Direct Regeneration of Spent Lithium-Ion Battery Cathodes: From Theoretical Study to Production Practice.

Direct regeneration method has been widely concerned by researchers in the field of battery recycling because of its advantages of in situ regeneration, short process and less pollutant emission. In this review, we firstly analyze the primary causes for the failure of three representative battery cathodes (lithium iron phosphate, layered lithium transition metal oxide and lithium cobalt oxide), targeting at illustrating their underlying regeneration mechanism and applicability. Efficient stripping of material from the collector to obtain pure cathode material has become a first challenge in recycling, for which we report several pretreatment methods currently available for subsequent regeneration processes. We review and discuss emphatically the research progress of five direct regeneration methods, including solid-state sintering, hydrothermal, eutectic molten salt, electrochemical and chemical lithiation methods. Finally, the application of direct regeneration technology in production practice is introduced, the problems exposed at the early stage of the industrialization of direct regeneration technology are revealed, and the prospect of future large-scale commercial production is proposed. It is hoped that this review will give readers a comprehensive and basic understanding of direct regeneration methods for used lithium-ion batteries and promote the industrial application of direct regeneration technology.

Bidirectional Enhancement of Nitrogen Removal by Indigenous Synergetic Microalgal-Bacterial Consortia in Harsh Low-C/N Wastewater.

Conventional microalgal-bacterial consortia have limited capacity to treat low-C/N wastewater due to carbon limitation and single nitrogen (N) removal mode. In this work, indigenous synergetic microalgal-bacterial consortia with high N removal performance and bidirectional interaction were successful in treating rare earth tailing wastewaters with low-C/N. Ammonia removal reached 0.89 mg N L-1 h-1, 1.84-fold more efficient than a common microalgal-bacterial system. Metagenomics-based metabolic reconstruction revealed bidirectional microalgal-bacterial interactions. The presence of microalgae increased the abundance of bacterial N-related genes by 1.5- to 57-fold. Similarly, the presence of bacteria increased the abundance of microalgal N assimilation by 2.5- to 15.8-fold. Furthermore, nine bacterial species were isolated, and the bidirectional promotion of N removal by the microalgal-bacterial system was verified. The mechanism of microalgal N assimilation enhanced by indole-3-acetic acid was revealed. In addition, the bidirectional mode of the system ensured the scavenging of toxic byproducts from nitrate metabolism to maintain the stability of the system. Collectively, the bidirectional enhancement system of synergetic microalgae-bacteria was established as an effective N removal strategy to broaden the stable application of this system for the effective treatment of low C/N ratio wastewater.

Metal element-based adsorbents for phosphorus capture: Chaperone effect, performance and mechanism.

Excessive phosphorus (P) enters the water bodies via wastewater discharges or agricultural runoff, triggering serious environmental problems such as eutrophication. In contrast, P as an irreplaceable key resource, presents notable supply-demand contradictions due to ineffective recovery mechanisms. Hence, constructing a system that simultaneously reduce P contaminants and effective recycling has profound theoretical and practical implications. Metal element-based adsorbents, including metal (hydro) oxides, layered double hydroxides (LDHs) and metal-organic frameworks (MOFs), exhibit a significant chaperone effect stemming from strong orbital hybridization between their intrinsic Lewis acid sites and P (Lewis base). This review aims to parse the structure-effect relationship between metal element-based adsorbents and P, and explores how to optimize the P removal properties. Special emphasis is given to the formation of the metal-P chemical bond, which not only depends on the type of metal in the adsorbent but also closely relates to its surface activity and pore structure. Then, we delve into the intrinsic mechanisms behind these adsorbents' remarkable adsorption capacity and precise targeting. Finally, we offer an insightful discussion of the prospects and challenges of metal element-based adsorbents in terms of precise material control, large-scale production, P-directed adsorption and effective utilization.

Selective recycling of lithium from spent LiNixCoyMn1-x-yO2 cathode via constructing a synergistic leaching environment.

The global response to lithium scarcity is overstretched, and it is imperative to explore a green process to sustainably and selectively recover lithium from spent lithium-ion battery (LIB) cathodes. This work investigates the distinct leaching behaviors between lithium and transition metals in pure formic acid and the auxiliary effect of acetic acid as a solvent in the leaching reaction. A formic acid-acetic acid (FA-AA) synergistic system was constructed to selectively recycle 96.81% of lithium from spent LIB cathodes by regulating the conditions of the reaction environment to inhibit the leaching of non-target metals. Meanwhile, the transition metals generate carboxylate precipitates enriched in the leaching residue. The inhibition mechanism of manganese leaching by acetic acid and the leaching behavior of nickel or cobalt being precipitated after release was revealed by characterizations such as XPS, SEM, and FTIR. After the reaction, 90.50% of the acid can be recycled by distillation, and small amounts of the residual Li-containing concentrated solution are converted to battery-grade lithium carbonate by roasting and washing (91.62% recovery rate). This recycling process possesses four significant advantages: i) no additional chemicals are required, ii) the lithium sinking step is eliminated, iii) no waste liquid is discharged, and iv) there is the potential for profitability. Overall, this study provides a novel approach to the waste management technology of lithium batteries and sustainable recycling of lithium resources.

Sulfidated nanoscale zero-valent iron derived from iron sludge for tetracycline removal: Role of sulfur and iron in reactivity and mechanisms.

Iron sludge, produced during the drinking water treatment process, can be recycled as potential iron resource to create environmental functional material. In this study, sulfur-iron composites derived from iron sludge (S-Fe composites) was synthesized through sulfidation and carbonization, and used for the tetracycline (TC) removal under aerobic and anoxic conditions. The reactivities of these as-prepared products were strongly depended on pyrolysis temperatures. In particular, sulfidated nanoscale zero-valent iron loaded on carbon (S-nFe0@CIS) carbonized at 800 °C exhibited the highest TC removal efficiency with 86.6% within 30 min at circumneutral pH compared with other S-Fe composites. The crystalline structure of α-Fe0, FeSx and S0 as main active sites in S-nFe0@CIS promoted the degradation of TC. Moreover, the Fe/S molar ratios significantly affected the TC removal rates, which reached the best value as the optimal S/Fe of 0.27. The results illustrated that the optimized extent of sulfidation could facilitate electron transfer from nFe0 towards contaminants and accelerate Fe(III)/Fe(II) cycle in reaction system compared to bared nFe0@CIS. We revealed that removal of TC by S-nFe0@CIS in the presence of dissolved oxygen (DO) is mainly attributed to oxidation, adsorption and reduction pathways. Their contribution to TC removal were 31.6%, 25.2% and 28.8%, respectively. Furthermore, this adsorption-oxygenation with the formation of S-nFe0@CIS-TC* complexes was a surface-mediated process, in which DO was transformed by the structural FeSx on complex surface to •OH with the generation of H2O2 intermediate. The intermediates of TC and toxicity analysis indicate that less toxicity products generated through degradation process. This study provides a new reclamation of iron sludge and offers a new insight into the TC removal by S-nFe0@CIS under aerobic conditions.

Regulating steric hindrance in difunctionalized porous aromatic frameworks for the selective separation of Pb(II).

Efficient and selective removal of Pb(II) from wastewater with complex matrix remains a challenging task. Porous aromatic frameworks (PAFs) with predesigned functional building blocks provide a favorable platform for the selective separation of Pb(II). Herein, the bifunctional SPAFs with the introduction of -OH and -SO3H were synthesized through rationally optimizing their steric hindrance. As a result, the SPAF-0.75 exhibits favorable adsorption capacity of Pb(II) (212.34 mg g-1), which is 22 times larger than pristine framework. Competition experiment indicates that SPAF-0.75 possess the selective removal of Pb(II) without interfering from co-existing metal ions. The removal rate of SPAF-0.75 still retain at 100% after six successive cycles. The DFT calculation illustrates that -OH and -SO3H are co-participate in the process of capturing Pb(II), revealing SPAF-0.75 preferred removal of Pb(II) owing to the lowest adsorption energy (ΔEab = -3.99 eV). This study extend the understanding of the structure-property relationship and facilitate new possibilities for PAFs.

Selective capture of palladium from acid wastewater by thiazole-modified activated carbon: Performance and mechanism.

As a kind of scarce metal, palladium is widely used in many chemical industries. It essential to recover palladium from secondary resources, especially acidic media, owing to high content of palladium in secondary wastes and widespread extraction of palladium via strong acids. Chemically modified carbon materials not only have the advantage of activated carbon but also achieve the precise removal of specific pollutants, which is a kind of adsorption material with broad application prospects. In this direction, we report a solid carbon material named AT-C, which is obtained by one-step synthesis of 2-aminothiazoles grafted to the carbon surface by amidation. The present adsorbent delivers a high palladium adsorption capacity of 178.9 mg g-1, and desirable thermal and chemical stability. The uniform presence of abundant sulfur atoms and CO in the porous network enables AT-C to achieve selective absorption and rapid adsorption kinetics of Pd2+ in the complex water mixture containing many competing ions in the acidic pH range. For the strongly acidic leachates of catalysts, AT-C exhibits outstanding stability in cyclic experiments. Meanwhile, the fixed-bed column test indicates that 1076 bed volumes of the feeding streams can be effectively treated. In addition, AT-C exhibits superior adsorption selectivity, and the recovery efficiency of Pd2+ in actual industrial wastewater is 96.6%. This work realizes an efficient, rapid, and selective removal of palladium under acidic conditions, and provides a reference for complex industrial water treatment and resource recovery of precious metals.

Tuning electronic structure of the carbon skeleton to accelerate electron transfer for promoting the capture of gold.

The efficient and selective recovery of gold from secondary sources is key to sustainable development. However, the complexity of the recovery environment can significantly complicate the compositions of utilized sorbents. Here, we report a straw-derived mesoporous carbon as an inexpensive support material. This mesoporous carbon is modified by anions (sulfur modulation, C-S-180) to improve its electron-transfer efficiency and tune the electronic structure of its skeleton toward enhanced gold reduction. The high surface area of C-S-180 (989.4 m2/g), as well as the presence of abundant C-S in the porous structure of the adsorbent, resulted in an outstanding Au3+-uptake capacity (3422.75 mg/g), excellent resistance to interference, and favorable Au3+ selectivity. Dissimilar to most existing carbon-based adsorbents, electrochemistry-based studies on the electron-transfer efficiencies of adsorbents reveal that sulfur modulation is crucial to optimizing their adsorption performances. Furthermore, the density functional theory reveals that the optimization mechanism is attributable to the adjustment of the electronic structure of the carbon skeleton by C-S, which optimizes the band-gap energy for enhanced Au3+ reduction. These findings offer a strategy for constructing green and efficient adsorbents, as well as a basis for extending the applications of inexpensive carbon materials in gold recovery from complex environments.

Investigating the potential of structurally defective UiO-66 for Sb (V) removal from tailing wastewater.

Antimony contamination of tailings from the mining process remain attracted a great amount of concern. In this study, defective UiO-66-X crystal materials are rationally constructed using trifluoroacetic acid and hydrochloric acid as modulators for the removal of Sb(V) from actual tailing sand leachates. XRD and TG characterizations reveal that the number and kind of defects in UiO-66 are influenced by the type of modulators and the addition of trifluoroacetic acid makes UiO-66-TFA contain both cluster and ligand defects. Adsorption experiments show that UiO-66 and UiO-66-HCl achieve 100% removal of Sb(V) at pH 7.5 of the tailing sand leachate, and up to 90% removal of Sb(V) by the three materials at pH 2.5. It is noteworthy that the removal rate of Sb(V) by UiO-66-HCl is still satisfactory even under strongly acidic conditions at pH 0.5, with good potential for practical applications. Four kinetic models are used to fit the adsorption data and the analysis shows that the mechanism of Sb(V) adsorption by three adsorbent is all pseudo-second order and chemisorption acts as an important role in the adsorption process. In addition, the fixed bed adsorption experiments show that the material exhibit good prospects for practical applications.

Thermodynamic and Kinetic Behaviors of Persulfate-Based Electron-Transfer Regime in Carbocatalysis.

A carbon-based advanced oxidation process is featured for the nonradical electron-transfer pathway (ETP) from electron-donating organic compounds to activated persulfate complexes, enabling it as a green technology for the selective oxidation of organic pollutants in complex water environments. However, the thermodynamic and kinetic behaviors of the nonradical electron-transfer regime had been ambiguous due to a neglect of the influence of pH on the mechanisms. In this study, three kinds of organic pollutants were divided in the carbon-based ETP regime: (i) physio-adsorption, (ii) adsorption-dominated ETP (oxidation rate slightly surpasses adsorption rate), and (iii) oxidation-dominated ETP (oxidation rate outpaces the adsorption rate). The differential kinetic behaviors were attributed to the physicochemical properties of the organic pollutants. For example, the hydrophobicity, molecular radius, and positive electrostatic potential controlled the mass-transfer process of the adsorption stage of the reactants (peroxydisulfate (PDS) and organics). Meanwhile, other descriptors, including the Fukui index, oxidation potential, and electron cloud density regulated the electron-transfer processes and thus the kinetics of oxidation. Most importantly, the oxidation pathways of these organic pollutants could be altered by adjusting the water chemistry. This study reveals the principles for developing efficient nonradical systems to selectively remove and recycle organic pollutants in wastewater.

Rationally designed calcium carbonate multifunctional trap for contaminants adsorption.

Adsorption technology has been widely developed to control environmental pollution, which plays an important role in the sustainable development of modern society. Calcium carbonate (CaCO3) is characterized by its flexible pore design and functional group modification, which meet the high capacity and targeting requirements of adsorption. Therefore, its charm of "small materials for great use" makes it a suitable candidate for adsorption. Firstly, we comprehensively review the research progress of controlled synthesis and surface modification of CaCO3, and its application for adsorbing contaminants from water and air. Then, we systematically examine the structure-effect relationship between CaCO3 adsorbents and contaminants, while also intrinsic mechanism of remarkable capacity and targeted adsorption. Finally, from the perspective of material design and engineering application, we offer insightful discussion on the prospects and challenges of calcium carbonate adsorbents, providing a valuable reference for the further research in this field.

Fluorine-Rich Supramolecular Nano-Container Crosslinked Hydrogel for Lithium Extraction with Super-High Capacity and Extreme Selectivity.

Extraction and recovery of lithium from reserves play a critical role in the sustainable development of energy due to the explosive growth of the lithium-battery market. However, the low efficiency of extraction and recovery seriously threatens the sustainability of lithium supply. In this contribution, we fabricate a novel mechanically robust fluorine-rich hydrogel, showing highly efficient Li+ extraction from Li-containing solutions. The hydrogel was facilely fabricated by simple one-pot polymerization of supramolecular nanosheets of fluorinated monomers, acrylic acid and a small amount of chemical crosslinkers. The hydrogel exhibits a remarkable lithium adsorption capacity (Qm Li+ =122.3 mg g-1 ) and can be reused. Moreover, it can exclusively extract lithium ions from multiple co-existing metal ions. Notably, the separation of Li+ /Na+ in actual wastewater is achieved with a surprising separation factor of 153.72. The detailed characterizations as well as calculation showed that the specific coordination of Li-F plays a central role for both of the striking recovery capability and selectivity for Li+ . Furthermore, an artificial device was constructed, displaying high efficiency of extracting lithium in various complex actual lithium-containing wastewater. This work provides a new and promising avenue for the efficient extraction and recovery of lithium resource from complex lithium-containing solutions.

A nanofiber with a p-π conjugated structure designed based on the Jahn-Teller effect for the removal of cupric tartrate from wastewater.

Copper organic complexes with strong chemical stability and high solubility in water are difficult to eliminate with traditional adsorbents. In this work, a novel amidoxime nanofiber (AO-Nanofiber) with the p-π conjugated structure was fabricated through homogeneous chemical grafting coupled with electrospinning and applied to capture cupric tartrate (Cu-TA) from aqueous solutions. The adsorption capacity of Cu-TA by AO-Nanofiber was 198.4 mg/g at an equilibrium time of 40 min, and the adsorption performance remains basically unchanged after 10 times adsorption-desorption cycles. The capture mechanism of Cu-TA by AO-Nanofiber was jointly validated by experiments and characterization such as Fourier Transform Infrared Spectrometer (FT-IR), X-ray Photoelectron Spectroscopy (XPS), and Density functional theory (DFT) calculations. These results demonstrated that the lone pair of electrons of the N atom from the amino groups and the O atom from hydroxyl groups in the AO-Nanofiber is partially transferred to the 3d orbital of the Cu(II) ions in Cu-TA, leading to the Jahn-Teller distortion of the Cu-TA and the more stable structure of AO-Nanofiber@Cu-TA was generated.

Targeting of platinum capture under 1+1 aqua regia using robust and recyclable polymeric polyamine resin: Adsorption performance and mechanism.

The targeted capture of platinum from complex and harsh acidic digests such as those platinum-containing secondary resources is essential from the perspectives of green development. Here, a polyamine chelating resin (CMPs-PEI) with excellent selectivity and acid resistance was prepared by a nucleophilic substitution reaction using chloromethylated polystyrene as the parent and polyethyleneimine as the modifier. The experimental results revealed that the adsorbent showed excellent adsorption effect on platinum under different acidities, and its maximum adsorption capacity was up to 337 mg/g at pH 2. More impressively, a rather high capacity of 162.41 mg/g was achieved in 1 + 1 aqua regia (pH -0.7), which was much higher than other adsorbent materials under the same conditions. In addition, the recovery of platinum by CMPs-PEI in practical platinum-containing iron concentrate abatement solution was 100 %. Mechanistic studies showed that the protonated amine groups on CMPs-PEI bound PtCl62- and partially reduced PtCl42- by electrostatic attraction. Meanwhile, the excellent regeneration performance of CMPs-PEI indicated that it showed great potential for green and economic recovery of precious metal ions.

A critical review on correlating active sites, oxidative species and degradation routes with persulfate-based antibiotics oxidation.

At present, numerous heterogeneous catalysts have been synthesized to activate persulfate (PS) and produce various reactive species for antibiotic degradation from water. However, the systematic summary of the correlation among catalyst active sites, PS activation pathway and pollutant degradation has not been reported. This review summarized the effect of metal-based, carbon-based and metal-carbon composite catalysts on the degradation of antibiotics by activating PS. Metal and non-metal sites are conducive to inducing different oxidation pathways (SO4•-, •OH radical oxidation and 1O2 oxidation, mediated electron transfer, surface-bound reactive complexes and high-valent metal oxidation). SO4•- and •OH are easy to attack CH, S-N, CN bonds, CC double bonds and amino groups in antibiotics. 1O2 is more selective to the structure of the aniline ring and amino group, and also to attacking CS, CN and CH bonds. Surface-bound active species can cleave CC, SN, CS and CN bonds. Other non-radical pathways may also induce different antibiotic degradation routes due to differences in oxidation potential and electronic properties. This critical review clarified the functions of active sites in producing different reactive species for selective oxidation of antibiotics via featured pathways. The outcomes will provide valuable guidance of oriented-regulation of active sites in heterogeneous catalysts to produce on-demand reactive species toward high-efficiency removing antibiotics from water.

Rapid extraction of valuable metals from spent LiNixCoyMn1-x-yO2 cathodes based on synergistic effects between organic acids.

The slow rate of organic acid leaching is the main factor hindering the ecological recycling of spent lithium-ion battery (LIB) cathode materials. Here, a mixed green reagent system of ascorbic acid and acetic acid is proposed to leach valuable metal ions from the spent LIBs cathode materials rapidly. In 10 min, 94.93% Li, 95.09% Ni, 97.62% Co, and 96.98% Mn were leached, according to the optimization results. Kinetic studies and material characterization technologies like XRD, SEM, XPS, UV-vis, and FTIR show that the "diffusion" and "stratification" effects of acetic acid contribute to the dual-function leaching agent ascorbic acid quickly extract metal ions from spent LiNi0.5Co0.3Mn0.2O2 (NCM532) materials at a mild temperature. In addition, the density-functional theory (DFT) calculations of spent NCM532 structural surfaces and leaching agents show that the fast leaching of valuable metal ions is due to the synergy between ascorbic acid and acetic acid. These results provided an approachable thinking for developing advanced and environmentally friendly strategies for recycling spent LIB cathode materials.

Integrated effect of bulk cations on nano-confined reactivity of clay-intercalated subnanoscale zero-valent iron in water-tetrahydrofuran mixtures.

Smectite clay-intercalated subnanoscale zero-valent iron (CSZVI) exhibits superior reactivity toward contaminants due to the small iron clusters (∼0.5 nm) under nano-confinement, which however is significantly influenced by the solution chemistry e.g., various cations, of polluted soil and water. This work was undertaken to elucidate the mechanisms of solution chemistry effects on dehalogenation ability of CSZVI in water-tetrahydrofuran solution using decabromodiphenyl ether as a model contaminant. By combined spectroscopic characterization and molecular dynamics simulation, it was revealed that bulk cations, i.e., Na+, K+, Mg2+ and Ca2+ collectively affected the interlayer distance, water content and Brønsted acidity of CSZVI and thus its degradation efficiency. Although causing inter-particle aggregation, Mg2+ induced optimal nano-confined interlayers at concentration of 20 mM, exhibiting a superior debromination efficiency with rate constant 9.84 times larger than that by the common nano-sized ZVI. Conversely, K+ rendered the interlayers less reactive, but protected CSZVI from corrosion loss with higher electron utilization efficiency, which was 1.7 times higher than CSZVI in presence of Mg2+. The findings provide new strategies to manipulate the reactivity of nano-confined CSZVI for effective wastewater and contaminated soil remediation.

Polyacrylamide-Based Block Copolymer Bearing Pyridine Groups Shows Unexpected Salt-Induced LCST Behavior.

Thermal-responsive block copolymers are a special type of macromolecule that exhibit a wide range of applications in various fields. In this contribution, we report a new type of polyacrylamide-based block copolymer bearing pyridine groups of polyethylene glycol-block-poly(N-(2-methylpyridine)-acrylamide; Px) that display distinct salt-induced lower critical solution temperature (LCST) behavior. Unexpectedly, the phase-transition mechanism of the salt-induced LCST behavior of Px block copolymers is different from that of the reported LCST-featured analogues. Moreover, their thermo-responsive behavior can be significantly regulated by several parameters such as salt species and concentration, urea, polymerization degree, polymer concentration and pH values. This unique thermal behavior of pyridine-containing block copolymers provides a new avenue for the fabrication of smart polymer materials with potential applications in biomedicine.