Constructing High-performance Cobalt-based Environmental Catalysts from Spent Lithium-Ion Batteries: Unveiling Overlooked Roles of Copper and Aluminum from Current Collectors.

Converting spent lithium-ion batteries (LIBs) cathode materials into environmental catalysts has drawn more and more attention. Herein, we fabricated a Co3O4-based catalyst from spent LiCoO2 LIBs (Co3O4-LIBs) and found that the role of Al and Cu from current collectors on its performance is nonnegligible. The density functional theory calculations confirmed that the doping of Al and/or Cu upshifts the d-band center of Co. A Fenton-like reaction based on peroxymonosulfate (PMS) activation was adopted to evaluate its activity. Interestingly, Al doping strengthened chemisorption for PMS (from -2.615 eV to -2.623 eV) and shortened Co-O bond length (from 2.540 Å to 2.344 Å) between them, whereas Cu doping reduced interfacial charge-transfer resistance (from 28.347 kΩ to 6.689 kΩ) excepting for the enhancement of the above characteristics. As expected, the degradation activity toward bisphenol A of Co3O4-LIBs (0.523 min-1) was superior to that of Co3O4 prepared from commercial CoC2O4 (0.287 min-1). Simultaneously, the reasons for improved activity were further verified by comparing activity with catalysts doped Al and/or Cu into Co3O4. This work reveals the role of elements from current collectors on the performance of functional materials from spent LIBs, which is beneficial to the sustainable utilization of spent LIBs.

Selective removal of thiosulfate from coke oven gas desulfurization wastewater by catalytic wet air oxidation with manganese-based oxide from spent ternary lithium-ion batteries.

Selective and efficient removal of thiosulfates (S2O32-) to recover high-purity and value-added thiocyanate products by fractional crystallization process is a promising route for the resource treatment of coke oven gas desulfurization wastewater. Herein, catalytic wet air oxidation (CWAO), with manganese-based oxide synthesized from spent ternary lithium-ion batteries (MnOx-LIBs), was proposed to selectively remove S2O32- from desulfurization wastewater. 98.0 % of S2O32- is selectively removed by the MnOx-LIBs CWAO system, which was 4.1 times that of the MnOx CWAO system. The synergistic effect among multiple metals from spent LIBs induces the enlarged specific surface area, increased reactive sites and formation of oxygen vacancy, promoting the adsorption and activation of O2, thereby realizing high-efficiency removal of S2O32-. The satisfactory selective removal efficiency can be maintained in the proposed system under complex environmental conditions. Notably, the proposed system is cost-effective and applicable to actual wastewater, in which 81.2 % of S2O32- is selectively removed from coke oven gas desulfurization wastewater. More importantly, compared with the typical processes, the proposed process is simpler and more environmentally-friendly. This work provides an alternative route to selectively remove S2O32- from coke oven gas desulfurization wastewater, expecting to drive the development of resource utilization of coke oven gas desulfurization wastewater.

Highly Dispersed FeAg-MCM41 Catalyst for Medium-Temperature Hydrogen Sulfide Oxidation in Coke Oven Gas.

The traditional hydrolysis-cooling-adsorption process for coke oven gas (COG) desulfurization urgently needs to be improved because of its complex nature and high energy consumption. One promising alternative for replacing the last two steps is selective catalytic oxidation. However, most catalysts used in selective catalytic oxidation require a high temperature to achieve effective desulfurization. Herein, a robust 30Fe-MCM41 catalyst is developed for direct desulfurization at medium temperatures after hydrolysis. This catalyst exhibits excellent stability for over 300 h and a high breakthrough sulfur capacity (2327.6 mgS gcat-1). Introducing Ag into the 30Fe-MCM41 (30Fe5Ag-MCM41) catalyst further enhances the H2S removal efficiency and sulfur selectivity at 120 °C. Its outstanding performance can be attributed to the synergistic effect of Fe-Ag clusters. During H2S selective oxidation, Fe serves as the active site for H2S adsorption and dissociation, while Ag functions as the catalyst promoter, increasing Fe dispersion, reducing the oxidation capacity of the catalyst, improving the desorption capacity of sulfur, and facilitating the reaction between active oxygen species and [HS]. This process provides a potential route for enhancing COG desulfurization.

Selective and efficient removal of emerging contaminants by sponge-like manganese ferrite synthesized using a solvent-free method: Crucial role of the three-dimensional porous structure.

Ubiquitous macromolecular natural organic matter (NOM) in wastewater seriously influences the removal of emerging small-molecule contaminants via heterogeneous advanced oxidation processes because this material covers active sites and quenches reactive oxygen species. Here, sponge-like magnetic manganese ferrite (MnFe2O4-S) with a three-dimensional hierarchical porous structure was prepared via a facile solvent-free molten method. Compared with the particle-like structure of MnFe2O4-P, the sponge-like structure of MnFe2O4-S presents an enlarged specific surface area (112.14 m2·g-1 vs. 58.73 m2·g-1) and a smaller macropore diameter (68.2-77.2 nm vs. 946.5 nm). Enlarging the specific surface area increases the exposure of active sites, and adjusting the pore size helps sieve NOM and emerging contaminants. These changes are expected to effectively improve the degradation activity and overcome interference. To confirm the superiority of the sponge-like structure, MnFe2O4-S was used to activate peroxymonosulfate (PMS) for the degradation of multiple emerging contaminants, and its ability to degrade bisphenol A with and without humic acid (HA) was compared with that of MnFe2O4-P. The degradation activity of MnFe2O4-S was 1.6 times greater than that of MnFe2O4-P. Moreover, 20 mg·L-1 HA inhibited the degradation activity of MnFe2O4-S by only 7.1%, which was much lower than that obtained for MnFe2O4-P (53.4%). In addition, the excellent performance was maintained in multiple water matrices. Notably, under lake water matrices, the degradation activity of MnFe2O4-P was inhibited by 35.6% while that of MnFe2O4-S was hardly inhibited. More importantly, the MnFe2O4-S/PMS system was also applicable to the treatment of actual wastewater and 73.0% and 90.1% of total organic carbon and chemical oxygen demand was removed from bio-treated coking wastewater containing non-biodegradable contaminants and NOM. This study provides an alternative route for the green production of high-activity porous spinel ferrites with environmental anti-interference properties.

Highly selective electrocatalytic reduction of nitrate to nitrogen in a chloride ion-free system by promoting kinetic mass transfer of intermediate products in a novel Pd-Cu adsorption confined cathode.

The mass transfer on the catalyst surface has a great influence on the selectivity of electrocatalytic nitrate reduction to nitrogen. In this study, a Pd-Cu adsorption confined nickel foam cathode is designed in the absence of both proton exchange membranes and chloride ions. The repulsion of the cathode enables intermediate products such as nitrite to accumulate in the confined region, resulting in an increase in the possibility of a second-order reaction to form nitrogen. The system can obtain more than 92% continuous N2 selectivity when it is used to treat 200 mg L-1 NO3--N under a current density of 8 mA cm-2, which is not only higher than those of semiconfined and nonconfined systems but also significantly better than the results obtained by Pd-Cu directly modified cathodes prepared by electrodeposition or impregnation. It is found that a high initial nitrate concentration and low current density are more beneficial for the accumulation of intermediates on Pd-Cu catalysts, thus improving the formation of nitrogen. A mechanism study reveals that the intermediates can completely occupy the active sites on the surface of Pd, avoiding the generation of active hydrogen, and therefore inhibiting the first-order reaction to produce ammonia. Moreover, the reducibility of Pd-Cu can also be gradually improved under the function of the cathode so that the system exhibits good stability. This study demonstrates an environmentally friendly and promising method for total nitrogen removal from industrial wastewater with high conductivity.

Insight into the Enhanced Removal of Water from Coal Slime via Solar Drying Technology: Dewatering Performance, Solar Thermal Efficiency, and Economic Analysis.

In this work, solar drying technology was applied for the deep dewatering of coal slime to save thermal energy and reduce the dust produced during the hot drying process of coal slime. Solar drying technology is used to dry coal slime to realize its resource utilization. The influence of solar radiation intensity and slime thickness is investigated on the drying process. The greater the solar radiation intensity (SRI) is, the faster the drying indoor air and coal slime are heated, and the faster the drying efficiency is. As the slime becomes thinner, the internal water diffusion resistance becomes smaller and the drying efficiency correspondingly becomes faster. In addition, to facilitate the application of coal slime drying in the actual project, the Page model is fitted and found to have a good fit for solar drying coal slime. Meanwhile, the optimal drying conditions are determined by analyzing the energy utilization under different conditions. It is found that the target moisture content of 10% is optimal for coal slime drying with the highest energy utilization. The laying thickness (L) of 1 cm has the highest solar thermal efficiency of 54.1%. More importantly, economic calculation and analysis are conducted in detail on solar drying. It is found that the cost of solar drying (¥38.59/ton) is lower than that of hot air drying (¥ 65.09/ton). Therefore, solar drying is a promising method for the drying of coal slime.

Sustainably recycling spent lithium-ion batteries to prepare magnetically separable cobalt ferrite for catalytic degradation of bisphenol A via peroxymonosulfate activation.

A selective separation-recovery process based on tuning organic acid was proposed to the resource recycling of spent lithium-ion batteries (LIBs) for the first time. The low-cost preparation of CoFe2O4, reuse of waste acid and recovery of Li can be realized in this process, simultaneously. Li and Co in spent LIBs can be leached efficiently using citric acid as a leaching agent, and separated effectively from leaching solution by tuning oxalic acid content. The results from the characterizations of the prepared CoFe2O4 (CoFe2O4-LIBs) show that it possesses higher ratio of Co(II)/Co(III) and Fe(II)/Fe(III), larger surface specific area and more number of acid sites in comparison with pure CoFe2O4. Besides, CoFe2O4-LIBs was used to activate peroxymonosulfate (PMS) for the degradation of bisphenol A (BPA). Interestingly, its degradation performance is superior to that of pure CoFe2O4 and the related Co-based catalysts. The excellent degradation performance can be maintained in presence of inorganic ions (e.g., Cl-, HCO3-, H2PO4- and NO3-) with high concentration or humic acid. Moreover, surface-bound SO4∙- is considered as the main reactive species for the degradation of BPA. More importantly, CoFe2O4-LIBs can be readily recycled by using an external magnet and own superior ability of regeneration.

Synthesis of MnO2 derived from spent lithium-ion batteries via advanced oxidation and its application in VOCs oxidation.

In this work, manganese is selectively and efficiently recovered from spent lithium-ion batteries via advanced oxidation by using potassium permanganate and ozone, and the transition metal-doped α-MnO2 and ß-MnO2 are one-step prepared for catalytic oxidation of VOCs. The recovery rate of manganese can be approximately 100% while the recovery efficiency of cobalt, nickel, and lithium is less than 15%, 2%, and 1%, respectively. Compared with pure α-MnO2 and ß-MnO2, transition metal-doped α-MnO2 and ß-MnO2 exhibit better catalytic performance in toluene and formaldehyde removal attributed to their lower crystallinity, more defects, larger specific surface area, more oxygen vacancies, and better low-temperature redox ability. Besides, the introduction of the appropriate proportion of cobalt or nickel into MnO2 can significantly improve its catalytic activity. Furthermore, the TD/GC-MS result indicates that toluene may be oxidized in the sequence of toluene - benzyl alcohol - benzaldehyde-benzoic acid - acetic acid, 2-cyclohexen-1-one, 4-hydroxy-, cyclopent-4-ene-1,3-dione - carbon dioxide. This method provides a route for the resource utilization of spent LIBs and the synthesis of MnO2.

Promotional removal of oxygenated VOC over manganese-based multi oxides from spent lithium-ions manganate batteries: Modification with Fe, Bi and Ce dopants.

In this work, cathode materials of spent lithium-ions manganate batteries are recovered as the precursor of manganese-based oxides catalysts and furthermore, different amount of Fe, Bi, Ce are introduced to modify their properties. A series of MnOx(MS)-X Fe, MnOx(MS)-X Bi and MnOx(MS)-X Ce samples with crystal phase of Mn5O8 are synthesized using combustion method and then the catalytic behavior and physicochemical properties of prepared catalysts are investigated. Compared to binary MnOx-5% Fe, MnOx-15% Bi and MnOx-10% Ce samples, multi MnOx(MS)-5% Fe, MnOx(MS)-15 Bi and MnOx(MS)-10% Ce catalysts display enhanced catalytic performance significantly in the removal of oxygenated VOC, which could be attributed to larger specific surface area, higher concentration of surface active oxygen species and Mn4+ ions and better reducibility at low temperature. In-situ DRIFTS results imply that main oxygen-containing functional groups such as carbonyl (-C=O), carboxyl (-COO), hydroxyl (-OH) can be observed during VOC oxidation and by comparison, it can be found that gas-phase O2 plays a crucial role in facilitating the further oxidation of by-products into CO2. In addition, TD/GC-MS results point out that the main by-products are formaldehyde; 2-propanol, 1-methoxy-; ethanol, 2-methoxy-, acetate; 2-ethoxyethyl acetate; acetic acid during VOC oxidation.

Constructing high-efficiency photocatalyst for degrading ciprofloxacin: Three-dimensional visible light driven graphene based NiAlFe LDH.

A three-dimensional (3D) graphene based photocatalyst, consisting of Fe(III)-doped NiAl layered double hydroxide (NiAlFe LDH), was prepared via a simple one-step hydrothermal approach for the first time. The growth of NiAlFe LDH nanoplates and the reduction of graphene oxide were accomplished simultaneously during hydrothermal process without adding toxic reductant and toxic solvent. No complex and time-consuming preparation steps were needed. The structural characterization shows that NiAlFe LDH nanoplates with a size of 100-150 nm vertically grow on the reduced graphene oxide (RGO) sheet, forming a unique 3D structured graphene based photocatalyst (NiAlFe LDH/RGO). The photocatalyst was applied for the first time to remove ciprofloxacin (CIP) in wastewater under visible-light illumination. Interestingly, after incorporating with an appropriate amount of Fe3+ and RGO, the NiAl LDH shows improved photocatalytic degradation performance in comparison with reported photocatalysts. The reaction rate in the presence of NiAlFe LDH/RGO is respectively 2.4 and 7.3 times faster than that in the presence of NiAl0.85Fe0.15 LDH and NiAl LDH, demonstrating that the addition of Fe3+ and RGO can improve synergistically the photocatalytic performance of the nanocomposite. Moreover, the photocatalytic mechanism of the 3D NiAlFe LDH/RGO photocatalyst was also investigated in detail.