Insight into the Mechanism of Cobalt-Nickel Separation Using DFT Calculations on Ethylenediamine-Modified Silica Gel.

The separation of Co(II) and Ni(II) from leaching solution is gaining interest because Co(II) and Ni(II) are increasingly used in emerging strategic areas, such as power batteries. Herein, the surface of silica gel is functionalized with 1,2-ethylenediamine and used for the separation of Co(II) and Ni(II). The Co(II) removal efficiency of the modified silica is 80.2%, with a 4-fold improvement in the separation factor. The geometry, frequency, and electrostatic potential of the ethylenediamine modified silica gel (en/SG) are calculated. The corresponding properties of M2+ (M-Co, Ni) adsorbed on en/SG in an aqueous solution are simulated and analyzed. The results show that ethylenediamine tends to form [Men(H2O)4]2+ after binding to M2+, and the binding ability of Co(II) to ethylenediamine is stronger. Besides, the thermodynamic calculations show that en/SG has a more negative Gibbs free energy when absorbing Co(II) in aqueous solution, so en/SG is more inclined to bind with Co(II) preferentially. It is the difference in complexation ability between Ni, Co, and ethylenediamine that enlarges the difference in the original physical adsorption, thus strengthening the separation performance. This work will provide guidance for a rational design of high-performance nickel-cobalt adsorption materials.

Study on Removal Mechanism for Copper Cyanide Complex Ions in Water: Ion Species Differences and Evolution Process.

A large amount of cyanide-containing wastewater is discharged during electrode material synthesis. Among them, cyanides will form metal-cyanide complex ions which possess high stability, making it challenging to separate them from these wastewaters. Therefore, it is imperative to understand the complexation mechanism of cyanide ions and heavy metal ions from wastewater in order to obtain a deep insight into the process of cyanide removal. This study employs Density Functional Theory (DFT) calculations to reveal the complexation mechanism of metal-cyanide complex ions formed by the interaction of Cu+ and CN- in copper cyanide systems and its transformation patterns. Quantum chemical calculations show that the precipitation properties of Cu(CN)43- can assist in the removal of CN-. Therefore, transferring other metal-cyanide complex ions to Cu(CN)43- can achieve deep removal. OLI studio 11.0 analyzed the optimal process parameters of Cu(CN)43- under different conditions and determined the optimal process parameters of the removal depth of CN-. This work has the potential to contribute to the future preparation of related materials such as CN- removal adsorbents and catalysts and provide theoretical foundations for the development of more efficient, stable, and environmentally friendly next-generation energy storage electrode materials.

Open-Framework Metal Oxides for Fast and Reversible Hydrated Zinc-Ion Intercalation.

The development of high capacity and stable cathodes is the key to the successful commercialization of aqueous zinc-ion batteries. However, significant solvation penalties limit the choice of available positive electrodes. Herein, hydrated intercalation is proposed to promote reversible (de)intercalation within host materials by rationally designing a matching electrode. In contrast to previously reported works, the as-prepared electrode (NHVO@CC) can achieve fast and reversible intercalation of hydrated zinc ions in the interlayer gap, leading to a high capacity of 517 mAh g-1 at 0.1 A g-1 and excellent electrode stability for long-term cycling. Besides, as a consequence of the flexibility of the NHVO@CC electrode, a quasi-solid-state battery was achieved with equally advantageous electrochemical behavior under various bending states. The proposed hydrated cation direct insertion/extraction sets up an efficient way of developing high-performance positive electrodes for aqueous batteries.

Deep understanding of sustainable vanadium recovery from chrome vanadium slag: Promotive action of competitive chromium species for vanadium solvent extraction.

The complete separation of vanadium (V) and chromium (Cr) from chrome vanadium slag is still challenging. Many studies focus on the activity of vanadium, while the effect of the other element chromium and their mutual interaction are ignored. Here, we found that proper concentration of chromium can promote the extraction efficiency of vanadium. The extraction of V and Cr with various mass ratios ranging from 8:1-4:3 at different initial pH values using primary amine N1923 were studied. The extraction efficiency of V reached nearly 100%, while none of Cr was extracted when the mass ratio of Cr and V is 0.5 under proper pH. Through the dynamic monitoring of species evolutions during extraction, the transformation of the two metals and advantage extracted species were analyzed. Cr would transfer H+ for the combination of V3O93-/V4O124-, providing a great contribution to the continuous extraction of V. The real leachate was applied and 99.9% vanadium pentoxide was produced at a scale of 50 L/h. This paper offers deep insights of the separation of similar metal elements, and guide sustainable vanadium recovery from hazardous waste.

Quantitative tuning of ionic metal species for ultra-selective metal solvent extraction toward high-purity vanadium products.

The essence behind metal solvent extraction is the interaction between metal species and organic extractants. Aqueous metal species tuning at the molecular level is critical to improve the extraction efficiency and selectivity of the target metal. Herein, we demonstrate a quantitative metal species tuning strategy which is capable of extracting the most critical metals (e.g., V, W, and Mo) in extraction systems constructed by amines. We reveal the superior activities of V4 and V10 species among various V and Cr species by calculations and experiments. In addition, the contribution of various Vn species was quantitatively evaluated via Ion Species Contribution Evaluation (ISCE). Our tuning strategy is rationally designed by bridging species characteristics and routine aqueous conditions with extraction activities. Consequently, a three-dimensional model of V and Cr solvent extraction is established for the prediction of reaction regions, and the reactivities of nearly 20 kinds of typical metal species are compared and predicted. Our strategy serves for industrial solvent extraction, and may provide inspiration for the traditional hydrometallurgical revolutionary.

Comprehensive characterization on Ga (In)-bearing dust generated from semiconductor industry for effective recovery of critical metals.

Gallium (indium)-bearing dust generated from semiconductor industry is an important secondary resource for critical metal recycling. However, the diverse and distinct physicochemical natures of such waste material have made its recycling less effective, e.g. low extraction rate and complex treatment procedures. This research is devoted to gaining in-depth knowledge of the physical and chemical properties of such waste, including the chemical composition, physical phases, particle size distribution and chemical-thermal properties with a series of technologies. As a consequence, the occurrence and distribution of GaN and metallic indium phases are found to be crucial to efficient metal recycling. The thermal-chemical behavior shows that continuous oxidation occurred in the air atmosphere, indicating that heat-treatment followed by acid leaching is feasible to improve their recycling efficiencies. This process is able to leach 80.35% of gallium and 95.78% of indium with one-step operation. Furthermore, different treatment strategies for the waste material are preliminarily evaluated and discussed for the aim of metal recovery. The results show that gallium can be selectively recycled with recycling rate of 89.59% using alkaline leaching. With this research, the understanding on the recyclability of different metals and possibilities of selective recovery can be improved. It provides guidelines during the stage of decision-making for critical metal recycling in order to achieve efficient resource circulation.

A novel phenol and ammonia recovery process for coal gasification wastewater altering the bacterial community and increasing pollutants removal in anaerobic/anoxic/aerobic system.

Coal gasification wastewater (CGWW) is a typical toxic and refractory industrial wastewater. Here, a novel phenol and ammonia recovery process (IPE) was employed for CGWW pretreatment, and the coupled system assemble by the IPE process with A2/O system (IPE-A2/O) were operated to enhance the treatment performance of CGWW. The results showed that the IPE pre-treated effluent had a higher BOD5/COD ratio and lower refractory compounds compared to a typical process (MIBK). Subsequent A2/O biological treatment indicated that the A2/O-p system (A2/O system followed IPE process) obtained a higher average COD removal of 92% compared to 87.7% of the control (A2/O-m, A2/O system followed MIBK). The GC-MS analysis suggested that the content of alkanes in the IPE-A2/O effluent was lower than that of the MIBK-A2/O. The high-throughput sequencing revealed Levilinea, Alcaligenes, Acinetobacter, Thauera and Thiobacillus were the core genera in A2/O system. The genera Alcaligenes, Acinetobacter, Thauera and Thiobacillus in the degrading consortium were enriched in the A2/O-p system, leading to increased removals of organic pollutants and TN. These results suggested that the IPE process was a feasible pretreatment method, and the coupled IPE-A2/O system was an alternative technique for treating CGWW.

Recycling of LiNi1/3Co1/3Mn1/3O2 cathode materials from spent lithium-ion batteries using mechanochemical activation and solid-state sintering.

The production of lithium-ion battery is around 9100 million sets in 2016 and is believed to further increase consecutively. This fact triggers the generation of spent cathode materials which contain metals of both valuable and hazardous. Their recycling corresponding to life cycle sustainability of lithium-ion battery has attracted significant attention. However, most technologies for recycling waste lithium-ion batteries are dependent on metallurgical based processes where secondary pollution is inevitable. This research demonstrates a process to directly regenerate LiNi1-x-yCoxMnyO2 cathode material by incorporating methods of mechanochemical activation and solid-state sintering, which can restore the layered structure and improve the lithium ion diffusion without introducing extra impurities. By understanding the effects of sintering temperature, the optimal conditions for direct regeneration of cathode materials with obvious improvement on electrochemical performance can be obtained. As a result, this research proves the possibility of direct regeneration of nickel-containing waste cathode materials with minimized chemical consumption.

Novel method for characterization of aqueous vanadium species: A perspective for the transition metal chemical speciation studies.

Identification the polymerization nature of vanadium bearing solution is difficult, yet it is of great environmental concern due to the possible carcinogenic effects as well as high-value sustainable necessities. Thus, seeking for simple and efficient characterization methods of tracking vanadium species is in urgent demand. In this work, high-resolution electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) coupled with thermodynamic calculations was employed to measure vanadium-containing samples. Evolutions of four characteristic vanadium species, H2VO4- (0-1%), V2 species (0-1%), V4 species (1-20%), and V10 species (60-95%), were comprehensively studied from acidic to neutral conditions, based on which thermodynamic model and vanadium phase diagram were established to visualize transformation pathways. More than 30 types of aqueous vanadium species could be semi-quantitatively detected by employing this method with less than 5% relative error, and the corresponding existing forms and concentration of these vanadium species could be well predicted. The vanadium species identified in MS results were confirmed by NMR. This method can be widely used for the understanding of vanadium speciation in practical examples, especially involving V(V), Cr(VI) ions or organic complexes.