Study on the occurrence state of main components of phosphogypsum dihydrate and its impurity distribution.

The dihydrate phosphoric acid process is the mainstream technique. However, the phosphogypsum (PG) produced contains high levels of impurities such as phosphorus and fluorine, severely constraining its valorization. In order to elucidate the occurrence patterns of phosphorus and fluorine impurities in PG, this study employed analytical methods including XRF, XRD, AMICS (Automated Mineralogy Integrated with Chemistry System), XPS, and chemical element balance analysis. We investigated the occurrence states of phosphorus, fluorine, silicon, iron, and aluminum elements in PG from wet-process phosphoric acid production, as well as the distribution characteristics of phosphorus and fluorine impurities. Additionally, we utilized Density Functional Theory (DFT) calculations to determine the binding energies of major minerals with water-soluble phosphate and fluoride groups, and analyzed the zeta potentials of gypsum and quartz mineral surfaces. The results indicate that the main mineral phases in PG are gypsum, quartz, potassium silicate minerals, aluminosilicate minerals, and hematite, predominantly occurring in monomineralic forms. Phosphorus impurities primarily exist in calcium silicate and hematite minerals, while fluorine is mainly associated with gypsum and potassium silicate minerals. DFT calculations demonstrate strong binding energies between calcium silicate and hematite minerals with PO4 3-, as well as between gypsum and quartz minerals with F-. The acidic conditions in the separation tank during wet-process phosphoric acid production may contribute to the distinctive distribution characteristics of phosphorus and fluorine impurities in PG.

The Impurity Removal and Comprehensive Utilization of Phosphogypsum: A Review.

Phosphogypsum (PG), a byproduct during the phosphoric acid production process, also known as the wet process, contains complex and diverse impurities, resulting in low utilization and considerable accumulation. This leads to a massive waste of land resources and a series of environmental pollution problems. Given the current urgent ecological and environmental situation, developing impurity removal processes with low energy consumption and high efficiency, exploring valuable resource recovery, preparing high value-added PG products, and broadening the comprehensive utilization ways of PG are significant strategies to promote the sustainable consumption of PG and sustainable development of the phosphorus chemical industry. This review comprehensively summarizes the advantages and disadvantages of existing PG impurity removal and utilization technologies and probes into the future development direction, which provides references and ideas for subsequent PG research.

Phosphorus immobilization/release behavior of lanthanum-modified bentonite amended sediment under the dual effects of pH and dissolved organic carbon.

Lanthanum modified bentonite (LMB) is typical P-inactivating agent that has been applied in over 200 lakes. Dissolved organic carbon (DOC) and high pH restrict the phosphorus (P) immobilization performance of LMB. However, the P immobilization/release behaviors of LMB-amended sediment when suspended to overlying water with high pH and DOC have not yet been studied. In the present work, batch adsorption and long-term incubation experiments were performed to study the combined effects of pH and DOC on the P control by LMB. The results showed that the coexistence of low concentration of DOC or preloading with some DOC had a negligible effect on P binding by LMB. In the presence of DOC, the P adsorption was more pronounced at pH 7.5 and was measurably less at pH 9.5. Additionally, the pH value was the key factor that decided the P removal at low DOC concentration. The increase in pH and DOC could significantly promote the release of sediment P with a higher EPC0. Under such condition, a higher LMB dosage was needed to effectively control the P releasing from sediment. In sediment/water system with intermittent resuspension, the alkaline conditions greatly facilitated the release of sediment P and DOC, which increased from 0.087 to 0.581 mg/L, and from 11.05 to 26.56 mg/L, respectively. Under the dual effect of pH and DOC, the P-immobilization performance of LMB was weakened, and a tailor-made scheme became essential for determining the optimum dosage. The desorption experiments verified that the previously loaded phosphorus on LMB was hard to be released even under high pH and DOC conditions, with an accumulative desorption rate of less than 2%. Accordingly, to achieve the best P controlling efficiency, the application strategies depending on LMB should avoid the high DOC loading period such as the rainy season and algal blooms.

Mechanistic investigation of Pb2+ adsorption on biochar modified with sodium alginate composite zeolitic imidazolate framework-8.

For the serious situation of heavy metal pollution, the use of cheap, clean, and efficient biochar to immobilize heavy metals is a good treatment method. In this paper, SA@ZIF-8/BC was prepared for the adsorption of Pb2+ in solution using sodium alginate (SA) and zeolitic imidazolate framework-8 (ZIF-8) modified corn cob biochar. The results showed that the specific surface area of modified biochar was greatly improved, with good adsorption capacity for Pb2+, strong anti-interference ability, and good economy. At the optimal adsorption pH of 5, the adsorption model of Pb2+ by SA@ZIF-8/BC was more consistent with the pseudo-second-order kinetic model and Langmuir isotherm model. This indicates that the adsorption of Pb2+ by SA@ZIF-8/BC is chemisorption and monolayer adsorption. The maximum adsorption of modified biochar was 300 mg g-1, which was 2.38 times higher than that of before modified BC (126 mg g-1). The shift in binding energy of functional groups before and after adsorption of SA@ZIF-8/BC was studied by XPS, and it was found that hydroxyl and carboxyl groups played an important role in the adsorption of Pb2+. It was demonstrated that this novel adsorbent can be effectively used for the treatment of Pb pollution in wastewater.

Direct Z-scheme system of UiO-66 cubes wrapped with Zn0.5Cd0.5S nanoparticles for photocatalytic hydrogen generation synchronized with organic pollutant degradation.

Optimized fabrication of Z-scheme photocatalyst based on MOF materials offers sustainable energy generation and environmental improvement due to their attractive properties. The Z-scheme heterojunctions consisting of UiO-66 cubes covered with Zn0.5Cd0.5S nanoparticles were fabricated by a facile solvothermal method. Thanks to the Z-scheme carrier transport under simulated sunlight irradiation, UiO-66@Zn0.5Cd0.5S exhibited enhanced photocatalytic performance of H2 generation synchronized with organic pollutant degradation in fluoroquinolone antibiotic wastewater. Synergistically, the highest comprehensive performance was obtained in ciprofloxacin solution. The H2 yield reached 224 µmol∙ g-1∙ h-1 and simultaneously the removal efficiency was up to 83.6 %. The degradation pathways revealed that the process of piperazine ring cleavage and decarboxylation also generates H protons, further promoting the production of H2. Therefore, the effective spatial separation and transfer of the photoinduced carriers are attributed to the good band structure, large specific surface area, and cooperative reduction and oxidation reactions of UiO-66@Zn0.5Cd0.5S, resulting in significant photocatalytic activity. The toxicity assessment of antibiotics and intermediate products during the photocatalytic reaction also verifies the reduction of environmental risk. This study highlights a promising way to expand the application of the MOFs-based photocatalyst in clean energy conversion coupling with water remediation.

Comparison of microbial communities in unleached and leached ionic rare earth mines.

The leaching of ionic rare earth elements has caused serious environmental pollution and ecological damage. Microorganisms play a crucial role in soil ecosystems and are one of the most important components of these systems. However, there are fewer studies related to the changes that occur in microbial community structure and diversity before and after leaching in ionic rare earth mines. In this study, Illumina high-throughput sequencing was used to examine the diversity and composition of soil microorganisms on the summit, hillside, and foot valley surfaces of unleached and leached mines after in situ leaching. The results showed that microbial diversity and abundance in the surface soil of the unleached mine were higher than those in the leached mine, and leaching had a significant impact on the microbial community of mining soil. pH was the main factor affecting the microbial community. Proteobacteria, Actinobacteriota, and Chloroflexi were phyla that showed high abundance in the soil. Network analysis showed that microbial interactions can improve microbial adaptation and stability in harsh environments. PICRUSt2 predictions indicate functional changes and linkages in soil microbial communities.

The investigation of ion association characteristics in lanthanum sulfate solution by the density functional theory and molecular dynamics simulations.

The ion association behavior in aqueous lanthanum sulfate solutions was investigated using density functional theory (DFT). The structures and properties of [La(SO4)m·(H2O)n](3-2m) clusters, where m = 1 to 3 and n = 1 to 9, were examined at the PBE0/6-311+G(d, p) level. The results show that Lanthanum sulfate hydrated clusters exist in the aqueous solution's microscopic state of contact ion pairs (CIP). [La(SO4)(H2O)n]+ and [La(SO4)2·(H2O)n]-, and [La(SO4)3·(H2O)n]3- clusters approximately reach the saturation of the first water shell at n = 7 and 6 and 3. [La(SO4)2·(H2O)6]- and [La(SO4)3·(H2O)3]3- clusters have lower binding energy than [LaSO4·(H2O)n]+. This indicates that lanthanum sulfate tends to aggregate in an aqueous solution. Compared to the gas-phase cluster structures, the distance of R(La-O)H2O expands in the PCM solvent model, while R(La-O)SO4 contracts. The hydration energy of LaSO4·(H2O)7, La(SO4)2·(H2O)6, and La(SO4)3·(H2O)3 were -76.5, -54.1 and -332.0 kcal/mol, respectively. The molecular dynamics simulation results show that La is more inclined to coordinate with sulfate's oxygen than water's oxygen, and the coordination number of water around La3+ is 6.075. These results are consistent with the calculated results by DFT.

Metagenomic analysis revealed the evolution of microbial communities, metabolic pathways, and functional genes in the heterotrophic nitrification-aerobic denitrification process under La3+ stress.

Trivalent lanthanum (La3+) exists widely in ammonia nitrogen (NH4+-N) tailing water from ionic rare earth mines; however, its effect on heterotrophic nitrification-aerobic denitrification (HN-AD) is unknown, thereby limiting the application of the HN-AD process in this field. In this study, we conducted an HN-AD process using a sequencing batch reactor (5 L) that was continuously operated to directly treat acidic (NH4)2SO4 wastewater (influent NH4+-N concentration of approximately 110 mg/L and influent pH of 5) containing different La3+ concentrations (0-100 mg/L). The NH4+-N removal efficiency of the reactor reached 98.25 % at a La3+ concentration of 100 mg/L. The reactor was in a neutral-to-alkaline environment, which favored La3+ precipitation and complexation. Metagenomic analysis revealed that the relative abundance of Thauera in the reactor remained high (88.62-92.27 %) under La3+ stress. The relative abundances of Pannonobacter and Hyphomonas significantly increased, whereas that of Azoarcus significantly decreased. Metabolic functions in the reactor were mainly contributed by Thauera, and the abundance of metabolic functions under low La3+ stress (≤5 mg/L) significantly differed from that under high La3+ stress (≥10 mg/L). The relative abundance of ammonia assimilation-related genes in the reactor was high and significantly correlated with ammonia removal. However, traditional ammonia oxidation genes were not annotated, and unknown ammonia oxidation pathways may have been present in the reactor. Moreover, La3+ stimulated amino acid biosynthesis and translocation, the citrate cycle, sulfur metabolism, and oxidative phosphorylation and promoted the overproduction of extracellular polymeric substances, which underwent complexation and adsorbed La3+ to reduce its toxicity. Our results showed that the HN-AD process had a strong tolerance to La3+, stable NH4+-N removal efficiency, the potential to recover La3+, and considerable application prospects in treating NH4+-N tailing water from ionic rare earth mines.

Sedimentation-Based Separation and Purification of Solid Industrial Waste: A Case Study of Phosphogpusym.

The continuous accumulation of solid industry waste, such as phosphogypsum, has emerged as a global environmental hazard and a significant obstacle to achieving a green and sustainable industry. To convert this industry waste to reusable resources, the development and implementation of simple and cost-efficient purification techniques is crucial. A sedimentation-based separation approach was developed to achieve this objective. Through a sedimentation process, a suspension of phosphogypsum particles is transformed into three distinct phases: a supernatant liquid, a concentrated slurry, and a solid precipitate. These phases primarily consist of soluble salts, a mixture of oxides and organic matter, and calcium phosphate dihydrates mixed with calcium phosphate, respectively. Through a sedimentation process, calcium sulfate dihydrate concentration can be significantly enhanced from 87.45 to 91.60% and further improved to 95.72% by repeating the sedimentation process three times. The various components obtained from this process can be effectively reused as mineral resources, soil amendment, and industry gypsum. The sedimentation process is expounded upon using both the classical mechanics model and Stokes' law. To foster a seamless industrial application, we have also designed a continuous settling skittle and a trail setup for industrial treatment of phosphogpysum. This innovative technique holds immense promise for its broader application, especially within but not limited to the phosphoric acid industry.

Synergistic leaching process for ion-exchange ammonium from weathered crust elution deposited rare earth tailings with potassium magnesium compound eluent.

The ion-exchangeable ammonium (IE-A) that accounts for 60-90% of the total residual ammonium in rare earth tailings has great potential to pollute the surrounding environment, and much research has been done to seek an effective elution method. However, the current study mainly focused on the single salt solution, which made it hard to reach the desired elution efficiency. In this study, the efficient binary compound eluent was prepared, and the response surface experiments and dynamic elution were performed to optimize the elution condition and evaluate the practical application prospect. Batch experimental results showed that the best IE-A elution efficiency could be achieved at the K:Mg molar ratio of 8:2, the liquid-solid ratio of 26:1, and the concentration of 0.1 mol/L at the natural solution pH. Dynamic experimental results indicated that a higher concentration, flow rate, and elution temperature could all accelerate the elution process, and the highest elution efficiency could reach 99%. The fitting results by shrinking core models show that the apparent activation energy of IE-A was 4.24 kJ/mol in the temperature range of 288-328 K, and the reaction order was 0.16. XPS and FTIR revealed that IE-A was effectively eluted by a potassium and magnesium compound leaching agent via an ion-exchange reaction. Overall, the developed compound solution with potassium and magnesium is a candidate for an elution agent that could be used to remove residual ammonium in a closed field of rare earth ores.

Performance Improvement and Microstructure Characterization of Cement-Stabilized Roadbase Materials Containing Phosphogypsum/Recycled Concrete Aggregate.

The proper reutilization of the phosphogypsum (PG) by-product derived from the production of phosphoric acid and recycled concrete aggregate (RCA) from waste concrete in roadbase materials is of great necessity and importance. This investigation tried seeking a new approach to reuse them to high quality, including turning PG into calcinated PG (CPG) via washing and calcination, as well as adopting sodium metasilicate nonahydrate (SMN) to strengthen the roadbase materials of cement-stabilized CPG and RCA. Upon the mix design, with a series of experiments including unconfined compressive strength, the wet-dry cycle, freeze-thaw cycle, and scanning electron microscopy, the comprehensive effects of PG treatment, the CPG to RCA mix ratio, SMN dosage, wet-dry cycle and freeze-thaw cycle on the road performance of roadbase materials were well evaluated, and the traffic bearing capacity and microstructure characteristics were also analyzed. The results demonstrate that the 7 d unconfined compressive strength of CPG/RCA roadbase materials can reach 5.34 MPa as the CPG and SMN dosage are 20% and 11%, respectively, which meets the requirements of an extremely and very heavy traffic grade. After five wet-dry cycles and freeze-thaw cycles, the resistance of the CPG/RCA roadbase materials to moisture and frost was significantly improved as 11% SMN was added. Meanwhile, SMN contributes to the reduction in crack width and densifies the microstructure of CPG/RCA roadbase materials. The research results can be used to provide new guidance for building more durable roadbase materials.

Mechanisms of combined bioremediation by phosphate-solubilizing fungus and plants and its effects on cadmium contamination in phosphate-mining wastelands.

Owing to uncontrolled mining activities and lack of ecological protection measures, phosphate-mining wastelands are contaminated with the heavy metal Cd. In this study, Penicillium oxalicum strain ZP6, a Cd-resistant phosphate-solubilizing fungus, was used in combination with the fast-growing, high-biomass plant Brassica juncea L. to enhance Cd remediation in phosphate-mining wastelands. Further, the bioremediation mechanisms were explored and elucidated. In pot experiments, strain ZP6 and Brassica juncea L. alone were significantly effective in removing Cd from phosphate-mining wastelands; however, their combination was more effective, exhibiting a high removal rate of 88.75%. The presence of phosphorite powder increases soil-enzyme activity, promotes plant growth, and reduces the bioaccumulation and translocation factors. However, Cd-inhibited plant growth and chlorophyll content increased malondialdehyde accumulation, which was alleviated by inoculation with strain ZP6. The results from the study indicate that bioremediation using a combination of strain ZP6 and plants is a restoration strategy with appreciable potential to resolve Cd contamination in phosphate-mining wastelands.

A Critical Review of the Enhanced Recovery of Rare Earth Elements from Phosphogypsum.

The increasing demand for rare earth elements (REEs), especially from new and innovative technology, has strained their supply, which makes the exploration of new REE sources necessary, for example, the recovery of REEs from phsophogypsum (PG). PG is a byproduct during the wet production of phosphoric acid, which is an attractive secondary resource for REEs due to a large amount of REEs locked in them. In most cases, REEs contained in PG are mainly encapsulated in the gypsum crystal, leading to a low leaching efficiency. Therefore, it is particularly important to use various methods to enhance the leaching of REEs from PG. In this review, we summarized and classified various enhanced leaching methods for the recovery of REEs from PG, and the advantages and disadvantages of different methods were compared. A joint method of recrystallization and RIL may be a promising enhanced leaching approach for the recovery of REEs from PG. Recrystallization could achieve both the complete REE release and simultaneous preparation of industrial materials with high value added, such as high-strength α-hemihydrate gypsum by phase transformation of PG, and the RIL technology could adsorb the releasing REEs and realize their efficient extraction. Such a combination appears to show significant advantages because of high REE recovery, as well as high value-added product preparation at low cost.

Treating waste with waste: Adsorption of anionic dyes in wastewater with surfactant-modified phosphogypsum.

Phosphogypsum (PG) is a solid waste generated during the wet process of phosphoric acid production. The environmental-friendly disposal and recycling of PG is vital in the field of environmental solid waste treatment. In this study, PG is used for adsorbent of dyes in wastewater to achieve the goal of recycling waste with waste. Surfactant-modified phosphogypsum (ODBAC@PG) was prepared using octadecyl dimethyl benzyl ammonium chloride (ODBAC) as modifier. ODBAC@PG exhibits high adsorption capability for anionic dyes (methyl blue (MeB) and indocyanine carmine (IC)). The pseudo-second-order kinetic model fits the kinetic experimental data for the adsorption of two organic anionic dyes. Langmuir adsorption isotherm fits the adsorption characteristics of MeB and IC on ODBAC@PG, exhibiting a monolayer adsorption pattern. Thermodynamic parameters indicate the spontaneous and exothermic properties of MeB and IC on ODBAC@PG. MeB and IC have antagonistic effects on each other in binary adsorption system. High adsorption capacity after six cycles of experiments demonstrates the high reusability of ODBAC@PG. The nature for the adsorption includes electrostatic interaction, hydrogen bond and hydrophobic interaction. Using ODBAC@PG for dyes wastewater treatment can accomplish the goal of treating waste with waste and turning waste into treasure.

Seaweed-like phosphates/MOF heterostructures as a synergistic electrocatalyst for alcohol oxidation.

A series of seaweed-like heterogeneous Co3(PO4)2/Ni3(PO4)2/MOF-74-x electrocatalysts were synthesized via a hydrothermal method. The optimal composite exhibits excellent catalytic performance toward methanol/ethanol oxidation reactions (MOR/EOR) with peak current densities reaching 27.5 and 32.6 mA cm-2, respectively. This work heralds the advent of more efficient heterogeneous electrocatalysts for DAFCs and other energy conversion systems.

Deep insight on mechanism and contribution of arsenic removal and heavy metals remediation by mechanical activation phosphogypsum.

Arsenic-containing wastewater and arsenic-contaminated soil can cause serious environmental pollution. In this study, phosphogypsum with partial mechanical activation of calcium oxide was used to prepare a new phosphogypsum-based passivate (Ca-mPG), and its remediation performance on arsenic-contaminated soil was evaluated in terms of both effectiveness and microbial response. The results showed that the optimum conditions for the preparation of the passivate were optimized in terms of single factor and response surface with a ball milling speed of 200 r/min, a material ratio of 6:4 and a ball milling time of 4 h. Under these conditions, the adsorption capacity was 37.75 mg/g. The leaching concentration of arsenic (As) in the contaminated soil after Ca-mPG modification decreased from 25.75 µg/L to 5.88 µg/L, which was lower than the Chinese national standard (GB/T 5085.3-2007); Ca-mPG also showed excellent passivation effect on other heavy Metals (copper, nickel, cadmium, zinc). In addition, As-resistant bacteria and passivators work together to promote the stabilization effect of contaminants during the remediation of As-contaminated soil. The mechanisms of Cu, As(III)/As(V), Zn, Cd, and Ni removal were related to ion exchange, electrostatic adsorption of substances on heavy metals, calcium binding to other substances to produce precipitation; and microbially induced stabilization of HMs, oxidized. Overall, this study demonstrates an eco-friendly "waste-soil remediation" strategy to solve problems associated with solid waste reuse and remediation of HM-contaminated soils.

Performance changes in the anammox process under the stress of rare-earth element Ce(III) and the evolution of microbial community and functional genes.

The high Ce(III) content in ionic rare-earth tailings wastewater has hindered the application of anammox process in this field. Here, the effect of Ce(III) on the performance of anammox processes was investigated, and the evolution of microbial communities and functional genes was explored using metagenomic sequencing. The results showed that the reactor nitrogen removal rate decreased when the Ce(III) concentration reached 25 mg/L, although ammonia nitrogen removal (92.31%) and nitrogen removal efficiency (81.33%) remained at a high level; however, both showed a significant decreasing trend. The relative abundance of anammox bacteria increased continuously from P1-P5, reaching 48.81%, whereas the relative abundance of Candidatus jettenia reached 33.71% at P5, which surpassed that of Candidatus brocadia as the most abundant anammox bacteria, and further analysis of functional genes and metabolic pathways revealed that Candidatus brocadia was richer in biochemical metabolic genes, whereas Candidatus jettenia had richer efflux genes.

Simultaneous immobilization of multiple heavy metals in polluted soils amended with mechanical activation waste slag.

Heavy metal soil contamination has become an increasingly serious problem in industrial development. However, industrial byproducts used for remediation are one aspect of green remediation that can contribute to sustainable practices in waste recycling. In this study, electrolytic manganese slags (EMS) were mechanically activated and modified into a passivator (M-EMS), and the heavy metal adsorption performance of M-EMS, heavy metal passivation ability in soil, dissolved organic matter (DOM) change and its effect on the microbial community structure of soil were investigated. The findings revealed that the maximum adsorption capacities of As(V), Cd2+, Cu2+ and Pb2+ were 76.32 mg/g, 301.41 mg/g, 306.83 mg/g and 826.81 mg/g, respectively, indicating that M-EMS demonstrated remarkable removal performance for different heavy metals. The Langmuir model fits Cd2+, Cu2+ and Pb2+ better than the Freundlich model, and monolayer adsorption is the main process. Surface complexation played a major role in the As(V) adsorption's on the surface of metal oxides in M-EMS. The passivation effect was ranked as Pb > Cr > As>Ni > Cd > Cu, with the highest passivation rate of 97.59 % for Pb, followed by Cr (94.76 %), then As (71.99 %), Ni (65.17 %), Cd (61.44 %), and the worst one was Cu (25.17 %). In conclusion, the passivator has the effect of passivation for each heavy metal. The addition of passivating agent can enhance the diversity of microorganisms. Then it can change the dominant flora and induce the passivation of heavy metals through microorganisms. XRD, FTIR, XPS and the microbial community structure of soil indicated that M-EMS can stabilize heavy metals in contaminated soils through four main mechanisms: ion exchange, electrostatic adsorption, complex precipitation and the microbially induced stabilization. The results of this study may provide new insights into the ecological remediation of multiple heavy-metal-contaminated soils and water bodies and research on the strategy of waste reduction and harmlessness by using EMS-based composites in combination with heavy metals in soil.

Rational design of dense microporous carbon derived from coal tar pitch towards high mass loading supercapacitors.

The compact carbon materials with huge specific surface area (SSA) and proper pore structure are highly desirable towards high-performance supercapacitors at the cell level. However, to well balance of porosity and density is still an on-going task. Herein, a universal and facile strategy of pre-oxidation-carbonization-activation is employed to prepare the dense microporous carbons from coal tar pitch. The optimized sample POCA800 not only possesses a well-developed porous structure with the SSA of 2142 m2 g-1 and total pore volume (Vt) of 1.540 cm3 g-1, but also exhibits a high packing density of 0.58 g cm-3 and proper graphitization. Owing to these advantages, POCA800 electrode at areal mass loading of 10 mg cm-2 shows a high specific capacitance of 300.8 F g-1 (174.5 F cm-3) at 0.5 A g-1 and good rate performance. The POCA800 based symmetrical supercapacitor with a total mass loading of 20 mg cm-2 displays a large energy density of 8.07 Wh kg-1 at 125 W kg-1 and remarkable cycling durability. It is revealed that the prepared density microporous carbons are promising for practical applications.

Ar plasma assists in enhanced oxygen evolution kinetics of MOG-derived multicomponent transition metal sulfides.

Transition metal sulfides are low-cost oxygen evolution reaction (OER) electrocatalysts that can potentially substitute noble metal catalysts. However, the adsorption process of their OER is impeded by their intrinsic poor catalytic activity. Constructing heterojunction and vacancy defects in transition metal sulfides is an efficient method to promote the process of oxygen evolution. Herein, a facile approach based on in situ sulfurization of metal-organic gels (MOGs) and a short-time plasma treatment was developed to fabricate vacancy-modified polymetallic sulfides heterojunction. The synergistic effect of the multi-component heterojunction and sulfur vacancy contributed greatly to improving the electron migration efficiency and OER ability of the electrocatalyst. As a result, the optimum oxygen evolution activity was achieved with appropriate surface vacancy concentrations by regulating the plasma radio frequency powers. The plasma-treated catalyst under 400 W showed the best OER performance (lower overpotential of 235 mV in 1 M KOH solution with the Tafel slope of 31 mV dec-1) and good durability over 11 h of chronopotentiometry testing. This work sheds new light on constructing multimetal-based heterojunction electrocatalysts with rich vacancy defects for oxygen evolution reactions.