Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Soybean(Glycine max)rhizosphere organic phosphorus recycling relies on acid phosphatase activity and specific phosphorusmineralizing-related bacteria in phosphate deficient acidic soils

Bacteria play critical roles in regulating soil phosphorus(P) cycling. The effects of interactions between crops and soil P-availability on bacterial communities and the feedback regulation of soil P cycling by the bacterial community modifications are poorly understood. Here, six soybean(Glycine max) genotypes with differences in P efficiency were cultivated in acidic soils with long-term sufficient or deficient P-fertilizer treatments. The acid phosphatase(AcP) activities, organic-P concentrations and associated bacterial community compositions were determined in bulk and rhizosphere soils. The results showed that both soybean plant P content and the soil AcP activity were negatively correlated with soil organic-P concentration in P-deficient acidic soils. Soil P-availability affected the ɑ-diversity of bacteria in both bulk and rhizosphere soils. However, soybean had a stronger effect on the bacterial community composition, as reflected by the similar biomarker bacteria in the rhizosphere soils in both P-treatments. The relative abundance of biomarker bacteria Proteobacteria was strongly correlated with soil organic-P concentration and AcP activity in low-P treatments. Further high-throughput sequencing of the phoC gene revealed an obvious shift in Proteobacteria groups between bulk soils and rhizosphere soils, which was emphasized by the higher relative abundances of Cupriavidus and Klebsiella, and lower relative abundance of Xanthomonas in rhizosphere soils. Among them, Cupriavidus was the dominant phoC bacterial genus, and it was negatively correlated with the soil organic-P concentration. These findings suggest that soybean growth relies on organic-P mineralization in P-deficient acidic soils, which might be partially achieved by recruiting specific phoCharboring bacteria, such as Cupriavidus.

Influencing factors analysis of hard limestone reformation and strength weakening under acidic effect

Roof disaster has always been an important factor restricting coal mine safety production.Acidic effect can reform the rock mass structure to weaken the macroscopic strength characteristics,which is an effective way to control the hard limestone roof.In this study,the effects of various factors on the reaction characteristics and mechanical properties of limestone were analyzed.The results show that the acid with stronger hydrogen production capacity after ionization(pK_(a)<0)has more prominent damage to the mineral grains of limestone.When pKa increases from−8.00 to 15.70,uniaxial compressive strength and elastic modulus of limestone increase by 117.22%and 75.98%.The influence of acid concentration is manifested in the dissolution behavior of mineral crystals,the crystal defects caused by large-scale acid action will lead to the deterioration of limestone strength,and the strength after 15%concentration reformation can be reduced by 59.42%.The effect of acidification time on limestone has stages and is the most obvious in the initial metathesis reaction stage(within 60 min).The key to the strength damage of acidified limestone is the participation of hydrogen ions in the reaction system.Based on the analytic hierarchy process method,the influence weights of acid type,acid concentration and acidification time on strength are 24.30%,59.54% and 16.16%,respectively.The research results provide theoretical support for the acidification control of hard limestone roofs in coal mines.

Application of organic fertilizer for improving soybean production under acidic stress

The presence of acidic soil in rural areas poses difficulties for agricultural production.One factor regulating soil pH is the overuse of inorganic fertilizer.The increased use of fertilizers in soybean production not only raises sustainability concerns but also contributes to soil acidity.Therefore,the use of organic fertilizer could offer a solution for addressing both issues related to soil acidity and sustainability.The purpose of this study was to investigate the manipulation of soil pH using organic fertilizer for soybean production under acidic stress.The planting medium,consisting of a mixture of topsoil,rice husk charcoal,and organic fertilizer(in a ratio of 2:1:1),was supplemented with 0.5 g of NPK fertilizer as a basal treatment in each planting medium.To regulate the soil acidity to pH 4,we added FeSO_(4) and allowed the mixture to incubate for 30 days.The results demonstrate that the application of three types of organic fertilizers chicken manure(P1),oil palm empty bunch fertilizer(P2),and vermicompost(P3)positively impacts the growth of three soybean varieties.The findings indicate that the application of P2 organic fertilizer can increase vegetative growth almost 50%in soybeans on acidic soil,including plant height,leaf count,and root length.Meanwhile,applying P3 organic fertilizer can boost reproductive growth responses in soybeans on acidic soil,such as pod number(from around 0-4 unit to 42-51 unit),grain number(from around 0-5 unit to 88-90 unit),and grain weight(from around 0-0.37 g to 12-25 g).Organic fertilizer has the potential to regulate soil pH,promoting higher yields of soybeans under acidic stress.

RuO_(2)/CoMO_(2)O_(x) Catalyst with Low Ruthenium Loading for Long-Term Acidic Oxygen Evolution

We must urgently synthesize highly efficient and stable oxygen-evolution reaction(OER) catalysts for acidic media. Herein, we constructed a series of Ti mesh(TM)-supported RuO_(2)/CoMo_(y)O_(x) catalysts(RuO_(2)/CoMo_(y)O_(x)/TM) with heterogeneous structures. By optimizing the ratio of Co to Mo, RuO_(2)/CoMO_(2)O_(x)/TM with low Ru loading(0.079 mg/cm^(2)) achieves remarkable OER performance(η = 243 mV at 10 mA/cm^(2)) and high stability(300 h @ 10 mA/cm^(2)) in 0.5 mol/L H_(2)SO_(4) electrolyte. The activity of RuO_(2)/CoMo_yO_x/TM can be maintained for 50 h at 100 mA/cm^(2), and a water electrolyzer with RuO_(2)/CoMO_(2)O_(x)/TM as anode can operate for 40 h at 100 mA/cm~2, suggesting the remarkable OER durability of RuO_(2)/CoMo__(y)O__(x)/TM in acidic electrolyte. Owing to the heterogeneous interface between CoMO_(2)O_(x) and RuO_(2), the electronic structure of Ru atoms was optimized and electron-rich Ru was formed. With modulated electronic properties, the dissociation energy of H_(2)O is weakened, and the OER barrier is lowered. This study provides the design of low-cost noble metal catalysts with long-term stability in an acidic environment.

Enhancing selectivity in acidic CO_(2) electrolysis:Cation effects and catalyst innovation

The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2) conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2) electrolysis.It commences with an overview of the latest advancements in acidic CO_(2) electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2) electrolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2) electrolysis are suggested.

Impact of wetting-drying cycles and acidic conditions on the soil aggregate stability of yellow‒brown soil

Soil aggregate is the basic structural unit of soil,which is the foundation for supporting ecosystem functions,while its composition and stability is significantly affected by the external environment.This study was conducted to explore the effect of external environment(wetting-drying cycles and acidic conditions)on the soil aggregate distribution and stability and identify the key soil physicochemical factors that affect the soil aggregate stability.The yellow‒brown soil from the Three Gorges Reservoir area(TGRA)was used,and 8 wetting-drying conditions(0,1,2,3,4,5,10 and 15 cycles)were simulated under 4 acidic conditions(pH=3,4,5 and 7).The particle size distribution and soil aggregate stability were determined by wet sieving method,the contribution of environmental factors(acid condition,wetting-drying cycle and their combined action)to the soil aggregate stability was clarified and the key soil physicochemical factors that affect the soil aggregate stability under wetting-drying cycles and acidic conditions were determined by using the Pearson’s correlation analysis,Partial least squares path modeling(PLS‒PM)and multiple linear regression analysis.The results indicate that wetting-drying cycles and acidic conditions have significant effects on the stability of soil aggregates,the soil aggregate stability gradually decreases with increasing number of wetting-drying cycles and it obviously decreases with the increase of acidity.Moreover,the combination of wetting-drying cycles and acidic conditions aggravate the reduction in the soil aggregate stability.The wetting-drying cycles,acidic conditions and their combined effect imposes significant impact on the soil aggregate stability,and the wetting-drying cycles exert the greatest influence.The soil aggregate stability is significantly correlated with the pH,Ca^(2+),Mg^(2+),maximum disintegration index(MDI)and soil bulk density(SBD).The PLS‒PM and multiple linear regression analysis further reveal that the soil aggregate stability is primarily influenced by SBD,Ca^(2+),and MDI.These results offer a scientific basis for understanding the soil aggregate breakdown mechanism and are helpful for clarifying the coupled effect of wetting-drying cycles and acid rain on terrestrial ecosystems in the TGRA.

Selection of Negative Charged Acidic Polar Additives to Regulate Electric Double Layer for Stable Zinc Ion Battery

Zinc-ion batteries are promising for large-scale electrochemical energy storage systems,which still suffer from interfacial issues,e.g.,hydrogen evolution side reaction(HER),self-corrosion,and uncontrollable dendritic Zn electrodeposition.Although the regulation of electric double layer(EDL)has been verified for interfacial issues,the principle to select the additive as the regulator is still misted.Here,several typical amino acids with different characteristics were examined to reveal the interfacial behaviors in regulated EDL on the Zn anode.Negative charged acidic polarity(NCAP)has been unveiled as the guideline for selecting additive to reconstruct EDL with an inner zincophilic H_(2)O-poor layer and to replace H_(2)O molecules of hydrated Zn^(2+)with NCAP glutamate.Taking the synergistic effects of EDL regulation,the uncontrollable interface is significantly stabilized from the suppressed HER and anti-self-corrosion with uniform electrodeposition.Consequently,by adding NCAP glutamate,a high average Coulombic efficiency of 99.83%of Zn metal is achieved in Zn|Cu asymmetrical cell for over 2000 cycles,and NH4V4O10|Zn full cell exhibits a high-capacity retention of 82.1%after 3000 cycles at 2 A g^(-1).Recapitulating,the NCAP principle posted here can quicken the design of trailblazing electrolyte additives for aqueous Zn-based electrochemical energy storage systems.

Acidic/hypoxia dual-alleviated nanoregulators for enhanced treatment of tumor chemo-immunotherapy

Chemotherapy plays a crucial role in triple-negative breast cancer (TNBC) treatment as it not only directly kills cancer cells but also induces immunogenic cell death. However, the chemotherapeutic efficacy was strongly restricted by the acidic and hypoxic tumor environment. Herein, we have successfully formulated PLGA-based nanoparticles concurrently loaded with doxorubicin (DOX), hemoglobin (Hb) and CaCO3 by a CaCO3-assisted emulsion method, aiming at the effective treatment of TNBC. We found that the obtained nanomedicine (DHCaNPs) exhibited effective drug encapsulation and pH-responsive drug release behavior. Moreover, DHCaNPs demonstrated robust capabilities in neutralizing protons and oxygen transport. Consequently, DHCaNPs could not only serve as oxygen nanoshuttles to attenuate tumor hypoxia but also neutralize the acidic tumor microenvironment (TME) by depleting lactic acid, thereby effectively overcoming the resistance to chemotherapy. Furthermore, DHCaNPs demonstrated a notable ability to enhance antitumor immune responses by increasing the frequency of tumor-infiltrating effector lymphocytes and reducing the frequency of various immune-suppressive cells, therefore exhibiting a superior efficacy in suppressing tumor growth and metastasis when combined with anti-PD-L1 (αPD-L1) immunotherapy. In summary, this study highlights that DHCaNPs could effectively attenuate the acidic and hypoxic TME, offering a promising strategy to figure out an enhanced chemo-immunotherapy to benefit TNBC patients.

Determination of total flavonoids content in buckwheat and inhibition of α-amylase activity

Diabetes is one of the most difficult chronic diseases to cure in the world,which seriously affects people’s health and quality of life.Flavonoids in buckwheat can regulate blood glucose levels by inhibitingα-amylase activity.Therefore,sweet buckwheat produced in Inner Mongolia was used as the research object,and buckwheat fl avonoids were extracted by ultrasonic-assisted extraction method.Total fl avonoids content was determined by ultraviolet-visible spectrophotometry.With acarbose as the positive control,the inhibition test ofα-amylase was carried out by DNS colorimetry to study the inhibition behavior of fl avonoids onα-amylase activity.The results showed that the extraction process of flavonoids was stable and reliable,and the established method for the determination of flavonoids was simple,accurate and reproducible.The total flavonoids content of buckwheat samples was 2.706 mg/g,buckwheat total fl avonoids extraction solution had an inhibitory eff ect onα-amylase,and its median inhibition concentration(IC_(50))was 38.53 mg/mL.The results of this experiment provide a technical reference for the development and utilization of fl avonoids in Inner Mongolia sweet buckwheat,and provide a theoretical reference for the development and application of flavonoid-rich hypoglycemic food.

Calcium-Magnesium Ca/Mg Ratios and Their Agronomic Implications for the Optimization of Phosphate Fertilization in Rainfed Rice Farming on Acidic Ferralsol in the Forest Zone of Ivory Coast

This study is a contribution to improving rice productivity on acidic plateau soils of the tropical rainforest zone. It is based on taking into account the cationic balances of the soil in order to optimize the phosphorus (P) nutrition of rice on these acidic soils, where this nutrient constitutes a limiting factor for agricultural production. Three (3) pot trials were conducted in Adiopodoumé in the forested south of Côte d’Ivoire. The interactive effects of calcium carbonate (0, 25, 50 and 75 kg Ca ha−1) and magnesium sulfate (0, 25, 50 and 75 kg Mg ha−1) were evaluated on the response of NERICA 5 rice at doses 0, 25, 50 and 75 kg P ha−1 of natural phosphate from Togo, applied only once at the start of the experiment. Additional fertilizers of nitrogen (N) (100 kg N ha−1) and potassium (K) (50 kg KCl ha−1) were added to each of the tests in a split-plot device. The test results revealed a paddy production potential of approximately 3 to 5 t⋅ha−1 for NERICA 5 on an acidic soil, under the effect of the interaction of P, Ca and Mg. The quadratic response of rice yield to the doses of these fertilizers would be more dependent on their balance, itself influenced by Ca nutrition. For the sustainability and maintenance of rice production in agro-ecology studied, it was recommended doses of 38 kg Ca ha−1, 34 kg Mg ha−1 in a Ca/Mg ratio (1/1) with intakes of 41 kg P ha−1, overall in a ratio 1/1/1 (P/Ca/Mg) more favorable to the availability of free iron considered a guiding element of mineral nutrition. Thus, these promising results should be confirmed in a real environment for better management of the fertilization of rice cultivated on acidic plateau soils in Côte d’Ivoire.

Comparative analysis of physicochemical properties,ginsenosides content andα-amylase inhibitory effects in white ginseng and red ginsen

Ginseng(Panax ginseng C.A.Meyer)as a common dietary adjunct is widely applied in Traditional Chinese Medicine due to its health-promoting properties,but the differences between white ginseng and red ginseng was rarely studied.In the present study,color parameters and scanning electron microscope(SEM)were determined to evaluate the differences of ginseng color and microstructure induced by processing procedure.Quantitative analysis of multi-components by a single-marker(QAMS)method and anti-α-amylase activity test were used to assess variations of chemical ingredients and pharmacological activity between white and red ginseng.Finally,molecular docking studies were carried out to screen out the most effective compound againstα-amylase.Results indicated that processing had a significant impact on the physicochemical properties and pharmacological activity of white and red ginseng.After processing,the color value of L*declined significantly.Red ginseng sample displayed a compact structure and presented of a gel layer on the surface compared to white ginseng.Additionally,the content of ginsenosides and the activity of anti-α-amylase decreased.The contents of total ginsenosides were positively correlated with the anti-α-amylase activities of ginseng,and ginsenoside Rb1 might be the most effective compound to inhibit the activity ofα-amylase.

Recent Advances and Perspectives of Lewis Acidic Etching Route:An Emerging Preparation Strategy for MXenes

Since the discovery in 2011,MXenes have become the rising star in the field of two-dimensional materials.Benefiting from the metallic-level conductivity,large and adjustable gallery spacing,low ion diffusion barrier,rich surface chemistry,superior mechanical strength,MXenes exhibit great application prospects in energy storage and conversion,sensors,optoelectronics,electromagnetic interference shielding and biomedicine.Nevertheless,two issues seriously deteriorate the further development of MXenes.One is the high experimental risk of common preparation methods such as HF etching,and the other is the difficulty in obtaining MXenes with controllable surface groups.Recently,Lewis acidic etching,as a brand-new preparation strategy for MXenes,has attracted intensive attention due to its high safety and the ability to endow MXenes with uniform terminations.However,a comprehensive review of Lewis acidic etching method has not been reported yet.Herein,we first introduce the Lewis acidic etching from the following four aspects:etching mechanism,terminations regulation,in-situ formed metals and delamination of multi-layered MXenes.Further,the applications of MXenes and MXene-based hybrids obtained by Lewis acidic etching route in energy storage and conversion,sensors and microwave absorption are carefully summarized.Finally,some challenges and opportunities of Lewis acidic etching strategy are also presented.

Progress on the mechanisms of Ru-based electrocatalysts for the oxygen evolution reaction in acidic media

Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the oxygen evolution reaction(OER).Nevertheless,a trade-off between activity and stability exists for most electrocatalytic materials in strong acids and oxidizing media,and the development of efficient and stable catalytic materials has been an important focus of research.In this view,gaining in-depth insights into the OER system,particularly the interactions between reaction intermediates and active sites,is significantly important.To this end,this review introduces the fundamentals of the OER over Ru-based materials,including the conventional adsorbate evolution mechanism,lattice oxygen oxidation mechanism,and oxide path mechanism.Moreover,the up-to-date progress of representative modifications for improving OER performance is further discussed with reference to specific mechanisms,such as tuning of geometric,electronic structures,incorporation of proton acceptors,and optimization of metal-oxygen covalency.Finally,some valuable insights into the challenges and opportunities for OER electrocatalysts are provided with the aim to promote the development of next-generation catalysts with high activity and excellent stability.

Dynamically-evolved surface heterojunction in iridium nanocrystals boosting acidic oxygen evolution and overall water splitting

Simultaneously realizing improved activity and stability of acidic oxygen evolution reaction(OER) electrocatalysts is highly promising for developing cost-effective sustainable energy in the splitting of water technique.Herein,we report iridium nanocrystals embedded into 3D conductive clothes(Ir-NCT/CC) as a low iridium electrocatalyst realizing ultrahigh acidic OER activity and robust stability.The well-designed Ir-NCT/CC requires a low overpotential of 202 mV to reach the current density of 10 mA cm^(-2)with a high mass activity of 1754 A g^(-1).Importantly,in acidic overall water splitting,Ir-NCT/CC merely delivers a cell voltage of 1.469 V at a typical current density of 10 mA cm^(-2)and also maintains robust durability under continuous operation.We identify that a low working voltage drives the formation of a highly stable amorphous IrOxactive phase over the surface of Ir nanocrystals(surface heterojunction IrOx/Ir-NCT) during operating conditions,which contributes to an effective and durable OER process.

Recent progress of advanced manganese oxide-based materials for acidic oxygen evolution reaction: Fundamentals, performance optimization,and prospects

The oxygen evolution reaction(OER) is the basis of various sustainable energy conversion and storage techniques,especially hydrogen production by water electrolysis.To realize the practical application of hydrogen energy and mass-scale hydrogen production via water electrolysis,several obstacles,such as the multi-electron transfer OER process with sluggish kinetics and overall high reaction barrier,should be overcome.Manganese oxide-based(MnOx) materials,especially MnO_(2),have emerged as promising non-noble electrocatalysts for water electro-oxidation under acidic conditions due to their wellbalanced properties between catalytic activity and stability.This review introduces the fundamental understanding of the catalytic OER process on MnOx-based materials,including the conventional adsorbate evolution mechanism(AEM) and emerging lattice oxygen oxidation mechanism(LOM).The rational screening and prediction of MnOx-based catalysts that can stably catalyze OER in acid are summarized based on Pourbaix diagram analysis and thermodynamic density functional theory(DFT) calculations.Then,the up-to-date progress of upgrading the OER catalytic performance of MnOx-based catalysts by composite construction is reviewed.Afterward,feasible strategies to improve the electrocatalytic activity and lifetime of MnOx-based catalysts are systemically discussed in terms of crystal structure control,reasonable setting of working potential and electrolyte environment,optimal selection of acid-stable conductive supports,and self-healing engineering.Finally,future scientific challenges and research directions are outlined to guide the construction of advanced MnOx-based electrocatalysts for OER in acid.

Differential Expression of Iron Deficiency Responsive Rice Genes under Low Phosphorus and Iron Toxicity Conditions and Association of OsIRO3 with Yield in Acidic Soils

With the hypothesis that iron(Fe) deficiency responsive genes may play a role in Fe toxicity conditions,we studied five such genes OsNAS1,OsNAS3,OsIRO2,OsIRO3 and OsYSL16 across six contrasting rice genotypes for expression under high Fe and low phosphorus(P) conditions,and sequence polymorphism.Genotypes Sahbhagi Dhan,Chakhao Poirieton and Shasharang were high yielders with no bronzing symptom visible under Fe toxic field conditions,and BAM350 and BAM811 were low yielders but did not show bronzing symptoms.Hydroponic screening revealed that the number of crown roots and root length can be traits for consideration for identifying Fe toxicity tolerance in rice genotypes.Fe contents in rice roots and shoots of a high-yielding genotype KMR3 showing leaf bronzing were significantly high.In response to 24 h high Fe stress,the expression levels of OsNAS3 were up-regulated in all genotypes except KMR3.In response to 48 h high Fe stress,the expression levels of OsNAS1 were3-fold higher in tolerant Shasharang,whereas in KMR3,it was significantly down-regulated.Even in response to 7 d excess Fe stress,the transcript abundances of OsIRO2 and OsNAS3 were contrasting in genotypes Shasharang and KMR3.This suggested that the reported Fe deficiency genes had a role in Fe toxicity and that in genotype KMR3 under excess Fe stress,there was disruption of metal homeostasis.Under the 48 h low P conditions,OsIRO2 and OsYSL16 were significantly up-regulated in Fe tolerant genotype Shasharang and in low P tolerant genotype Chakhao Poirieton,respectively.In silico sequence analysis across 3 024 rice genotypes revealed polymorphism for 4 genes.Sequencing across OsIRO3and OsNAS3 revealed nucleotide polymorphism between tolerant and susceptible genotypes for Fe toxicity.Non-synonymous single nucleotide polymorphisms and insertion/deletions(InDels) differing in tolerant and susceptible genotypes were identified.A marker targeting 25-bp InDel in OsIRO3,when run on a diverse panel of 43 rice genotypes and a biparental population,was associated with superior performance for yield under acidic lowland field conditions.This study highlights the potential of one of the vital genes involved in Fe homeostasis as a genic target for improving rice yield in acidic soils.

Effects of deep alkaline and acidic fluids on reservoir developed in fault belt of saline lacustrine basin

Through the long development processes of reservoir sedimentation and diagenesis, acidic and alkaline fluids play key roles in controlling deep reservoir development. However, the ways in which deep fluids control and transform the reservoir under complex fault conditions remain unclear. In this study, a 2D model was established based on a typical sub-salt to intra-salt vertical profile in the Qaidam Basin, China. Based on measured data, multiphase flow reaction and solute transport simulation technology were used to analyze fluids flow and migration in the intra-salt and sub-salt reservoirs, determine the mineral dissolution, precipitation, and transformation in the reservoir caused by the deep fluids, and calculate the changes in reservoir porosity. Results show that deep fluid migrates preferentially along dominant channels and triggers a series of fluid–rock chemical reactions. In the first stage, a large amount of anhydrite precipitated in the fault as a result of upward migration of deep saline fluid, resulting in the formation of anhydrite veins and blockage at the base of the fault. In the second stage, organic acids caused minerals dissolution and a vertical channel was opened in previously blocked area, which promoted continuous upward migration of organic acids and the formation of secondary pores. This study clarifies the transformative effects of deep alkaline and acidic fluids on the reservoir. Moreover, the important fluid transport role of faults and their effect on reservoir development were determined.

Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid

Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the leachate.These methods usually are followed by a series of separation steps such as precipitation,extraction,and stripping to separate the individual valuable metals.In this study,we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids.Under optimal leaching conditions(leaching time of 1.5 h,leaching temperature of 70°C,liquid-solid ratio of 4 mL/g,oxalic acid ratio of 1.3,and sulfuric acid ratio of 1.3),the lithium leaching efficiency reached89.6%,and the leaching efficiencies of Ni,Co,and Mn were 12.8%,6.5%,and 21.7%.X-ray diffraction(XRD)and inductively coupled plasma optical emission spectrometer(ICP-OES)analyses showed that most of the Ni,Co,and Mn in the raw material remained as solid residue oxides and oxalates.This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.

Recovery of Li, Ni, Co and Mn from spent lithium-ion batteries assisted by organic acids: Process optimization and leaching mechanism

The proper recycling of spent lithium-ion batteries(LIBs)can promote the recovery and utilization of valuable resources,while also negative environmental effects resulting from the presence of toxic and hazardous substances.In this study,a new environmentally friendly hydro-metallurgical process was proposed for leaching lithium(Li),nickel(Ni),cobalt(Co),and manganese(Mn)from spent LIBs using sulfuric acid with citric acid as a reductant.The effects of the concentration of sulfuric acid,the leaching temperature,the leaching time,the solid-liquid ratio,and the reducing agent dosage on the leaching behavior of the above elements were investigated.Key parameters were optimized using response surface methodology(RSM)to maximize the recovery of metals from spent LIBs.The maxim-um recovery efficiencies of Li,Ni,Co,and Mn can reach 99.08%,98.76%,98.33%,and 97.63%.under the optimized conditions(the sulfuric acid concentration was 1.16 mol/L,the citric acid dosage was 15wt%,the solid-liquid ratio was 40 g/L,and the temperature was 83℃ for 120 min),respectively.It was found that in the collaborative leaching process of sulfuric acid and citric acid,the citric acid initially provided strong reducing CO_(2)^(-),and the transition metal ions in the high state underwent a reduction reaction to produce transition metal ions in the low state.Additionally,citric acid can also act as a proton donor and chelate with lower-priced transition metal ions,thus speeding up the dissolution process.