter than that in subsurface layer (20-30 cm), mainly due to the recovery of soil organic carbon (SOC) and macro-aggregate after cropland abandonment. Moreover, the eluviation process mainly caused a decrease in soil Fe contents and enrichment of heavy Fe isotope in deeper soils (below 40 cm). The positive correlation between oxidized Fe and SOC contents suggested the accumulation of mobile Fe in soils after agricultural abandonment, which is beneficial for Fe uptake and assimilation by plants. This study suggests that agricultural abandonment significantly reduce soil Fe leaching loss and improve plant Fe supply by SOC accumulation in surface soil, which gives an environmental implication for the management of soil nutrients.

Potentially toxic elements in cascade dams-influenced river originated from Tibetan Plateau.

Rivers originated from Tibetan Plateau are of great significance due to their environmental sensibility and fragility. However, the pollution of suspended particulate matter (SPM) in these rivers is rarely reported, in particular, the potentially toxic elements (PTEs) contamination. To clarify the status, sources, behavior, and risks of PTEs in SPM, a full investigation was conducted in dams-influenced Lancangjiang River basin. The findings revealed that the PTEs content (mg kg-1) ranked Mn (766) > V (151.7) > Zn (131.0) > Cr (94.6) > Ni (44.2) > Pb (36.7) > Cu (29.4) > Co (14.6) > Sb (2.6) > Mo (1.6) > Tl (0.78) > Cd (0.48). The multi-index assessment suggested that Sb and Cd were moderately severe to severe enriched PTEs with the enrichment factor values of 10.0 and 8.8 and the geo-accumulation index values of 2.2 and 2.0, respectively, while the rest of PTEs were minor/no enrichment. In contrast, Cr and Ni were major toxic elements in SPM which contributed 25 ± 10%, 24 ± 8% to the total toxic risk index. The high partition coefficients (e.g., 6.1 for Cr) were observed in most PTEs and resulted in the 96.3% of Cr, 85.2% of Zn, 83.6% of Pb, 77.8% of Ni, and 63.2% of Cu transportation in the SPM form. Natural inputs (e.g., soil erosion) are the main source (53.6%∼61.9%) of V, Cr, Mn, Co, Ni, and Tl, while fuel burning contributed 40.9% of Zn, 32.5% of Pb, and 37.3% of Cd. Moreover, 51.2% of Sb was attributed to industrial waste source, while porphyry copper/molybdenum deposits related milltailings were the co-source of Mo (54.4%) and Cu (34.8%). Overall, the PTEs geochemistry of SPM showed the potential in tracing regional environmental change.

Multicolour Fluorescence Based on Excitation-Dependent Electron Transfer Processes in o-Carborane Dyads.

Organic materials with excitation wavelength-dependent (Ex-de) emission are highly attractive for anticounterfeiting, optoelectronics and bioassay applications; however, the realization of Ex-de fluorescence, independent of aggregation states, remains a challenge. We herein report a photoinduced electron transfer (PeT) strategy to design Ex-de fluorescence materials by manipulating the relaxation pathways of multiple excited states. As expected, the o-carborane dyad presents a clear Ex-de fluorescence colour in the aggregated states, resulting from the tunable relative intensity of the dual-fluorescence spectra. Taking TP[1]B as an example, the amorphous powders emitted bright blue-violet, white and yellow colours under 390 nm, 365 nm and 254 nm UV illumination, respectively. Importantly, multicolour, flexible and transparent films as well as an anticounterfeiting application using this o-carborane dyad are demonstrated.

Metal-Organic Framework@Metal Oxide Heterostructures Induced by Electron-Beam Radiation.

Metal organic frameworks (MOFs) are a distinct family of crystalline porous materials finding extensive applications. Their synthesis often requires elevated temperature and relatively long reaction time. We report here the first case of MOF synthesis activated by high-energy (1.5 MeV) electron beam radiation from a commercially available electron-accelerator. Using ZIF-8 as a representative for demonstration, this type of synthesis can be accomplished under ambient conditions within minutes, leading to energy consumption about two orders of magnitude lower than that of the solvothermal condition. Interestingly, by controlling the absorbed dose in the synthesis, the electron beam not only activates the formation reaction of ZIF-8, but also partially etches the material during the synthesis affording a hierarchical pore architecture and highly crystalline ZnO nanoparticles on the surface of ZIF-8. This gives rise to a new strategy to obtain MOF@metal oxide heterostructures, finding utilities in photocatalytic degradation of organic dyes.

Achieving full-color emission of Cu nanocluster self-assembly nanosheets by the virtue of halogen effects.

Fluorescent Cu nanoclusters (NCs) have shown potential in lighting and display, because Cu is cheap and easily available. Despite recent successes in improving the emission intensity of Cu NCs on the basis of aggregation-induced emission enhancement and self-assembly-induced emission enhancement, the difficulty in tuning the emission color sheds the doubt for achieving high-performance white light-emitting diodes (WLEDs). In this work, halogen effects are utilized to tune the emission color of Cu nanocluster self-assembly nanosheets (NSASs). By altering the adsorbed halogens from Cl, Br to I, the emission peak of Cu NSASs is tunable from 495 to 674 nm. In this context, halogen atoms are capable of improving the charge transfer and molecular spin coupling of Cu NCs, and thereby narrow the S0T1 gap and facilitate the intersystem crossing of excitons from a singlet to triplet state. As a result, emission spectra redshift and the population of the exiton recombination via the triplet state pathway is increased, which leads to the improvement of the photoluminescence quantum yield (PLQY). By simply introducing and/or mixing different types of cuprous halides, Cu nanocluster co-assembly nanosheets (NCASs) with full-color emission are obtained. The as-prepared Cu NSASs and NCASs are further employed to fabricate monochrome and white LEDs.

Long-term trends in the incidence of endometriosis in China from 1990 to 2019: a joinpoint and age-period-cohort analysis.

BACKGROUND: Trends in the incidence of endometriosis in China remain unknown. The purpose of this study was to examine the trends in the incidence of endometriosis and the effects of age, period, and cohort on them. METHODS: Trends in endometriosis incidence were estimated using joinpoint regression. Age-period-cohort analysis was used to analyze the effects of age, period, and cohort on these trends. Endometriosis incidences in China (1990-2019) were retrieved from the Global Burden of Disease Study 2019. Annual percentage change and average annual percent change (AAPC) were analyzed by joinpoint regression, and relative risks were analyzed using an age-period-cohort model. RESULTS: Age-standardized incidence rates (ASIRs) declined between 1990 and 2019 in China, with an overall AAPC of -1.2% (95% CI: -1.20, -1.10). Compared to 1990, the ASIR in 2019 decreased by almost 30%. Moreover, the joinpoint regression analysis revealed that endometriosis ASIRs showed a downward trend across all age groups. A significant age-related effect was seen for endometriosis incidence among young women aged 15-24 years, which then decreased with advancing age. Consistently, the effect of the period on endometriosis incidence showed a declining trend, and the effect of birth cohort decreased by 0.53 (42.7%) from 1938-1942 to 1998-2002. CONCLUSIONS: Endometriosis ASIRs declined from 1990 to 2019. The effects of period and birth cohort on endometriosis incidence exhibited a declining trend across all age groups. The effect of age on endometriosis incidence showed an increasing trend before the age of 24, followed by a decreasing trend with subsequent advancing age.

A Novel Deep Blue LE-Dominated HLCT Excited State Design Strategy and Material for OLED.

Deep blue luminescent materials play a crucial role in the organic light-emitting diodes (OLEDs). In this work, a novel deep blue molecule based on hybridized local and charge-transfer (HLCT) excited state was reported with the emission wavelength of 423 nm. The OLED based on this material achieved high maximum external quantum efficiency (EQE) of 4% with good color purity. The results revealed that the locally-excited (LE)-dominated HLCT excited state had obvious advantages in short wavelength and narrow spectrum emission. What is more, the experimental and theoretical combination was used to describe the excited state characteristic and to understand photophysical property.

Uterine Massage to Reduce Blood Loss Before Delivery of the Placenta in Caesarean Section: A Retrospective Cohort Study.

BACKGROUND/OBJECTIVE: To estimate the effectiveness of uterine massage UM in reducing blood loss before delivery of placenta in CS. METHODS: This was a retrospective cohort study of 1393 women who delivered with CS. Patients who underwent UM (671women) were compared with those who underwent controlled cord traction (722 women). According to risk assessment of PPH, 2 groups were both divided to low risk group and high risk group. Outcomes included blood loss amount within 2 h after delivery, incidence of PPH and intractable PPH. RESULTS: Blood loss amount within 2 h was lower in UM group than CCT group(516.6±196.5 ml compared with 674.1±272.2 ml, P<0.01). The incidence of PPH and intractable PPH didn't differ significantly between the 2 groups (6.7% compared with 9.1%, P=0.09 and 3.9% compared with 5.3%, P=0.22,respectively).In high risk group, the amount of blood loss within 2 h and the incidence of PPH were both lower in UM group (n=382) than CCT group (n=407) (576.8±228.1 ml compared with 854.9±346.1 ml, P<0.01 and 7.1% compared with 11.3%,P=0.04 ,respectively). The incidence of intractable PPH didn't differ significantly between the 2 groups (4.7% compared with 6.9%,P=0.19). In low risk group, the 3 outcomes didn't differ significantly between the 2 groups(n=289 vs. 315) (428.5±172.6 ml compared with 447.9±180.5 ml; 6.2% compared with 6.3%; 2.8% compared with 3.2%; P=0.56, 0.95 and 0.77,respectively). CONCLUSION: In high risk patients of PPH, UM before delivery of placenta contributed to reduce blood loss in CS.

Poly(3-hexylthiophene)s Functionalized with N-Heterocyclic Carbenes as Robust and Conductive Ligands for the Stabilization of Gold Nanoparticles.

Recently, N-heterocyclic carbenes (NHCs) are explored as anchor groups to bind organic ligands to colloidal gold (i.e. gold nanoparticles, Au NPs), yet these efforts are confined to non-conjugated ligands so far-that is, focused solely on exploiting the stability aspect. Using NHCs to link Au NPs and electronically active organic components, for example, conjugated polymers (CPs), will allow capitalizing on both the stability as well as the inherent conductivity of the NHC anchors. Here, we report three types of Br-NHC-Au-X (X=Cl, Br) complexes, which, when used as starting points for Kumada polymerizations, yield regioregular poly(3-hexylthiophenes)-NHC-Au (P3HTs-NHC-Au) with narrow molecular weight distributions. The corresponding NPs are obtained via direct reduction and show excellent thermal as well as redox stability. The NHC anchors enable electron delocalization over the gold/CP interface, resulting in an improved electrochromic response behavior in comparison with P3HT-NHC-Au.

Pressure-Induced Blue-Shifted and Enhanced Emission: A Cooperative Effect between Aggregation-Induced Emission and Energy-Transfer Suppression.

Most organic piezochromic materials exhibit red-shifted and quenched emission as pressure increases. However, an abnormal phenomenon of pressure-induced blue-shifted and enhanced emission is observed in a 9-(3-(1,2,2-triphenylvinyl)phenyl)anthracene crystal, which is based on discrete π-π anthracene (AN) dimers stacking with tetraphenylethylene (TPE) as spacer. A blue-shifted emission appears and strengthens when the pressure is more than 1.23 GPa, and it reaches the maximum when the pressure is 4.28 GPa. This phenomenon is ascribed to the cooperative effect between the aggregation-induced emission of TPE units and energy-transfer suppression from TPE to an AN excimer. This work reports a new concept in the piezochromic field and provides a novel strategy to achieve luminescence from a high-lying excited state.

Electron Beam Irradiation as a General Approach for the Rapid Synthesis of Covalent Organic Frameworks under Ambient Conditions.

Crystalline porous materials such as covalent organic frameworks (COFs) are advanced materials to tackle challenges of catalysis and separation in industrial processes. Their synthetic routes often require elevated temperatures, closed systems with high pressure, and long reaction times, hampering their industrial applications. Here we use a traditionally unperceived strategy to assemble highly crystalline COFs by electron beam irradiation with controlled received dosage, contrasting sharply with the previous observation that radiation damages the crystallinity of solids. Such synthesis by electron beam irradiation can be achieved under ambient conditions within minutes, and the process is amendable for large-scale production. The intense and targeted energy input to the reactants leads to new reaction pathways that favor COF formation in nearly quantitative yield. This strategy is applicable not only to known COFs but also to new series of flexible COFs that are difficult to obtain using traditional methods.

Molcontroller: A VMD Graphical User Interface Featuring Molecule Manipulation.

Visual Molecular Dynamics (VMD) is one of the most widely used molecular graphics software in the community of theoretical simulations. So far, however, it still lacks a graphical user interface (GUI) for molecular manipulations when doing some modeling tasks. For instance, translation or rotation of a selected molecule(s) or part(s) of a molecule currently only can be achieved using tcl scripts. Here, we use the Tcl/Tk toolkit to develop a user-friendly GUI for VMD, named Molcontroller, which is featured by allowing users to quickly and conveniently perform various molecular manipulations. This GUI might be helpful for improving the modeling efficiency of VMD users.

Thermoplastic Membranes Incorporating Semiconductive Metal-Organic Frameworks: An Advance on Flexible X-ray Detectors.

Semiconductive metal-organic frameworks (MOFs) have emerged in applications such as chemical sensors, electrocatalysts, energy storage materials, and electronic devices. However, examples of semiconductive MOFs within flexible electronics have not been reported. We present flexible X-ray detectors prepared by thermoplastic dispersal of a semiconductive MOF (SCU-13) through a commercially available polymer, poly(vinylidene fluoride). The flexible detectors exhibit efficient X-ray-to-electric current conversion with enhanced charge-carrier mobility and low trap density compared to pelleted devices. A high X-ray detection sensitivity of 65.86 µCGyair -1 cm-2 was achieved, which outperforms other pelleted devices and commercial flexible X-ray detectors. We demonstrate that the MOF-based flexible detectors can be operated at multiple bending angles without a deterioration in detection performance. As a proof-of-concept, an X-ray phase contrast under bending conditions was constructed using a 5×5 pixelated MOF-based imager.

Visualization of Ultrasensitive and Recyclable Dual-Channel Fluorescence Sensors for Chemical Warfare Agents Based on the State Dehybridization of Hybrid Locally Excited and Charge Transfer Materials.

Simple and fast detection of chemical warfare agents vapor is necessary and urgent to fight against uncertain terrorist attacks and wars. In this contribution, inspired by the design of the hybrid locally excited and charge transfer (HLCT) excited state, two fast and highly sensitive visualization and fluorescence probes for DCP detection with relative small interstate coupling (J) TPA-2AC and TPA-9AC are reported. Upon exposure to saturated DCP vapor, the TPA-9AC test strips exhibited a rapid fluorescent response in no more than 1 s, accompanied by a change of the color from green to red. The detection limit of the test strips can be estimated as sensitive as 0.15 ppb, which is far superior to the "harmless" level (7 ppb) of human response to acute sarin exposure. More impressively, the fluorescent intensity of the test strips can be quickly restored when exposed to ammonia vapor for cyclic utilization, demonstrating an application prospect in the real-time detection of chemical warfare agents.

Unusual temperature-sensitive excimer fluorescence from discrete π-π dimer stacking of anthracene in a crystal.

Herein, an unusual blue shift in excimer fluorescence with increasing temperature was observed from a crystal with a discrete π-π anthracene dimer, originating from the more temperature-sensitive intermolecular geometry of the π-π dimer (e.g., π-π distance) compared to the intramolecular geometry of the monomer, which is confirmed by temperature-dependent single-crystal X-ray diffraction (XRD) measurements.