Photovoltaic-driven dual-oxidation seawater electrolyzer for sustainable lithium recovery.

The insatiable demand for lithium in portable energy storage necessitates a sustainable and low-carbon approach to its recovery. Conventional hydrometallurgical and pyrometallurgical methods heavily involve hazardous chemicals and significant CO2 emissions. Herein, by integrating electrode oxidation with electrolyte oxidation, we establish a photovoltaic-driven "dual-oxidation" seawater electrolyzer system for low-carbon footprint and high lithium recovery. A 98.96% lithium leaching rate with 99.60% product purity was demonstrated for lithium recovery from spent LiFePO4 cathode materials. In-depth mechanism studies reveal that the electric field-driven electrode oxidation and in situ generated oxidative electrolyte synergetically contributes to lithium ions leaching via a structural framework elements oxidation and particle corrosion splitting synergy. This dual-oxidation mechanism facilitates rapid and efficient lithium extraction with broad universality, offering significant economic and environmental benefits. Our work showcases a promising strategy for integrating dual oxidation within a photovoltaic-driven seawater electrolyzer, paving the way for low-carbon lithium recovery from diverse solid wastes and minerals within a sustainable circular economy.

Regulating the reduction reaction pathways via manipulating the solvation shell and donor number of the solvent in Li-CO2 chemistry.

Transforming CO2 into valuable chemicals is an inevitable trend in our current society. Among the viable end-uses of CO2, fixing CO2 as carbon or carbonates via Li-CO2 chemistry could be an efficient approach, and promising achievements have been obtained in catalyst design in the past. Even so, the critical role of anions/solvents in the formation of a robust solid electrolyte interphase (SEI) layer on cathodes and the solvation structure have never been investigated. Herein, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in two common solvents with various donor numbers (DN) have been introduced as ideal examples. The results indicate that the cells in dimethyl sulfoxide (DMSO)-based electrolytes with high DN possess a low proportion of solvent-separated ion pairs and contact ion pairs in electrolyte configuration, which are responsible for fast ion diffusion, high ionic conductivity, and small polarization. The 3 M DMSO cell delivered the lowest polarization of 1.3 V compared to all the tetraethylene glycol dimethyl ether (TEGDME)-based cells (about 1.7 V). In addition, the coordination of the O in the TFSI- anion to the central solvated Li+ ion was located at around 2 Å in the concentrated DMSO-based electrolytes, indicating that TFSI- anions could access the primary solvation sheath to form an LiF-rich SEI layer. This deeper understanding of the electrolyte solvent property for SEI formation and buried interface side reactions provides beneficial clues for future Li-CO2 battery development and electrolyte design.

The circadian clock gene bmal1 is necessary for co-ordinated circatidal rhythms in the marine isopod Eurydice pulchra (Leach).

Circadian clocks in terrestrial animals are encoded by molecular feedback loops involving the negative regulators PERIOD, TIMELESS or CRYPTOCHROME2 and positive transcription factors CLOCK and BMAL1/CYCLE. The molecular basis of circatidal (~12.4 hour) or other lunar-mediated cycles (~15 day, ~29 day), widely expressed in coastal organisms, is unknown. Disrupting circadian clockworks does not appear to affect lunar-based rhythms in several organisms that inhabit the shoreline suggesting a molecular independence of the two cycles. Nevertheless, pharmacological inhibition of casein kinase 1 (CK1) that targets PERIOD stability in mammals and flies, affects both circadian and circatidal phenotypes in Eurydice pulchra (Ep), the speckled sea-louse. Here we show that these drug inhibitors of CK1 also affect the phosphorylation of EpCLK and EpBMAL1 and disrupt EpCLK-BMAL1-mediated transcription in Drosophila S2 cells, revealing a potential link between these two positive circadian regulators and circatidal behaviour. We therefore performed dsRNAi knockdown of Epbmal1 as well as the major negative regulator in Eurydice, Epcry2 in animals taken from the wild. Epcry2 and Epbmal1 knockdown disrupted Eurydice's circadian phenotypes of chromatophore dispersion, tim mRNA cycling and the circadian modulation of circatidal swimming, as expected. However, circatidal behaviour was particularly sensitive to Epbmal1 knockdown with consistent effects on the power, amplitude and rhythmicity of the circatidal swimming cycle. Thus, three Eurydice negative circadian regulators, EpCRY2, in addition to EpPER and EpTIM (from a previous study), do not appear to be required for the expression of robust circatidal behaviour, in contrast to the positive regulator EpBMAL1. We suggest a neurogenetic model whereby the positive circadian regulators EpBMAL1-CLK are shared between circadian and circatidal mechanisms in Eurydice but circatidal rhythms require a novel, as yet unknown negative regulator.

Chemically coupling SnO2 quantum dots and MXene for efficient CO2 electroreduction to formate and Zn-CO2 battery.

Electrochemical conversion of CO2 into formate is a promising strategy for mitigating the energy and environmental crisis, but simultaneously achieving high selectivity and activity of electrocatalysts remains challenging. Here, we report low-dimensional SnO2 quantum dots chemically coupled with ultrathin Ti3C2Tx MXene nanosheets (SnO2/MXene) that boost the CO2 conversion. The coupling structure is well visualized and verified by high-resolution electron tomography together with nanoscale scanning transmission X-ray microscopy and ptychography imaging. The catalyst achieves a large partial current density of -57.8 mA cm-2 and high Faradaic efficiency of 94% for formate formation. Additionally, the SnO2/MXene cathode shows excellent Zn-CO2 battery performance, with a maximum power density of 4.28 mW cm-2, an open-circuit voltage of 0.83 V, and superior rechargeability of 60 h. In situ X-ray absorption spectroscopy analysis and first-principles calculations reveal that this remarkable performance is attributed to the unique and stable structure of the SnO2/MXene, which can significantly reduce the reaction energy of CO2 hydrogenation to formate by increasing the surface coverage of adsorbed hydrogen.

SESAM mode-locked Yb:GdScO3 laser.

We report on the investigation of continuous-wave (CW) and SEmiconductor Saturable Absorber Mirror (SESAM) mode-locked operation of a Yb:GdScO3 laser. Using a single-transverse-mode, fiber-coupled InGaAs laser diode at 976 nm as a pump source, the Yb:GdScO3 laser delivers 343 mW output power at 1062 nm in the CW regime, which corresponds to a slope efficiency of 52%. Continuous tuning is possible across a wavelength range of 84 nm (1027-1111 nm). Using a commercial SESAM to initiate mode-locking and stabilize soliton-type pulse shaping, the Yb:GdScO3 laser produces pulses as short as 42 fs at 1065.9 nm, with an average output power of 40 mW at 66.89 MHz. To the best of our knowledge, this is the first demonstration of passively mode-locking with Yb:GdScO3 crystal.

Continuous-wave and SESAM mode-locked operation of a Yb:YSr3(PO4)3 laser.

We report on the continuous-wave (CW) and, for what we believe to be the first time, passively mode-locked (ML) laser operation of an Yb3+-doped YSr3(PO4)3 crystal. Utilizing a 976-nm spatially single-mode, fiber-coupled laser diode as pump source, the Yb:YSr3(PO4)3 laser delivers a maximum CW output power of 333 mW at 1045.8 nm with an optical efficiency of 55.7% and a slope efficiency of 60.9%. Employing a quartz-based Lyot filter, an impressive wavelength tuning range of 97 nm at the zero level was achieved in the CW regime, spanning from 1007 nm to 1104 nm. In the ML regime, incorporating a commercially available semiconductor saturable absorber mirror (SESAM) to initiate and maintain soliton-like pulse shaping, the Yb:YSr3(PO4)3 laser generated pulses as short as 61 fs at 1062.7 nm, with an average output power of 38 mW at a repetition rate of ∼66.7 MHz.

Growth, spectroscopy and laser operation of Tm,Ho:GdScO3 perovskite crystal.

We report on the growth, polarized spectroscopy and first laser operation of an orthorhombic (space group Pnma) Tm3+,Ho3+-codoped gadolinium orthoscandate (GdScO3) perovskite-type crystal. A single crystal of 3.76 at.% Tm, 0.35 at.% Ho:GdScO3 was grown by the Czochralski method. Its polarized absorption and fluorescence properties were studied revealing a broadband emission around 2 µm. The parameters of the Tm3+ ↔ Ho3+ energy transfer was quantified, P28 = 1.30 × 10-22 cm3µs-1, and P71 = 0.99 × 10-23 cm3µs-1, and the thermal equilibrium lifetime was measured to be 3.5 ms. The crystal-field splitting of Tm3+ and Ho3+ multiplets in Cs symmetry sites of the perovskite structure was determined by low-temperature spectroscopy and the mechanism of spectral line broadening is discussed. The continuous-wave Tm,Ho:GdScO3 laser generated 1.16 W at ∼2.1 µm with a slope efficiency of 50.5%, a laser threshold of 184 mW, a linear laser polarization (E || c) and a spatially single-mode output. The Tm,Ho:GdScO3 crystal is promising for broadly tunable and femtosecond mode-locked lasers emitting above 2 µm.

Growth, spectroscopy and SESAM mode-locking of a "mixed" Yb:Ca(Gd,Y)AlO4 disordered crystal.

We present the growth, spectroscopy, continuous-wave (CW) and passively mode-locked (ML) operation of a novel "mixed" tetragonal calcium rare-earth aluminate crystal, Yb3+:Ca(Gd,Y)AlO4. The absorption, stimulated-emission, and gain cross-sections are derived for π and σ polarizations. The laser performance of a c-cut Yb:Ca(Gd,Y)AlO4 crystal is studied using a spatially single-mode, 976-nm fiber-coupled laser diode as a pump source. A maximum output power of 347 mW is obtained in the CW regime with a slope efficiency of 48.9%. The emission wavelength is continuously tunable across 90 nm (1010 - 1100 nm) using a quartz-based Lyot filter. With a commercial SEmiconductor Saturable Absorber Mirror to initiate and maintain ML operation, soliton pulses as short as 35 fs are generated at 1059.8 nm with an average output power of 51 mW at ∼65.95 MHz. The average output power can be scaled to 105 mW for slightly longer pulses of 42 fs at 1063.5 nm.

Selective Capacitive Recovery of Rare-Earth Ions from Wastewater over Phosphorus-Modified TiO2 Cathodes via an Electro-Adsorption Process.

Large amounts of wastewater containing low-concentration (<10 ppm) rare-earth ions (REIs) are discharged annually in China's rare-earth mining and processing industry, resulting in severe environmental pollution and economic losses. Hence, achieving efficient selective recovery of low-concentration REIs from REIs-containing wastewater is essential for environmental protection and resource recovery. In this study, a pseudocapacitance system was designed for highly efficient capacitive selective recovery of REIs from wastewater using the titanium dioxide/P/C (TiO2/P/C) composite electrode, which exhibited over 99% recovery efficiency for REIs, such as Eu3+, Dy3+, Tb3+, and Lu3+ in mixed solution. This system maintained high efficiency and more than 90 times the enrichment concentration of REIs even after 100 cycles. Ti4+ of TiO2 was reduced to Ti3+ of Ti3O5 under forward voltage in the system, which trapped the electrons of phosphorus site and caused it to be oxidized to phosphate with a strong affinity for REIs, thus improving the selectivity of REIs. Under reverse voltage, Ti3O5 was oxidized to TiO2, which transferred electrons to phosphate and transformed to the phosphorus site, resulting in the desorption and enrichment of REIs and the regeneration of the electrode. This study provides a promising method for the efficient recovery of REIs from wastewater.

Lack of causal association between epilepsy and dementia: A Mendelian randomization analysis.

OBJECTIVE: Epidemiological studies have reported an association between epilepsy and dementia. However, the causal relationship between epilepsy and the risk of dementia is not clear. We aimed to inspect the causal effect of epilepsy on memory loss and dementia. METHODS: We analyzed summary data of epilepsy, memory loss, and dementia from the genome-wide association study (GWAS) using the two-sample Mendelian randomization (MR) method. We used the estimated odds ratio of memory loss and dementia associated with each of the genetically defined traits to infer evidence for a causal relationship with the following exposures: all epilepsy, focal epilepsy (including focal epilepsy with hippocampal sclerosis, lesion-negative focal epilepsy, and focal epilepsy with other lesions), and genetic generalized epilepsy (including childhood absence epilepsy, generalized tonic-clonic seizures alone, Juvenile absence epilepsy, and Juvenile myoclonic epilepsy). RESULTS: According to the result of MR using the inverse variance weighted method (IVW), we found that genetically predicted epilepsy did not causally increase the risk of memory loss and dementia (p > 0.05). Results of the MR-Egger and weighted median method were consistent with the IVW method. CONCLUSIONS: No evidence has been found to support the notion that epilepsy can result in memory loss and dementia. The associations observed in epidemiological studies could be attributed, in part, to confounding or nongenetic determinants.

Cooling has stimulated soil carbon storage in forest ecosystems.

The interactive effect of soil cooling and nitrogen (N) addition can accurately simulate climatic and anthropogenic effects on terrestrial and other land-based ecosystems, but direct empirical measurements on the effects of cooling and N addition on soil carbon (C) and N are lacking. Hence, transplanting soils into colder regions was used to evaluate the effects of cooling and N addition on soil C and N. We used PVCs of 30 cm in height and 8 cm in diameter to extract soil samples. Soil C and N were significantly (P < 0.05) increased by transplanting soils into colder regions. In contrast, cooling has insignificantly (P > 0.05) increased the soil dissolved organic C (DOC) and dissolved organic (DON), but the effect was negatively significant on soil pH compared to the C/N ratio. Similarly, N addition significantly increased the measured soil N stock. However, the effect was negatively significant on soil pH (P < 0.05) compared to the C/N ratio (P > 0.05). Nevertheless, the interaction of cooling and N addition did not affect the soil C and N storage. A similar effect was observed on the soil DOC and DON. The results presented here illustrate that transplanting soils into colder regions and N deposition has perfectly simulated the effects of climate-forcing factors on soil C and N storage in terrestrial and other land-based ecosystems. Accordingly, this study suggests that low temperatures have stimulated the accumulation of the measured soil organic and dissolved properties, but the effect is less consequential when low temperature interacts with N addition in high-elevation areas where ecosystem structures and functions are limited by temperature and may serve as a baseline for future research on land feedbacks to the climate system.

Long-Term Autotrophic Growth and Solar-to-Chemical Conversion in Shewanella Oneidensis MR-1 through Light-Driven Electron Transfer.

Members of the genus Shewanella are known for their versatile electron accepting routes, which allow them to couple decomposition of organic matter to reduction of various terminal electron acceptors for heterotrophic growth in diverse environments. Here, we report autotrophic growth of Shewanella oneidensis MR-1 with photoelectrons provided by illuminated biogenic CdS nanoparticles. This hybrid system enables photosynthetic oscillatory acetate production from CO2 for over five months, far exceeding other inorganic-biological hybrid system that can only sustain for hours or days. Biochemical, electrochemical and transcriptomic analyses reveal that the efficient electron uptake of S. oneidensis MR-1 from illuminated CdS nanoparticles supplies sufficient energy to stimulate the previously overlooked reductive glycine pathway for CO2 fixation. The continuous solar-to-chemical conversion is achieved by photon induced electric recycling in sulfur species. Overall, our findings demonstrate that this mineral-assisted photosynthesis, as a widely existing and unique model of light energy conversion, could support the sustained photoautotrophic growth of non-photosynthetic microorganisms in nutrient-lean environments and mediate the reversal of coupled carbon and sulfur cycling, consequently resulting in previously unknown environmental effects. In addition, the hybrid system provides a sustainable and flexible platform to develop a variety of solar products for carbon neutrality.

Aqueous Electroreduction of Nitric Oxide to Ammonia at Low Concentration via Vacancy Engineered FeOCl.

Electroreduction of nitric oxide (NO) to NH3 (NORR) has gained extensive attention for the sake of low carbon emission and air pollutant treatment. Unfortunately, NORR is greatly hindered by its sluggish kinetics, especially under low concentrations of NO. Herein, we developed a chlorine (Cl) vacancy strategy to overcome this limitation over FeOCl nanosheets (FeOCl-VCl ). Density functional theory (DFT) calculations revealed that the Cl vacancy resulted in defective Fe with sharp d-states characteristics in FeOCl-VCl to enhance the absorption and activation of NO. In situ X-ray absorption near-edge structure (XANES) and attenuated total reflection-infrared spectroscopy (ATR-IR) verified the lower average oxidation state of defective Fe to enhance the electron transfer for NO adsorption/activation and facilitate the generation of key NHO and NHx intermediates. As a result, the FeOCl-VCl exhibited superior NORR activities with the NH3 Faradaic efficiency up to 91.1 % while maintaining a high NH3 yield rate of 455.4 µg cm-2 h-1 under 1.0 vol % NO concentration, competitive with those of previously reported literatures under higher NO concentration. Further, the assembled Zn-NO battery utilizing FeOCl-VCl as cathode delivered a record peak power density of 6.2 mW cm-2 , offering a new route for simultaneous NO removal, NH3 production, and energy supply.

Anionic Sublattices in Halide Solid Electrolytes: A Case Study with the High-Pressure Phase of Li3ScCl6.

The Li3MX6 compounds (M=Sc, Y, In; X=Cl, Br) are known as promising ionic conductors due to their compatibility with typical metal oxide cathode materials. In this study, we have successfully synthesized γ-Li3ScCl6 using high pressure for the first time in this family. Structural analysis revealed that the high-pressure polymorph crystallizes in the polar and chiral space group P63mc with hexagonal close-packing (hcp) of anions, unlike the ambient-pressure α-Li3ScCl6 and its spinel analog with cubic closed packing (ccp) of anions. Investigation of the known Li3MX6 family further revealed that the cation/anion radius ratio, rM/rX, is the factor that determines which anion sublattice is formed and that in γ-Li3ScCl6, the difference in compressibility between Sc and Cl exceeds the ccp rM/rX threshold under pressure, enabling the ccp-to-hcp conversion. Electrochemical tests of γ-Li3ScCl6 demonstrate improved electrochemical reduction stability. These findings open up new avenues and design principles for lithium solid electrolytes, enabling routes for materials exploration and tuning electrochemical stability without compositional changes or the use of coatings.

Kerr-lens mode-locking of an Yb:CLNGG laser.

We report on a Kerr-lens mode-locked laser based on an Yb3+-doped disordered calcium lithium niobium gallium garnet (Yb:CLNGG) crystal. Pumping by a spatially single-mode Yb fiber laser at 976 nm, the Yb:CLNGG laser delivers soliton pulses as short as 31 fs at 1056.8 nm with an average output power of 66 mW and a pulse repetition rate of ∼77.6 MHz via soft-aperture Kerr-lens mode-locking. The maximum output power of the Kerr-lens mode-locked laser amounted to 203 mW for slightly longer pulses of 37 fs at an absorbed pump power of 0.74 W, which corresponds to a peak power of 62.2 kW and an optical efficiency of 20.3%.

Diode-pumped mode-locked Yb:Sc2SiO5 laser generating 38 fs pulses.

We report on sub-40 fs pulse generation from a Yb:Sc2SiO5 laser pumped by a spatially single-mode fiber-coupled laser diode at 976 nm. A maximum output power of 545 mW was obtained at 1062.6 nm in the continuous-wave regime, corresponding to a slope efficiency of 64% and a laser threshold of 143 mW. A continuous wavelength tuning across 80 nm (1030 -1110 nm) was also achieved. Implementing a SESAM for starting and stabilizing the mode-locked operation, the Yb:Sc2SiO5 laser delivered soliton pulses as short as 38 fs at 1069.5 nm with an average output power of 76 mW at a pulse repetition rate of ∼79.8 MHz. The maximum output power was scaled to 216 mW for slightly longer pulses of 42 fs, which corresponded to a peak power of 56.6 kW and an optical efficiency of 22.7%. To the best of our knowledge, these results represent the shortest pulses ever achieved with any Yb3+-doped rare-earth oxyorthosilicate crystal.

56-fs diode-pumped SESAM mode-locked Yb:YAl3(BO3)4 laser.

We report on the first sub-60 fs pulse generated from a diode-pumped SESAM mode-locked Yb-laser based on a non-centrosymmetric Yb:YAl3(BO3)4 crystal as a gain medium. In the continuous-wave regime, pumping with a spatially single-mode, fiber-coupled 976 nm InGaAs laser diode, the Yb:YAl3(BO3)4 laser generated 391 mW at 1041.7 nm with a slope efficiency as high as 65.1%, and a wavelength tuning across 59 nm (1019 to 1078 nm) was achieved. By implementing a commercial SESAM to initiate and sustain the soliton type mode-locking, and using only a 1 mm-thick laser crystal, the Yb:YAl3(BO3)4 laser delivered pulses as short as 56 fs at a central wavelength of 1044.6 nm with an average output power of 76 mW at a pulse repetition rate of ∼67.55 MHz. To the best of our knowledge, this result represents the shortest pulses ever achieved from Yb:YAB crystal.

Sub-50 fs diode-pumped SESAM mode-locked Yb:SrF2 laser.

We report on sub-50 fs pulse generation from a passively mode-locked Yb:SrF2 laser pumped with a spatially single-mode, fiber-coupled laser diode at 976 nm. In the continuous-wave regime, the Yb:SrF2 laser generated a maximum output power of 704 mW at 1048 nm with a threshold of 64 mW and a slope efficiency of 77.2%. A continuous wavelength tuning across 89 nm (1006 - 1095 nm) was achieved with a Lyot filter. By implementing a SEmiconductor Saturable Absorber Mirror (SESAM) for initiating and sustaining the mode-locked operation, soliton pulses as short as 49 fs were generated at 1057 nm with an average output power of 117 mW at a pulse repetition rate of ∼75.9 MHz. The maximum average output power of the mode-locked Yb:SrF2 laser was scaled up to 313 mW for slightly longer pulses of 70 fs at 1049.4 nm, corresponding to a peak power of 51.9 kW and an optical efficiency of 34.7%.

Highly Selective Monomethylation of Amines with CO2 /H2 via Ag/Al2 O3 as a Catalyst.

The selective synthesis of monomethylated amines with CO2 is particularly challenging because the formation of tertiary amines is thermodynamically more favorable. Herein, a new strategy for the controllable synthesis of N-monomethylated amines from primary amines and CO2 /H2 is explored. First-principle calculations reveal that the dissociation of H2 via an heterolytic route reduces the reactivity of methylated amines and thus inhibit successive methylation. In situ DRIFTS proves the process of formation and decomposition of ammonium salt by secondary amine reversible binding with H+ on the Ag/Al2 O3 catalyst, thereby reducing its reactivity. Meanwhile, the energy barrier for the rate-determining step of monomethylation was much lower than that of overmethylation (0.34 eV vs. 0.58 eV) means amines monomethylation in preference to successive methylation. Under optimal reaction conditions, a variety of amines were converted to the corresponding monomethylated amines in good to excellent yields, and more than 90 % yield of product was obtained.

Intermediates-induced CO2 Reduction Reaction Activity at Single-Atom M-N2 (M=Fe, Co, Ni) Sites.

Single-atom M-N2 (M=Fe, Co, Ni) catalysts exhibit high activity for CO2 reduction reaction (CO2 RR). However, the CO2 RR mechanism and the origin of activity at the single-atom sites remain unclear, which hinders the development of single-atom M-N2 catalysts. Here, using density functional theory calculations, we reveal intermediates-induced CO2 RR activity at the single-atom M-N2 sites. At the M-N2 sites, the asymmetric *O*CO configuration tends to split into *CO and *OH intermediates. Intermediates become part of the active moiety to form M-(CO)N2 or M-(OH)N2 sites, which optimizes the adsorption of intermediates on the M sites. The maximum free energy differences along the optimal CO2 RR pathway are 0.30, 0.54, and 0.28 eV for Fe-(OH)N2 , Co-(CO)N2 , and Ni-(OH)N2 sites respectively, which is lower than those of Fe-N2 (1.03 eV), Co-N2 (1.24 eV) and Ni-N2 (0.73 eV) sites. The intermediate modification can shift the d-band center of the spin-up (minority) state downward by regulating the charge distribution at the M sites, leading to less charge being accepted by the intermediates from the M sites. This work provides new insights into the understanding of the activity of single-atom M-N2 sites.