Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid

Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the leachate.These methods usually are followed by a series of separation steps such as precipitation,extraction,and stripping to separate the individual valuable metals.In this study,we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids.Under optimal leaching conditions(leaching time of 1.5 h,leaching temperature of 70°C,liquid-solid ratio of 4 mL/g,oxalic acid ratio of 1.3,and sulfuric acid ratio of 1.3),the lithium leaching efficiency reached89.6%,and the leaching efficiencies of Ni,Co,and Mn were 12.8%,6.5%,and 21.7%.X-ray diffraction(XRD)and inductively coupled plasma optical emission spectrometer(ICP-OES)analyses showed that most of the Ni,Co,and Mn in the raw material remained as solid residue oxides and oxalates.This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.

Enhancing selectivity in acidic CO_(2) electrolysis:Cation effects and catalyst innovation

The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2) conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2) electrolysis.It commences with an overview of the latest advancements in acidic CO_(2) electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2) electrolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2) electrolysis are suggested.

No difference in high-magnification morphology and hyaluronic acid binding in the selection of euploid spermatozoa with intact DNA

In this study, we compared conventional sperm selection with high-magnification morphology based on the motile sperm organellar morphology examination （MSOME） criteria, and hyaluronic acid （HA） binding for sperm chromosome aneuploidy and DNA fragmentation rates. Semen from 50 severe male factor cases was processed through density gradient centrifugation, and subjected to sperm selection by using the conventional method （control）, high magnification at x6650 or HA binding. Aneuploidy was detected by fluorescence in situ hybridization with probes for chromosomes 13, 18, 21, X and Y, and DNA fragmentation by the terminal deoxynucleotidyl transferase dUTP nick end labelling （TUNEL） method. Spermatozoa selected under high-magnification had a lower DNA fragmentation rate （2.6% vs. 1.7%; P=0.032）, with no significant difference in aneuploidy rate （0.8% vs0.7%; P=0.583）, than those selected by the HA binding method. Spermatozoa selected by both methods had much lower aneuploidy and DNA fragmentation rate than the controls （7% aneuploidy and 26.8% DNA fragmentation rates, respectively）. In the high-magnification group, the aneuploidy rate was lower when the best spermatozoa were selected than when only the second-best spermatozoa were available for selection, but the DNA fragmentation rate was not different. In conclusion, sperm selection under high magnification was more effective than under HA binding in selecting spermatozoa with low DNA fragmentation rate, but the small difference （0.9%） might not be clinically meaningful. Both methods were better than the conventional method of sperm selection.

Oxygen-doped Carbon Nitride Nanocages with Efficient Photon-to-Electron Conversion for Selective Oxidation of Xylose/Xylan to Yield Xylonic Acid

Highly efficient photon-to-electron conversion is crucial for achieving photocatalytic conversion.In this study,oxygen-doped carbon nitride nanocages(O@CNNCs)were engineered via dual strategies of morphology-controlled heteroatom doping,which was successfully used in the photocatalytic selective oxidation of xylose/xylan to xylonic acid.The nanocage-shaped O@CNNCs had a larger surface area,which was 4.02 times of carbon nitride(CN).Furthermore,with the assistance of morphology regulation and O-doping,O@CNNCs exhibit highly efficient photon-to-electron conversion,enhanced visible-light utilization,high photocurrent,low resistance,and fast separation/migration of electron-hole pairs.Correspondingly,the photocatalytic oxidation of xylose to xylonic acid using O@CNNCs was successfully achieved under mild reaction conditions with a yield of 83.4%.O@CNNCs have excellent recyclability,in which the yield of xylonic acid in the 5th cycle was 98.2%of its initial use.The O@CNNC photocatalytic system was also suitable for macromolecular xylan,and a xylonic acid yield of 77.34 mg was obtained when 100 mg xylan was used.The oxidation-active species captured experiments indicated that holes were crucial for the selective oxidation of xylose to xylonic acid.Overall,this study provides a new strategy for the preparation of photocatalysts with excellent photon-to-electron conversion and selective oxidation of biomass-derived feedstocks to xylonic acid.

Enhancing photo-generated carriers transfer of K-C_(3)N_(4)/UiO-66-NH_(2) with Er doping for efficient photocatalytic oxidation of furfural to furoic acid

Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visible light.The Er@K-C_(3)N_(4)/UiO-66-NH_(2) catalyst was synthesized using a straight-forward hydrothermal technique,and exhibited exceptional efficiency in the photocatalytic oxidation of furfural to furoic acid.The catalyst was thoroughly characterized,confirming the effective adjustment of the band gap energy of Er@K-C_(3)N_(4)/UiO-66-NH_(2).Upon the optimized reaction conditions,the conversion rate of furfural reached 89.3%,with a corresponding yield of furoic acid at 79.8%.The primary reactive oxygen species was identified as·O_(2)^(-) from ESR spectra and scavenger tests.The incorporation of Er and K into the catalyst enhanced the photogenerated carriers transfer rate,hence increasing the separating efficiency of photogenerated electron-hole pairs.This study expands the potential applications of rare earth element doped g-C_(3)N_(4) in the photocatalytic selective oxidation of furfurans.

Cu,N codoped carbon nanosheets encapsulating ultrasmall Cu nanoparticles for enhancing selective 1,2-propanediol oxidation

In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.

Understanding the roles of Brønsted/Lewis acid sites on manganese oxide-zeolite hybrid catalysts for low-temperature NH_(3)-SCR

Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.

Dendrite Spacing Selection during Directional Solidification of Pivalic Acid-Ethanol System

Unidirectional solidification of pivalic acid （PVA）-ethanol （Eth） mixture was performed to examine whether an allowable range of primary dendrite spacing definitely exists at a given growth velocity and how the range is history-dependent. PVA-0.59 wt pct Eth was unidirectionally solidified in the range of growth velocity 0.5-64 μm/s at the temperature gradient of 2.3 K/ram. Sequential change in growth velocity was imposed to determine the upper and lower limits for the allowable range of stable spacing. An allowable range of the steady state primary spacing was observed at a given growth velocity, and the extent of the range seems to be dependent on the degree to which step-increase or step-decrease in growth velocity is accomplished. As the degree of sequential change in growth velocity increases, the history-dependence of the selection for the primary dendrite spacing tends to disappear.

Natural selection in vertebrate evolution under genomic and biosphere biases based on amino acid content: Primitive vertebrate hagfish (<i>Eptatretus burgeri</i>)

Cluster analyses using the amino acid content predicted from the coding regions (13 genes) of complete vertebrate mitochondrial genomes as traits grouped selected vertebrates into two clusters, terrestrial and aquatic vertebrates. Exceptions were the hagfish (Eptatretus burgeri), thought to be an early ancestor of vertebrates, and the black spotted frog (Rana nigromaculata), which is terrestrial as an adult and aquatic as a larva. These two species fall into the terrestrial and aquatic clusters, respectively. Using the nucleotide (G, C, T and A) content in the coding and non-coding regions, and in the complete genome as traits, similar results were obtained but with some additional exceptions. In addition, phylogenetic analyses of 16S rRNA sequences produced a consistent result. The results of this study indicated that vertebrate evolution is controlled by natural selection under both an internal bias as a result of nucleotide replacement genomic rules, and an external bias caused by environmental biospheric conditions.

Selective oxidation of propane to acrylic acid over mixed metal oxide catalysts

The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid have been investigated and discussed. Among the catalysts studied, it was found that the MoVTeNbO catalyst calcined at a temperature of 600 ℃ showed the best performance in terms of propane conversion and selectivity for acrylic acid under an atmosphere of nitrogen. An effective MoVTeNbO oxide catalyst for propane selective oxidation to acrylic acid was obtained with a combination of a preferred metal atomic ratio （Mo1V0.31Te0.23Nb0.12）. The optimum reaction condition for the selective oxidation of propane was the molar ratio of C3H8 ：O2 ： H2O ： N2 = 4.4： 12.8 ： 15.3 ： 36.9. Under such conditions, the conversion of propane and the maximum yield of acrylic acid reached about 50% and 21%, respectively.

Morphology evolution of acetic acid-modulated MIL-53(Fe)for efficient selective oxidation of H2S

MIL-53(Fe)was synthesized using a“modulator approach”that utilizes acetic acid(HAc)as an additive to control the size and morphology of the resulting crystals.We demonstrate that after activation under vaccum at 100℃,the MIL-53(Fe)functions well for H2S selective oxidation.The introduction of acetic acid in the presence of benzene-1,4-dicarboxylic acid(H2BDC)would result in a series of MIL-53(Fe)nanocrystals(denoted as MIL-53(Fe)-xH,x stands for the volume of added HAc with morphology evoluting from irregular particles to short hexagonal columns.The vacuum treatment facilitates the removal of acetate groups,thus generating Fe3+Lewis acid sites.Consequently,the resulted MIL-53(Fe)-xH exhibits good catalytic activity(98%H2S conversion and 92%sulfur selectivity)at moderate reaction temperatures(100–190℃).The MIL-53(Fe)-5H is superior to the traditional iron-based catalysts,showing stable performance in a test period of 55 h.

Excitatory amino acid changes in the brains of rhesus monkeys following selective cerebral deep hypothermia and blood flow occlusion

Selective cerebral deep hypothermia and blood flow occlusion can enhance brain tolerance to ischemia and hypoxia and reduce cardiopulmonary complications in monkeys. Excitotoxicity induced by the release of a large amount of excitatory amino acids after cerebral ischemia is the major mechanism underlying ischemic brain injury and nerve cell death. In the present study, we used selective cerebral deep hypothermia and blood flow occlusion to block the bilateral common carotid arteries and/or bilateral vertebral arteries in rhesus monkey, followed by reperfusion using Ringer＇s solution at 4~C. Microdialysis and transmission electron microscope results showed that selective cerebral deep hypothermia and blood flow occlusion inhibited the release of glutamic acid into the extracellular fluid in the brain frontal lobe and relieved pathological injury in terms of the ultrastructure of brain tissues after severe cerebral ischemia. These findings indicate that cerebral deep hypothermia and blood flow occlusion can inhibit cytotoxic effects and attenuate ischemic/ hypoxic brain injury through decreasing the release of excitatory amino acids, such as glutamic acid.

A New Type of Dibenzoyl Tartaric Acid Selective Electrode Based on Polymer Membrane Containing Calixarene Ionophore

A new type of di benzoyl tartaric acid selective electr ode has been developed. Three double\| arm calixarene derivatives were emp loyed as the neutral ionophores. The poly(vinyl chloride) membrane electrode containing an amide derivative of ca lixarene as the neutral carrier an d a dibutyl phthalate as the plastici zer exhibited the highest sensitivity for dibenzoyl tartaric acid. The slop e of linear portion was 27.8 mV per c oncertration decade. The electrode has a fast response and a long lifetime .

Enzyme‐like mechanism of selective toluene oxidation to benzaldehyde over organophosphoric acid‐bonded nano‐oxides

The completely selective oxidation of toluene to benzaldehyde with dioxygen,without the need touse H_(2)O_(2),halogens,or any radical initiators,is a reaction long desired but never previously successful.Here,we demonstrate the enzyme‐like mechanism of the reaction over hexadecylphosphateacid(HDPA)‐bonded nano‐oxides,which appear to interact with toluene through specific recognition.The active sites of the catalyst are related to the ability of HDPA to change its bonding to theoxides between monodentate and bidentate during the reaction cycle.This greatly enhances themobility of the crystal oxygen or the reactivity of the catalyst,specifically in toluene transformations.The catalytic cycle of the catalyst is similar to that of methane monooxygenase.In thepresence of catalyst and through O_(2)oxidation,the conversion of toluene to benzaldehyde is initiatedat 70°C.We envision that this novel mechanism reveals alternatives for an attractive route to designhigh‐performance catalysts with bioinspired structures.

Evaluation of fatty acid metabolism and innate immunity interactions between commercial broiler, F1 layer × broiler cross and commercial layer strains selected for different growth potentials

Background： The broiler industry has undergone intense genetic selection over the past 50 yr. resulting in improvements for growth and feed efficiency, however, significant variation remains for performance and growth traits. Production improvements have been coupled with unfavourable metabolic consequences, including immunological trade-offs for growth, and excess fat deposition. To determine whether interactions between fatty acid（FA） metabolism and innate immunity may be associated with performance variations commonly seen within commercial broiler flocks, total carcass lipid %, carcass and blood FA composition, as wel as genes involved with FA metabolism, immunity and cel ular stress were investigated in male birds of a broiler strain, layer strain and F1 layer × broiler cross at d 14 post hatch. Heterophil：lymphocyte ratios, relative organ weights and bodyweight data were also compared.Results： Broiler bodyweight（n = 12） was four times that of layers（n = 12） by d 14 and had significantly higher carcass fat percentage compared to the cross（n = 6; P = 0.002） and layers（P = 0.017） which were not significantly different from each other（P = 0.523）. The carcass and whole blood FA analysis revealed differences in the FA composition between the three groups indicating altered FA metabolism, despite al being raised on the same diet. Genes associated with FA synthesis andβ-oxidation were upregulated in the broilers compared to the layers indicating a net overal increase in FA metabolism,which may be driven by the larger relative liver size as a percentage of bodyweight in the broilers. Genes involved in innate immunity such as TLR2 and TLR4, as wel as organel e stress indicators ERN1 and XBP1 were found to be nonsignificant, with the exception of high expression levels of XBP1 in layers compared to the cross and broilers. Additional y there was no difference in heterophil： lymphocytes between any of the birds.Conclusions： The results provide evidence that genetic selection may be associated with altered metabolic processes between broilers, layers and their F1 cross. Whilst there is no evidence of interactions between FA metabolism, innate immunity or cel ular stress, further investigations at later time points as growth and fat deposition increase would provide useful information as to the effects of divergent selection on key metabolic and immunological processes.

The nature of active sites in Pt–ReO_X/TiO_2 catalysts for selective hydrogenation of carboxylic acids to alcohols

The highly dispersed Pt-ReOx （x _〈 1 ） sites ca. 0.5 nm in size were formed via a successive and strong inter- action of the Re precursor with titania and then of the Pt complex with deposited low-valent rhenium oxide clusters. The size, charge and chemical composition were characterized by means of HRTEM/STEM with EDX mapping, XPS, and FTIRS. These sites with Re/Pt = 2 were shown to be highly active and selective in the hydrogenation of carboxylic acid to alcohol under very mild conditions （T = 130 ℃, P = 50 bar）. The reaction rate constant for the hydrogenation of hexanoic acid increased linearly with the Pt content. As for the homogeneous pincer-type Ru-organic complexes, the active Pt-ReOx sites can dissociate heterolytically the molecular hydrogen with the formation of hydroxyl groups and Pt hydride for hydrogenation of the carboxylic group. Indeed, TOF of 20 h 1 and selectivity of 98%-99% are approaching the values typical of homogeneous catalysts. The first order kinetics described well the experimental data obtained in a wide range of reaction conditions.

Design of 2,4-Dichlorophenoxyacetic Acid Imprinted Polymer with High Specificity and Selectivity

A widely used herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was imprinted on poly (4-vinylpyridine) (4-VP) using (40%) ethyleneglycol dimethacrylate (EGDMA) as crosslinking agent. The classical imprinting technology makes use of a high degree of crosslinking which does not allow the template molecules to move freely. So the binding sites, located in the central area of the three dimensional polymer matrix are hard to be accessed and the template molecules cannot be extracted totally. But here we propose a low crosslinked system with high specificity and selectivity. The imprinted and non-imprinted polymers were characterized by various spectroscopic techniques. The extent of binding was followed by batch equilibration method and compared with the respective non-imprinted polymer. Conditions for maximum specific rebinding were set by altering certain factors like template/monomer ratio, concentration of template solution, rebinding medium, mass of polymer and time of incubation. The selectivity of the imprinted polymer was investigated by comparing the binding with structural analogues of 2,4-D like, phenoxyacetic acid (POA), 4-chlorophenoxyacetic acid (4-CPOA) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). The imprinted polymer exhibited high affinity towards the template molecule and was selectively rebound to the specific sites. The binding towards the structural analogues depends on the number of chlorine in the benzene ring.

Effect of preparation conditions on selective oxidation of propane to acrylic acid

The effects of chemical composition and preparation conditions,especially calcination atmosphere and water content on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid were investigated.Among the catalysts studied,Mo_(1.0)V_(0.3)Te_(0.23)Nb_(0.12)O_(x) catalyst calcined in inert atmosphere at 600℃shows the best performance in terms of propane conversion and selectivity to acrylic acid.The results reveal that proper chemical composition, calcination atmosphere and water content affect greatly the catalysts in many ways including structure,chemical composition,which are related to their catalytic performances;and 51.0%propane conversion and 30.5%one-pass yield to acrylic acid can be achieved at the same time.

Sequential Extraction of Aluminum and Iron from Acidic Soils by Chemical Selective Dissolution Methods

Potassium chloride, Na-pyrophosphate, CuCl2, NH4-oxalate, dithionite-citrate-bicarbonate (DCB) and Na-citrate solutions were employed to extract aluminum (Al) and iron (Fe) sequentially and separately from 15 acidic soils located at the Mangshan Mountains, Hunan Province, China. Many evidences showed that separate pyrophosphate extracted mainly KCI-extractable Al, organo-Al complexes and some inorganic Al compounds, whereas separate CuCl2 extracted KCl-extractable Al and some organo-Al complexes. CuCl2 extracted much less amounts of Al than pyrophosphate did from the soils. Separate oxalate did not extract all KCl-Pyrophosphate- CuCl2 -oxalate sequentially extractable Al and Fe. Also, separate DCB did not extract all KCl- pyrophosphate- CuCl2 -oxalate- DCB sequentially extractable Al. The forms of Al extracted by oxalate and DCB from the soils were majorly noncrystalline. The interlayered materials of 1.4-nm intergrade minerals of the soils were attributed mainly to hydroxy Al polymers.

Biomass-based N doped carbon as metal-free catalyst for selective oxidation of D-xylose into D-xylonic acid

Rational design and facile preparation of low-cost and efficient catalysts for the selective converting of biomass-derived monosaccharides into high value-added chemicals is highly demanded,yet challenging.Herein,we first demonstrate a N doped defect-rich carbon(NC-800-5)as metal-free catalyst for the selective oxidation of D-xylose into D-xylonic acid in alkaline aqueous solution at 100℃ for 30 min,with 57.4%yield.The doped graphitic N is found to be the active site and hydroxyl ion participating in the oxidation of D-xylose.Hydroxyl ion and D-xylose first adsorb on NC-800-5 surface,and the aldehyde group of D-xylose is catalyzed to form germinal diols ion.Then,C–H bond break to yield carboxylic group.Furthermore,NC-800-5 catalyst shows high stability in recycled test.