Isomorphous Replacement Research Articles

Selective extraction of Li and Mn from spent lithium-ion battery smelting slag: Insights from isomorphous replacement in minerals

Recycling the high content of valuable metal elements contained in spent lithium-ion batteries (SLIBs) has attracted significant interest. By leveraging the concept of substitution of isomorphous replacement in earth minerals, this study proposes a novel approach for the selective extraction of Li and Mn from the artificial spodumene-type lithium-rich slag comprising LiAlSi2O6 and Mn2SiO4 through two-step selective roasting process with Na2SO4 and CaCl2, respectively. The thermodynamic calculations confirmed the feasibility of selective Li extraction by Na2SO4 roasting, with the experimental results showing that over 99 % Li was preferentially extracted as LiNaSO4. In the subsequent CaCl2 roasting step for Mn recovery, the Mn2SiO4 was effectively transformed into soluble Na2MnCl4, achieving a maximum Mn extraction efficiency of 86.5 %. The leaching kinetics of the Na2SO4 roasting products were investigated, revealing that the leaching of Li was governed by diffusion and chemical reactions in line with the shrinking core model. Characterization methods such as XRD, SEM, XPS, and TG-DSC were employed to reveal the phase transformation mechanisms of Li and Mn during Na2SO4 and CaCl2 roasting, respectively. The proposed process introduces a novel paradigm for its remarkable selective recovery of Li and Mn from SLIBs smelting slag.

One-step removal of anionic/cationic heavy metal ions from wastewater by magnetic amphoteric adsorbent

Simultaneous treatment of wastewater containing anionic and cationic pollutants in an easy-to-operate and environmentally friendly manner is a formidable challenge in environmental remediation. This work designed a low-cost and high-efficient amphoteric adsorbent Fe3O4/Mg-Al LDOs/AlS (SMA) for the simultaneous removal of Cr (VI) and Cu (II) pollutants from wastewater in one step. SMA is prepared with waterworks aluminum-containing sludge (AlS) from typical municipal engineering waste as the base material and loaded with magnetic nanoparticles to enhance recycling process after adsorption. SMA exhibits large specific surface area (∼418 m2/g), thereby providing sufficient adsorption active sites. Adsorption studies indicate that the adsorption of SMA toward two pollutants conforms to the pseudo-second-order kinetic model, while the Langmuir model is used to simulate the adsorption isotherm. The maximum adsorption capacity is calculated to be 235.3 mg/g for Cr (VI) and 669.2 mg/g for Cu (II). Thermodynamic studies reveal the process's spontaneous nature. The main adsorption mechanisms involve electrostatic attraction, surface complexation, isomorphic replacement, and chemical precipitation. Notably, SMA exhibits excellent adsorption performance in a wide pH range and water system containing multiple anions and cations. Moreover, the strong magnetic property facilitates easy separation and recovery through an external magnetic field, maintaining stable adsorption performance even after five cycles. Therefore, this study provides a win-win strategy for promoting environmental safety, not only proposing feasible approaches for the high value-added utilization of waste sludge, but also efficiently addressing the purification problem of complex anionic and cationic coexisting wastewater.

Adsorption behavior of Mg–Al layered double hydroxide on Pb(Ⅱ), Zn(Ⅱ), Cd(Ⅱ), and As(V) coexisting in aqueous solution

MgAl-layered double hydroxide（MgAl-LDH）was synthesized via hydrothermal method, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption-desorption, energy dispersive spectrum (EDS). The results proved that the prepared MgAl-LDH exhibited a well-defined layered structure and mesoporous morphology with a large specific surface area, which endowed them with abundant adsorption sites and diffusion mass transfer channels for heavy metal ions. Subsequently, the MgAl-LDH was used to evaluate the adsorption efficiency for Pb(Ⅱ), Zn (Ⅱ), Cd (Ⅱ), and As(V) coexisting in aqueous solutions by batch equilibrium experiments. The results showed favorable adsorption performance of MgAl-LDH toward four coexisting ionic species, with competitive adsorption among the heavy metal ions. Under the experimental conditions, the removal rates of Pb(Ⅱ), Zn (Ⅱ), Cd (Ⅱ), and As(V) ions were 96.7%, 97.1%, 65.2%, and 98.7%, respectively, and the selective order for cation adsorption followed Pb(Ⅱ) > Zn (Ⅱ) > Cd (Ⅱ). Furthermore, the adsorption mechanisms of Pb(Ⅱ), Zn (Ⅱ), Cd (Ⅱ) and As(V) by MgAl-LDH were detailed conducted by XRD, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis, and could be ascribed to the surface complexation, precipitation and isomorphic replacement for Pb(Ⅱ), Zn (Ⅱ), Cd (Ⅱ) while surface complexation, ion exchange and electrostatic adsorption for As(V).

Preparation and Properties of Expansive Backfill Material Based on Municipal Solid Waste Incineration Fly Ash and Coal Gangue

To realize the large-scale utilization of municipal solid waste incineration (MSWI) fly ash in the field of building materials and to reduce the cost of coal mine backfill mining, the effects of the mixing ratio of cementitious materials, the particle size distribution of aggregates, and the amount and mass concentration of cementitious materials on the properties of backfill materials were experimentally investigated, and the microstructure of the hydration products was analyzed. The results showed that as the mass ratio of MSWI fly ash to bottom ash increased, the rate of expansion of the cementitious system continued to increase, and the compressive strength of the cementitious system continued to decrease. The Al (aluminum) and AlN (aluminum nitride) in the fly ash reacted with water to generate gas, causing the expansion of the cementitious materials; NaOH increased the alkalinity of the solution, which promoted the formation of more bubbles, thereby improving the expansion performance of the cementitious material. When the content of NaOH was 0.9%, the sample rate of expansion could reach 15.9%. The addition of CaCl2 promoted the early hydration reaction of the cementitious material, forming a dense microstructure, thus improving the early strength and rate of expansion of the cementitious material. The compressive strength of the backfill body increased as the fractal dimension of the aggregate particles increased, and the particle grading scheme of group S1 was optimal. The 1-day, 3-day, and 28-day strengths of the backfill body of group S1 reached 0.72 MPa, 1.43 MPa, and 3.26 MPa, respectively. It is recommended to choose a backfill paste concentration ranging between 78.5% and 80% and a reasonable amount of cementitious material between 20% and 25%. After the MSWI fly ash was prepared as a backfill material, the leaching of potentially harmful elements in the fly ash was greatly reduced, and the concentration of dioxin was reduced to 13 ng TEQ/kg. This was attributed to the dilution of the cement, the physical encapsulation of gel products, and the isomorphous replacement of Ca2+ in calcium aluminate chloride hydrate.

Comparison of hexavalent chromium and cadmium removal from wastewater in constructed rapid infiltration system with layered double hydroxides (LDHs) modified maifanite substrates: Physical, chemical and microbial mechanism

In order to protect the ecological environment on which human beings depend, it is of great practical significance to prevent and control the heavy metal pollution in surface water. Cr(VI) in anionic form and Cd(II) in cationic form were selected to conduct the heavy metal purification experiments. Cr(VI) and Cd(II) removal by constructed rapid infiltration systems (CRIS) contain Zn-CO3-LDHs (ZnAl-CO3-LDHs and ZnFe-CO3-LDHs) coated maifanite substrates were compared. After ZnAl-CO3-LDHs coated, the Cr(VI) and Cd(II) removal amount increased by 87.53 % and 19.00 %, respectively. It could be inferred from XRD, FTIR, and Zeta potential results that the Cr(VI) physicochemical removal mechanism of maifanite changed to anion exchange, chemical bonding and electrostatic adsorption from electrostatic adsorption and chemical bonding after Zn-CO3-LDHs coated. By contrast, isomorphous replacement, electrostatic adsorption and chemical bonding of Cd(II) induced by Zn-CO3-LDHs replaced the electrostatic adsorption by natural maifanite. Additionally, the effective Cr(VI)/Cd(II) accumulation on Zn-CO3-LDHs modified maifanite reduced the microbial quantity, but increased EPS secretion and changed the community structure, which achieved the microbial Cr(VI)/Cd(II) removal through extracellular complexation and intracellular accumulation. This research result may provide essential reference for exploring the feasibility of heavy metal removal of CRIS with LDHs modified substrate.

Effect of long-term dry-wet circulations on the Solidification/stabilization of Municipal solid waste incineration fly ash using a novel cementitious material.

Solidification/stabilization (S/S) is a typical technique to immobilize toxic heavy metals in Municipal solid waste incineration fly ash (MSWI FA). This study utilized blast furnace slag, steel slag, desulfurization gypsum, and phosphoric acid sludge to develop a novel metallurgical slag based cementing material (MSCM). Its S/S effects of MSWI FA and long-term S/S effectiveness under dry-wet circulations (DWC) were evaluated and compared with ordinary Portland cement (OPC). The MSCM-FA block with 25 wt.% MSCM content achieved 28-day compressive strength of 9.38MPa, indicating its high hydration reactivity. The leaching concentrations of Pb, Zn and Cd were just 51.4, 1895.8 and 36.1 μg/L, respectively, well below the limit standard of Municipal solid wastes in China (GB 16889-2008). After 30 times' DWC, leaching concentrations of Pb, Zn and Cd for MSCM-FA blocks increased up to 130.7, 9107.4 and 156.8 μg/L, respectively, but considerably lower than those for OPC-FA blocks (689, 11,870.6 and 185.2 μg/L, respectively). The XRD and chemical speciation analysis revealed the desorption of Pb, Zn and Cd attached to surface of C-S-H crystalline structure during the DWC. The XPS and SEM-EDS analysis confirmed the formation of Pb-O-Si and Zn-O-Si bonds via isomorphous replacement of C-A-S-H in binder-FA blocks. Ettringite crystalline structure in OPC-FA block was severely destructed during the DWC, resulting in the reduced contents of PbSO4 and CaZn2Si2O7·H2O and the higher leachability of Pb2+ and Zn2+.

Bridging organic, molecular, macromolecular, supramolecular and biological sciences to create functions via fluorine chemistry and fluorinated reagents

After a brief introduction highlighting the challenges of fluorine chemistry and the latest developments in the field, this Perspective will discuss how a combination of fluorine and fluorous chemistry together with fluorinated reagents helped to bridge between organic, molecular, macromolecular, supramolecular and biological sciences to create functions in the laboratory of the corresponding author. The reactivity of fluoride as a leaving group is best illustrated by SNAr reactions when it helped to demonstrate single electron transfer-mediated side reactions and through molecular design replaced activated aryl fluorides with aryl chlorides in the synthesis of poly(etherketone)s. Subsequently it was demonstrated how Ni(II) sigma complexes provided an orthogonal approach to the Suzuki-type cross-coupling of arylfluorides, other halides and all aryl C–O based electrophiles. Fluorinated reagents facilitated cylotrimetrization vs cyclotetramerization of bis(methoxy)benzyl chloride and alcohol and the synthesis of the simplest molecular liquid crystals. Triflic acid, methyl triflate facilitated the most tolerant living polymerizations including of cyclic siloxanes, functional vinyl ethers and oxazolines to generate self-organizable dendronized polymers while fluorine, trifluoromethyl and trifluoromethoxy groups facilitated disassembly and reassembly of liquid crystal polyethers and poly(p-phenylenes). Fluorinated stereocenters accessed the first heterochiral recognition in side-chain liquid crystal poly(vinyl ether)s and their model compounds. Alkali metal triflates mediated self-organization of supramolecular nonfluorinated and fluorinated self-assembling minidendrons, dendrons, dendrimers and self-organizable dendronized polymers. The role of fluorinated alkyl groups and of alkali metal triflates in the self-assembly, disassembly and isomorphic replacement analysis, of supramolecular helical columns, of the assembly of helical cogwheel coat and of spherical supramolecular dendrimers forming Frank-Kasper periodic and quasiperiodic arrays was highlighted. A brief discussion of fluorinated amino acids, peptides and peptoids and their potential role in the self-assembly and functions resulted from dendritic dipeptides followed by a discussion of semifluorinated amphiphilic Janus dendrimers as models of biological membranes, including for cell fusion and fission, concludes this Perspective.

Facing the phase problem.

The marvel of X-ray crystallography is the beauty and precision of the atomic structures deduced from diffraction patterns. Since these patterns record only amplitudes, phases for the diffracted waves must also be evaluated for systematic structure determination. Thus, we have the phase problem as a central complication, both intellectually for the field and practically so for many analyses. Here, I discuss how we - myself, my laboratory and the diffraction community - have faced the phase problem, considering the evolution of methods for phase evaluation as structural biology developed to the present day. During the explosive growth of macromolecular crystallography, practice in diffraction analysis evolved from a universal reliance on isomorphous replacement to the eventual domination of anomalous diffraction for de novo structure determination. As the Protein Data Bank (PDB) grew and familial relationships among proteins became clear, molecular replacement overtook all other phasing methods; however, experimental phasing remained essential for molecules without obvious precedents, with multi- and single-wavelength anomalous diffraction (MAD and SAD) predominating. While the mathematics-based direct methods had proved to be inadequate for typical macromolecules, they returned to crack substantial selenium substructures in SAD analyses of selenomethionyl proteins. Native SAD, exploiting the intrinsic S and P atoms of biomolecules, has become routine. Selenomethionyl SAD and MAD were the mainstays of structural genomics efforts to populate the PDB with novel proteins. A recent dividend has been paid in the success of PDB-trained artificial intelligence approaches for protein structure prediction. Currently, molecular replacement with AlphaFold models often obviates the need for experimental phase evaluation. For multiple reasons, we are now unfazed by the phase problem. Cryo-EM analysis is an attractive alternative to crystallography for many applications faced by today's structural biologists. It simply finesses the phase problem; however, the principles and procedures of diffraction analysis remain pertinent and are adopted in single-particle cryo-EM studies of biomolecules.

Effective adsorption of heavy metals on layered double hydroxides modify through dithiocarbamate prepared by CS2 and different molecular weight of polyethyleneimine

Dithiocarbamate (DTC) with different molecular weight were prepared to modify Mg-Al layered double hydroxides (LDH-DTC) for adsorbing Cu(II), Pb(Ⅱ), Zn(Ⅱ), Cd(Ⅱ) from contaminated soil. The structural and morphology characterization indicated that DTC was wrapped outsides LDHs layer, and the coating layer became thicker with the increase of DTC molecular weight. The adsorption performance of LDH-DTC for heavy metal was investigated and adsorption kinetics was well followed pseudo-second-order and intraparticle diffusion model. The data of adsorption isotherm showed that the adsorption of Cu/Pb fitted Freundlich model, while the adsorption process of Zn/Cd fitted Langmuir model. Additionally, adsorption mechanism of LDH-DTC for Cu(II)/Pb(Ⅱ)/Zn(Ⅱ)/Cd(Ⅱ) with different concentration was explored. As the concentration of heavy metals was low, heavy metals first react with DTC encapsulated outside LDHs. With the increase of concentration, adsorption site of DTC was completely occupied, Cu(Ⅱ)/Pb(Ⅱ) began to react with the exposed LDHs layer to form precipitation, and Zn(Ⅱ)/Cd(Ⅱ) were immobilized on the LDHs layer by isomorphous replacement. The effects of pH, coexistence ions, heavy metal leaching, reuse, column leaching, and metal morphology classification experiments were also conducted, and these results revealed a high stability and favorable interception. The excellent adsorption performance suggested LDHs modified by DTC offered a promising method to immobilize heavy metals from soil and into practical application.

Effect of isomorphic replacement of palygorskite on its heavy metal adsorption performance

Isomorphism is a common phenomenon in clay minerals, which is one of the main reasons for the change of mineral chemical composition and physical and chemical properties. In this study, four kinds of palygorskite with different degrees of isomorphic replacement of octahedral cations were selected. The microstructure and surface-interface properties of different Mg2+/Al3+ palygorskite were analyzed by X-ray diffraction, infrared spectroscopy, N2 adsorption-desorption method, X-ray fluorescence spectroscopy and other characterization methods, and the effects of isomorphic replacement on microstructure such as Mg content and surface-interface properties such as hydroxyl concentration and acid content were discussed. Taking Cu2+ as the target pollutant, the adsorption capacity of different palygorskite to Cu2+ was measured and discussed. Combining the surface hydroxyl concentration and acid amount of palygorskite, as well as the concentration, time and temperature of the reaction system, the rule of adsorption of the four palygorskite for Cu2+ was Mg-rich palygorskite (a-ATP) > palygorskite with equal Mg and Al (c-ATP) > Al-rich palygorskite (d-ATP) > palygorskite with the most Mg (b-ATP), demonstrating that when Mg was partially replaced by Al, palygorskite contained appropriate hydroxyl concentration and acid amount, resulting in the best adsorption effect for Cu2+ (29.2 mg/g). It is of great significance for resource utilization of palygorskite to reveal the regularity of heavy metal adsorption by isomorphic replacement of palygorskite.

Releasing mechanism of ammonium during clayey sediments compaction and its impact on groundwater environment

Compaction of clayey aquitard would release pore water containing high levels of ammonium to adjacent aquifers, potentially affecting the concentration of groundwater ammonium. However, the releasing process and impact effect of ammonium within clayey aquitard during compaction remain unknown. Four groups of pre-experiments and two groups of simulation experiments were conducted to reveal the releasing mechanism of ammonium during clayey sediment compaction. (1) The results of Experiment A simulating continuous sedimentation conditions showed that the sediment ammonium transferred into pore water sequentially through desorption of ion exchange form, degradation of organic matter, and simultaneous release of mineral-bound ammonium. The concentration of pore water ammonium was 3.54–8.20 mg N/L, with a significant periodical variation due to sediment ammonium transformation. The lower moisture content (<42.4 %) in the later stage of compaction inhibited the biological transformation of ammonium, and the change in mineral structure caused the isomorphic replacement of K to capture ammonium, resulting in a decrease in ammonium concentration in released pore water. (2) The results of Experiment B simulating artificial compaction conditions (such as land subsidence) showed that the pore water ammonium was primarily caused by desorption of ion exchange form ammonium due to changes in pore structure and moisture content. The ammonium concentration in pore water was 4.72–9.91 mg N/L, with a significant increase in response to a large change in pressure in the short term. (3) The estimate results in the Chen Lake wetland suggested that the contribution of clayey aquitard compaction to groundwater ammonium concentration in the adjacent aquifer would be 2.68–4.29 mg N/L, which accounted for a considerable portion of groundwater ammonium concentration and was far higher than that of advection and diffusion. The findings of this study reveal the releasing mechanism of ammonium during clayey sediments compaction, in which reaction products may affect adjacent aquifers.

Study on the Performance and Mechanism of Cement Solidified Desulfurization Manganese Residue.

Desulfurized manganese residue (DMR) is an industrial solid residue produced by high-temperature and high-pressure desulfurization calcination of electrolytic manganese residue (EMR). DMR not only occupies land resources but also easily causes heavy metal pollution in soil, surface water, and groundwater. Therefore, it is necessary to treat the DMR safely and effectively so that it can be used as a resource. In this paper, Ordinary Portland cement (P.O 42.5) was used as a curing agent to treat DMR harmlessly. The effects of cement content and DMR particle size on flexural strength, compressive strength, and leaching toxicity of a cement-DMR solidified body were studied. The phase composition and microscopic morphology of the solidified body were analyzed by XRD, SEM, and EDS, and the mechanism of cement-DMR solidification was discussed. The results show that the flexural strength and compressive strength of a cement-DMR solidified body can be significantly improved by increasing the cement content to 80 mesh particle size. When the cement content is 30%, the DMR particle size has a great influence on the strength of the solidified body. When the DMR particle size is 4 mesh, the DMR particles will form stress concentration points in the solidified body and reduce its strength. In the DMR leaching solution, the leaching concentration of Mn is 2.8 mg/L, and the solidification rate of Mn in the cement-DMR solidified body with 10% cement content can reach 99.8%. The results of XRD, SEM, and EDS showed that quartz (SiO2) and gypsum dihydrate (CaSO4·2H2O) were the main phases in the raw slag. Quartz and gypsum dihydrate could form ettringite (AFt) in the alkaline environment provided by cement. Mn was finally solidified by MnO2, and Mn could be solidified in C-S-H gel by isomorphic replacement.

Topotactic transition of Ti4AlN3 MAX phase in Lewis acid molten salt

MAX phases and its derived two-dimensional MXenes have attracted considerable interest because of their rich structural chemistry and multifunctional applications. Lewis acid molten salt route provides an opportunity for structure design and performance manipulation of new MAX phases and MXenes, Although a series of new MAX phases and MXenes were successfully prepared via Lewis acid melt route in recent years, few work is explored on nitride MAX phases and MXenes. Herein, a new copper-based 413-type Ti4CuN3 MAX phase was synthesized through isomorphous replacement reaction using Ti4AlN3 MAX phase precursor in molten CuCl2. In addition, it was found that at high temperature Ti4N3Clx MXene will transform into two-dimensional cubic TiNα nanosheets with improved structural stability.

Multiprincipal Element M2 FeC (M = Ti,V,Nb,Ta,Zr) MAX Phases with Synergistic Effect of Dielectric and Magnetic Loss.

Electromagnetic (EM) wave pollution is harmful to human health and environment, thus it is absolutely important to develop new electromagnetic wave absorbing materials. MAX phases have been attracted more attention as a potential candidate for electromagnetic wave absorbing materials due to their high conductivity and nanolaminated structure. Herein, two new magnetic MAX phases with multiprincipal elements ((Ti1/3 Nb1/3 Ta1/3 )2 FeC and (Ti0.2 V0.2 Nb0.2 Ta0.2 Zr0.2 )2 FeC) in which Fe atoms replace Al atoms in the A sites are successfully synthesized by an isomorphous replacement reaction of multiprincipal (Ti1/3 Nb1/3 Ta1/3 )2 AlC and (Ti0.2 V0.2 Nb0.2 Ta0.2 Zr0.2 )2 AlC MAX phases with Lewis acid salt (FeCl2 ). (Ti1/3 Nb1/3 Ta1/3 )2 FeC and (Ti0.2 V0.2 Nb0.2 Ta0.2 Zr0.2 )2 FeC exhibit ferromagnetic behavior, and the Curie temperature (Tc ) are 302 and 235 K, respectively. The dual electromagnetic absorption mechanisms that include dielectric and magnetic loss, which is realized in these multiprincipal MAX phases. The minimum reflection loss (RL) of (Ti1/3 Nb1/3 Ta1/3 )2 FeC is -44.4dB at 6.56GHz with 3mm thickness, and the effective bandwidth is 2.48GHz. Additionally, the electromagnetic wave absorption properties of the magnetic MAX phases indicate that magnetic loss also plays an important role besides dielectric loss. This work shows a promising composition-design strategy to develop MAX phases with good EM wave absorption performance via simultaneously regulating dielectric and magnetic loss together.

Modulating Thermal Properties of Polymers through Crystal Engineering.

Crystal engineering has exclusively focused on the development of advanced materials based on small organic molecules. We now demonstrate how the cocrystallization of a polymer yields a material with significantly enhanced thermal stability but equivalent mechanical flexibility. Isomorphous replacement of one of the cocrystal components enables the formation of solid solutions with melting points that can be readily fine-tuned over a usefully wide temperature range. The results of this study credibly extend the scope of crystal engineering and cocrystallization from small molecules to polymers.

Modulating Thermal Properties of Polymers through Crystal Engineering

AbstractCrystal engineering has exclusively focused on the development of advanced materials based on small organic molecules. We now demonstrate how the cocrystallization of a polymer yields a material with significantly enhanced thermal stability but equivalent mechanical flexibility. Isomorphous replacement of one of the cocrystal components enables the formation of solid solutions with melting points that can be readily fine‐tuned over a usefully wide temperature range. The results of this study credibly extend the scope of crystal engineering and cocrystallization from small molecules to polymers.

Solidification of glass-ceramics of simulated fission products RE3+, Sr2+, Ba2+ in chlorine-containing waste molten salt

Embedding nuclear waste in glass-ceramic and immobilizing nuclides in ceramic lattice is an effective way for the disposal of high-level radioactive waste. In this paper, a method of solidification of simulated various nuclides was proposed, i.e., RE3+(RE = La, Sm, Nd, Dy), Sr2+ and Ba2+ precipitated from waste molten salt in the form of REPO4, SrCO3 and BaCO3 were solidified in glass-ceramics. To avoid the decomposition of SrCO3 and BaCO3 at high temperature, SrCO3/BaCO3 containing Cl− salt was further sintered with NH4H2PO4 to form Sr5(PO4)3Cl/Ba5(PO4)3Cl ceramics. It was found that the prepared REPO4 belonged to monoclinic or tetragonal crystal system, while Sr5(PO4)3Cl and Ba5(PO4)3Cl belonged to hexagonal crystal system. REPO4, Sr5(PO4)3Cl and Ba5(PO4)3Cl ceramics were co-solidified in iron phosphate glass. BET results showed that the ceramics had a dense structure without any pore inside. XRD, TEM and HRTEM results showed all ceramics had high crystallinity, and nuclides could enter the lattice structure of ceramics through isomorphic replacement, which made the nuclides stable in the crystal structure. The effects of embedding rate on the volume density, Vickers hardness and wettability of glass-ceramics were explored. It was found that the density of the glass-ceramics gradually increased with the increase of ceramic embedding rate, however, the Vickers hardness firstly increased and then decreased. When the embedding rate reached 20 wt%, the Vickers hardness of the glass-ceramics could reach 583.90 GPa. The water contact angles of glass-ceramics with an embedding rate 0–40 wt% were measured to be 70.45°–84.05°, indicating glass-ceramics having a good water leaching resistance. Furthermore, the normalized leaching rate NRi of La3+, Sm3+, Nd3+, Dy3+, Sr2+, Ba2+, Cl− on the 28th day were estimated to be 7.53 × 10−7, 5.02 × 10−7, 5.12 × 10−7, 4.04 × 10−7, 1.22 × 10−3, 1.59 × 10−4, 1.07 × 10−4 g‧m−2‧d−1, which indicating that all elements remained good leaching resistance.

The Z-scheme photocatalyst S-BiOBr/Bi2Sn2O7 with 3D/0D interfacial structure for the efficient degradation of organic pollutants

The establishment of heterojunction photocatalysts with significant degradation ability is identified as an effective strategy to address refractory pollutants. S-BiOBr nano-flowers were successfully synthesized by the isomorphous replacement combined self-assembly methods, and then Bi2Sn2O7 was deposited in-situ on the surface to construct a 3D/0D interfacial Z-scheme S-BiOBr/Bi2Sn2O7 heterojunction. The S-BiOBr/Bi2Sn2O7 maintained high activity on the degradation of rhodamine B, tetracycline and the inactivation of Spirulina, and three-dimensional excitation-emission matrix fluorescence spectroscopy was used to track the dynamic degradation process of pollutants. Mechanism analysis revealed that the h+ and O2− radicals played a leading role in the photocatalytic process, and OH played an assisting role. This enhanced activity can be attributed to the formation of oxygen vacancies at the interface when BiOBr is doped with S, which not only promoted the upward shift of the conduction band and thus improving the oxidation ability, but also narrowed the bandgap and thus boosting the visible light harvesting of BiOBr. Semiconductor produced photogenerated electron-hole pairs are effectively separated, and the redox ability of photogenerated carriers is maintained. These results provide a reasonable design method of high-efficiency heterojunction photocatalysis for refractory pollutants’ removal from wastewater.

Effective adsorption of Pb(ii) from wastewater using MnO2 loaded MgFe-LD(H)O composites: adsorption behavior and mechanism.

Pb(ii) adsorption by MnO2/MgFe-layered double hydroxide (MnO2/MgFe-LDH) and MnO2/MgFe-layered metal oxide (MnO2/MgFe-LDO) materials was experimentally studied in lab-scale batches for remediation property and mechanism analysis. Based on our results, the optimum adsorption capacity for Pb(ii) was achieved at the calcination temperature of 400 °C for MnO2/MgFe-LDH. Langmuir and Freundlich adsorption isotherm models, pseudo-first-order and pseudo-second-order kinetics, Elovich model, and thermodynamic studies were used for exploring the Pb(ii) adsorption mechanism of the two composites. In contrast to MnO2/MgFe-LDH, MnO2/MgFe-LDO400 °C has a stronger adsorption capacity and the Freundlich adsorption isotherm model (R2 > 0.948), the pseudo-second-order kinetic model (R2 > 0.998), and the Elovich model (R2 > 0.950) provide great fits to the experimental data, indicating that the adsorption occurs predominantly via chemisorption. The thermodynamic model suggests that MnO2/MgFe-LDO400 °C is spontaneously heat-absorbing during the adsorption process. The maximum adsorption capacity of MnO2/MgFe-LDO400 °C for Pb(ii) was 531.86 mg g-1 at a dosage of 1.0 g L-1, pH of 5.0, and temperature of 25 °C. Through characterization analysis, the main mechanisms involved in the adsorption process were precipitation action, complexation with functional groups, electrostatic attraction, cation exchange and isomorphic replacement, and memory effect. Besides, MnO2/MgFe-LDO400 °C has excellent regeneration ability in five adsorption/desorption experiments. The above results highlight the powerful adsorption capacity of MnO2/MgFe-LDO400 °C and may inspire the development of new types of nanostructured adsorbents for wastewater remediation.

Minerals phase transformation by hydrogen reduction technology: A new approach to recycle iron from refractory limonite for reducing carbon emissions

Limonite is a potentially vital iron ore resource, but it is hard to be effectively utilized by conventional mineral processing methods due to the high aluminum, silicon and water content. This paper proposed the phase transformation by hydrogen reduction technology to treat refractory limonite ore. The optimal conditions were determined as a roasting temperature of 500 °C, the reducing gas concentration of 20 % (H2:CO = 3:1), roasting time of 25 min, grinding fineness of 85 % passing 0.038 mm, the magnetic field strength of 187.5 kA/m. Under the above conditions, the concentrate with an iron grade of 59.85 % and recovery of 98.47 % was obtained. X-ray diffraction, iron chemical phase analysis and Vibrating Sample Magnetometer showed that the phase transformation of iron oxide was goethite/hematite → magnetite. Thus, the magnetism was significantly enhanced, which was conducive to magnetic separation. Electron Probe Micro Analysis indicated that it was difficult to further improve the quality of iron concentrate due to the existence of aluminum in the form of extremely fine minerals and the isomorphic replacement between aluminum and iron.