Coupling redox flow desalination with lithium recovery from spent lithium-ion batteries.

Electrochemical redox flow desalination is an emerging method to obtain freshwater; however, the costly requirement for continuously supplying and regenerating redox species limits their practical applications. Recycling of spent lithium-ion batteries is a growing challenge for their sustainable utilization. Existing battery recycling methods often involve massive secondary pollution. Here, we demonstrate a redox flow system to couple redox flow desalination with lithium recovery from spent lithium-ion batteries. The spontaneous reaction between a battery cathode material (LiFePO4) and ferricyanide enables the continuous regeneration of the redox species required for desalination. Several critical operating parameters are optimized, including current density, the concentrations of redox species, salt concentrations of brine, and the amounts of added LiFePO4. With the addition of 0.5920 g of spent LiFePO4 in five consecutive batches, the system can operate over 24 h, achieving 70.46 % lithium recovery in the form of LiCl aqueous solution at the concentration of 6.716 g·L-1. Simultaneously, the brine (25 mL, 10000 ppm NaCl) was desalinated to freshwater. Detailed cost analysis shows that this redox flow system could generate a revenue of ¥ 13.66 per kg of processed spent lithium-ion batteries with low energy consumption (0.77 MJ kg-1) and few greenhouse gas emissions indicating excellent economic and environmental benefits over existing lithium-ion battery recycling technologies, such as pyrometallurgical and hydrometallurgical methods. This work opens a new approach to holistically addressing water and energy challenges to achieve sustainable development.

Ammonia Electrosynthesis from Nitrate Using a Ruthenium-Copper Cocatalyst System: A Full Concentration Range Study.

Electrochemical synthesis of ammonia via the nitrate reduction reaction (NO3RR) has been intensively researched as an alternative to the traditional Haber-Bosch process. Most research focuses on the low concentration range representative of the nitrate level in wastewater, leaving the high concentration range, which exists in nuclear and fertilizer wastes, unexplored. The use of a concentrated electrolyte (≥1 M) for higher rate production is hampered by poor hydrogen transfer kinetics. Herein, we demonstrate that a cocatalytic system of Ru/Cu2O catalyst enables NO3RR at 10.0 A in 1 M nitrate electrolyte in a 16 cm2 flow electrolyzer, with 100% faradaic efficiency toward ammonia. Detailed mechanistic studies by deuterium labeling and operando Fourier transform infrared (FTIR) spectroscopy allow us to probe the hydrogen transfer rate and intermediate species on Ru/Cu2O. Ab initio molecular dynamics (AIMD) simulations reveal that adsorbed hydroxide on Ru nanoparticles increases the density of the hydrogen-bonded water network near the Cu2O surface, which promotes the hydrogen transfer rate. Our work highlights the importance of engineering synergistic interactions in cocatalysts for addressing the kinetic bottleneck in electrosynthesis.

AcMADS32 positively regulates carotenoid biosynthesis in kiwifruit by activating AcBCH1/2 expression.

Fruits provide abundant carotenoid nutrients for humans, whereas the understanding of the transcriptional regulatory mechanisms of carotenoids in fruits is still limited. Here, we identified a transcription factor AcMADS32 in kiwifruit, which was highly expressed in the fruit, correlated with carotenoid content and localized in the nucleus. The silencing expression of AcMADS32 significantly reduced the content of ß-carotene and zeaxanthin and expression of ß-carotene hydroxylase gene AcBCH1/2 in kiwifruit, while transient overexpression increased the accumulation of zeaxanthin, suggesting that AcMADS32 was an activator involved in the transcriptional regulation of carotenoid in fruit. When AcMADS32 was further stably transformed into kiwifruit, the content of total carotenoid and components in the leaves of transgenic lines significantly increased, and the expression level of carotenogenic genes was up-regulated. Moreover, Y1H and dual luciferase reporter experiments confirmed that AcMADS32 directly bound the AcBCH1/2 promoter and activated its expression. Through Y2H assays, AcMADS32 can interact with other MADS transcription factor AcMADS30, AcMADS64 and AcMADS70. These findings will contribute to our understanding of the transcriptional regulation mechanisms underlying carotenoid biosynthesis in plants.

Fabrication of copper phthalocyanine/reduced graphene oxide nanocomposites for efficient photocatalytic reduction of hexavalent chromium.

Copper(II) phthalocyanine (CuPc) and non-peripheral octamethyl-substituted copper(II) phthalocyanine (N-CuMe2Pc) were combined with reduced graphene oxide (rGO) via a precipitation method to form CuPc/rGO and N-CuMe2Pc/rGO nanocomposites, respectively. CuPc nanorods are distributed on rGO, and N-CuMe2Pc exists as nanorods and nanoparticles on rGO. The Cr(VI) removal ratio of N-CuMe2Pc/rGO exposed in simulated sunlight is 99.0% with a fast photocatalytic reaction rate of 0.0320 min-1, which is approximately 1.5 times faster than that of CuPc/rGO (0.0215 min-1) and far surpasses that of pristine phthalocyanine and rGO. As an electron acceptor, rGO can suppress the recombination of photo-induced electron-hole pairs and also can provide a large surface area for Cr(VI) removal, both of which are beneficial to the reducing capacity of the nanocomposites. The higher removal efficiency of N-CuMe2Pc/rGO compared with that of CuPc/rGO is attributed to the higher specific surface area, higher light harvesting, higher conductivity and more negative lowest unoccupied molecular orbital level of N-CuMe2Pc/rGO. The N-CuMe2Pc/rGO nanocomposite shows excellent photochemical recyclability which is essential for application in wastewater treatment.

In situ synthesis of N-CoMe2Pc/rGO nanocomposite with enhanced photocatalytic activity and stability in Cr(VI) reduction.

Graphene-based composites are widely used in the photocatalytic treatment of heavy-metal ions or dyes. In this study, we developed a facile in situ precipitation method for preparing a non-peripheral octamethyl-substituted cobalt(II)phthalocyanine (N-CoMe2Pc)/reduced graphene oxide (rGO) nanocomposite as an efficient photocatalyst. The physical and chemical properties of the nanocomposite were investigated by scanning electron microscopy, transmission electron microscopy, x-ray diffraction, and ultraviolet-visible, ultraviolet photoelectron, Fourier-transform infrared, Raman, and x-ray photoelectron spectroscopies. The results showed that the N-CoMe2Pc nanoparticles were immobilized on rGO nanosheets via π-π stacking interactions. The photocatalytic activity of the nanocomposite in the reduction of hexavalent chromium [Cr(VI), 10 mg/l] under visible-light irradiation was investigated. The Cr(VI) removal ratio reached 99.5% with a high photocatalytic rate of 0.0359 min-1, which is ten times faster than that achieved with pristine N-CoMe2Pc. The high removal efficiency is attributed to the following: (1) the number of active sites provided by nanodot-like N-CoMe2Pc is larger than that provided by bulk Pc, which can increase the production of photogenerated carriers, and (2) enhanced charge carrier separation resulting from intimate contact between N-CoMe2Pc nanodots and GO nanosheets. The N-CoMe2Pc/rGO also showed excellent stability and reusability. The Cr(VI) removal efficiency was 93.2% after eight photocatalytic test cycles.

Molecular Design Strategy in Developing Titanyl Phthalocyanines as Dopant-Free Hole-Transporting Materials for Perovskite Solar Cells: Peripheral or Nonperipheral Substituents?

We demonstrate a molecular design strategy to enhance the efficiency of phthalocyanine (Pc)-based hole-transporting materials (HTMs) in perovskite solar cells (PSCs). Herein, two titanyl phthalocyanine (TiOPc) derivatives are designed and applied as dopant-free HTMs in planar n-i-p-structured PSCs. The newly developed TiOPc compounds possess eight n-hexylthio groups attached to either peripheral (P-SC6-TiOPc) or nonperipheral (NP-SC6-TiOPc) positions of the Pc ring. Utilizing these dopant-free HTMs in PSCs with a mixed cation perovskite as the light-absorbing material and tin oxide (SnO2) as the electron-transporting material (ETM) results in a considerably enhanced efficiency for NP-SC6-TiOPc-based devices compared to PSCs using P-SC6-TiOPc. Hence, all of the photovoltaic parameters, including power conversion efficiency (PCE), fill factor, open-circuit voltage, and short-circuit current density, are remarkably improved from 5.33 ± 1.01%, 33.34 ± 3.45%, 0.92 ± 0.18 V, and 17.33 ± 2.08 mA cm-2 to 15.83 ± 0.44%, 69.03 ± 1.59%, 1.05 ± 0.01 V, and 21.80 ± 0.36 mA cm-2, respectively, when using the nonperipheral-substituted TiOPc derivative as the HTM in a PSC. Experimental and computational analysis suggests more compact molecular packing for NP-SC6-TiOPc than P-SC6-TiOPc in the solid state due to stronger π-π interactions, leading to thin films with better quality and higher performance in hole extraction and transportation. PSCs with NP-SC6-TiOPc also offer much higher long-term stability than P-SC6-TiOPc-based devices under ambient conditions with a relative humidity of 75%.