Study on synergistic leaching of potassium and phosphorus from potassium feldspar and solid waste phosphogypsum via coupling reactions

To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.

In situ atomic-scale tracking of unusual interface reaction circulation and phase reversibility in(de)potassiated alloy-typed anode

Alloy-typed anode materials,endowed innately with high theoretical specific capacity,hold great promise as an alternative to intercalation-typed counterparts for alkali-ion batteries.Despite tremendous efforts devoted to addressing drastic volume change and severe pulverization issues of such anodes,the underlying mechanisms involving dynamic phase evolutions and reaction kinetics have not yet been fully comprehended.Herein,taking antimony(Sb)anode as a representative paradigm,its microscopic operating mechanisms down to the atomic scale during live(de)potassiation cycling are systematically unraveled using in situ transmission electron microscopy.Highly reversible phase transformations at single-particle level,that are Sb←→KSb_(2)←→KSb←→K_5Sb_(4)←→K_(3)Sb,were revealed during cycling.Meanwhile,multiple phase interfaces associated with different reaction kinetics coexisted and this phenomenon was properly elucidated in the context of density functional theory calculations.Impressively,previously unexplored unidirectional circulation of reaction interfaces within individual Sb particle is confirmed for both potassiation and depotassiation.Based on the empirical results,the surface diffusion-mediated potassiation-depotassiation pathways at single-particle level are suggested.This work affords new insights into energy storage mechanisms of Sb anode and valuable guidance for targeted optimization of alloy-typed anodes(not limited to Sb)toward advanced potassium-ion batteries.

Modulating Co-Co bonds average length in Co_(0.85)Se_(1-x)S_(x) to enhance conversion reaction for potassium storage

While alloying transition metal chalcogenides(TMCs)with other chalcogen elements can effectively improve their conductivity and electrochemical properties,the optimal alloying content is still uncertain.In this study,we study the influence of dopant concentration on the chemical bonds in TMC and reveal the associated stepwise conversion reaction mechanism for potassium ion storage.According to density function theory calculations,appropriate S-doping in Co0.85Se(Co_(0.85)Se_(1-x)S_(x))can reduce the average length of Co-Co bonds because of the electronegativity variation,which is thermodynamically favourable to the phase transition reactions.The optimal Se/S ratio(x=0.12)for the conductivity has been obtained from experimental results.When assembled as an anode in potassium-ion batteries(PIBs),the sample with optimized Se/S ratio exhibits extraordinary electrochemical performance.The rate performance(229.2 mA h g^(-1)at 10 A g^(-1))is superior to the state-of-the-art results.When assembled with Prussian blue(PB)as a cathode,the pouch cell exhibits excellent performance,demonstrating its great potential for applications.Moreover,the stepwise K+storage mechanism caused by the coexistence of S and Se is revealed by in-situ X-ray diffraction and ex-situ transmission electron microscopy techniques.Hence,this work not only provides an effective strategy to enhance the electrochemical performance of transition metal chalcogenides but also reveals the underlying mechanism for the construction of advanced electrode materials.

长链非编码RNA POT1-AS1在宫颈癌顺铂耐药中的作用研究

背景同步放化疗是晚期宫颈癌(cervical cancer,CC)的治疗方法,顺铂(cisplatin,CDDP)是目前临床化疗使用的主要药物之一,CDDP耐药的发生严重制约了其临床应用,因此针对CDDP耐药发生机制的研究对CC的治疗至关重要。目的探索长链非编码RNA(long non-coding RNA,lncRNA)POT1-AS1在宫颈癌CDDP耐药中的作用。方法基于TCGA数据库,分析POT1-AS1在CC组织及正常组织中的表达情况,并分析POT1-AS1的表达量与预后的关系。采用CCK-8实验评估CDDP处理后的耐药细胞系和亲本细胞系、siPOT1-AS1组和siNC组的活力并测定相应的半抑制浓度(the half maximal inhibitory concentration,IC50)。实时荧光定量PCR(quantitative real-time PCR,qPCR)检测POT1-AS1在耐药细胞系及相应亲本细胞系中的表达以及POT1-AS1表达与CDDP作用时间的相关性。克隆形成实验检测POT1-AS1对CDDP耐药细胞增殖情况的影响。PI/DAPI双染荧光用于评估POT1-AS1与CDDP诱导的细胞死亡的相关性。结果POT1-AS1在CC肿瘤组织中高表达,并与不良预后相关。耐药细胞系的细胞活力及IC50值显著高于亲本细胞系(P<0.001),POT1-AS1沉默组的细胞活力及IC50值显著低于阴性对照(negative control,NC)组(P<0.001),差异均有统计学意义。POT1-AS1在耐药细胞系中的表达显著高于亲本细胞系(P<0.001),且随着CDDP给药时间的延长而增加。沉默POT1-AS1后可显著抑制耐药细胞的增殖能力(P<0.01)。与NC组相比,POT1-AS1沉默组的CC耐药细胞死亡率显著增加(P<0.01),尤其是在加入CDDP作用后(P<0.01)。结论POT1-AS1与宫颈癌CDDP耐药密切相关,并通过抑制CDDP诱导的细胞死亡发挥促癌作用。

Theoretical uncertainties of(d,^(3)He)and(^(3)He,d)reactions owing to the uncertainties of optical model potentials

The theoretical uncertainties of single proton transfer cross sections of the(^(3)He,d)and(d,^(3)He)reactions,owing to the uncertainties of the entrance-and exit-channel optical model potentials,are examined with the^(30)Si(^(3)He,d)^(31)P,^(13)B(d,^(3)He)^(12)Be,and^(34)S(^(3)He,d)^(35)Cl reactions at incident energies of 25,46,and 25 MeV,respectively,within the framework of the distorted wave Born approximation.The differential cross sections at the first peaks in the angular distributions of these reactions are found to have uncertainties of approximately 5%,owing to the uncertainties in the optical model potentials from 20,000 calculations of randomly sampled parameters.This amount of uncertainty is found to be nearly independent of the angular momentum transfer and the target masses within the studied range of incident energies.Uncertainties in the single proton spectroscopic factors obtained by matching the theoretical and experimental cross sections at different scattering angles are also discussed.

Reaction视频中用户弹幕信息交互行为的情感反应生成机理研究

深入挖掘Reaction视频中弹幕信息交互行为的情感反应机理有助于理解用户弹幕创作背后的情感生成原因及情感变化过程。本文基于情感反应模型,利用定向内容分析法对哔哩哔哩网站中11个热门视频的弹幕信息资源、视频内容以及reactor反应情况展开编码研究,构建了Reaction视频中用户弹幕信息交互行为的情感反应生成机理模型。研究发现,Reaction视频弹幕信息交互行为中的情感反应生成机理总体上遵循“信息刺激-情感反应”的路径,信息刺激有时会独立唤醒情绪或特定情感态度,有时也会通过唤醒特定情感态度进而影响情绪或内化情感态度的生成。该模型有助于提升情感反应理论在计算机协助交流中的情境化探索,也将为社交媒体中用户与信息交互提供优化建议。

基于改进POT模型的混凝土浇筑仓温度双控指标拟定

基于小概率法或最大熵法拟定浇筑仓温度双控指标时对样本数据的极端值保留程度欠缺,而现有文献关于温度双控指标拟定所选取的典型龄期没有明确的物理意义。为避免混凝土浇筑仓温度超过容许最高温度,结合某混凝土坝在高温季节浇筑仓实测温度,采用POT模型拟定了混凝土浇筑仓在绝热温升半熟龄期下的温度双控指标。为了提高结果可靠性,选用基于3σ准则改进的阈值确定方法,并提出了一种改进的POT模型条件概率确定方法。工程实例分析表明:采用改进POT模型与典型小概率法拟定的温度双控指标较为接近,但由于POT模型重点考虑了极端条件下的浇筑仓温度,对极端事件概率下的估计更为准确,由此求出的温度双控指标更合理。此外,选取混凝土浇筑仓在绝热温升半熟龄期作为拟定温度双控指标的典型龄期更利于工程推广。

极值BMM模型与POT模型对面板堆石坝安全监控指标拟定的比较研究

研究极值理论中极值BMM模型和POT模型在大坝安全监控指标拟定上的运用,通过引用经济学上的分位数和极端风险(VaR)值的概念,根据对应公式计算出相应数值进行量化比较分析。研究结果表明,极值BMM模型和POT模型在高置信水平下均能反映出数据的极端风险状况;在99%置信水平下两模型VaR值均大于在95%置信水平下的VaR值;在99%置信水平下极值BMM模型计算出的VaR值比POT模型下的VaR值更大,且接近于拟定指标,表明极值BMM模型下VaR值更能反映出数据的极值状态;在指标拟定方面,极值BMM模型较为适合拟定数据范围内的警戒指标,而POT模型指标拟定结果是超越样本数据本身,具有一定的预测性,适合拟定为样本数据的预测指标。

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.

Exciting lattice oxygen of nickel–iron bi-metal alkoxide for efficient electrochemical oxygen evolution reaction

High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.

Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

Precisely Control Relationship between Sulfur Vacancy and H Absorption for Boosting Hydrogen Evolution Reaction

Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.

Particle agglomeration and inhibition method in the fluidized pyrolysis reaction of waste resin

This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and defluidization.Adding kaolin could effectively inhibit the particle agglomeration during the fluidized pyrolysis reaction through physical isolation and chemical reaction.On the one hand,kaolin could form a coating layer on the surface of ceramic particles to prevent the adhesion of organic ash generated by the pyrolysis of resin.On the other hand,when a sufficient amount of kaolin(-0.2%(mass))was added,the activated kaolin could fully contact with the Na+ ions generated by the pyrolysis of resin and react to form a high-melting aluminosilicate mineral(nepheline),which could reduce the formation of low-melting-point sodium sulfate and thereby avoid the agglomeration of ceramic particles.

Optimizing 3d spin polarization of CoOOH by in situ Mo doping for efficient oxygen evolution reaction

Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will benefit their quick transition to the next catalysts.Herein,Mo-doped CoOOH was designed as a high-performance model electrocatalyst with durability for 20 h at 10 mAcm−2.Additionally,it had an overpotential of 260 mV(glassy carbon)or 215 mV(nickel foam),which was 78 mV lower than that of IrO_(2)(338 mV).In situ,Raman spectroscopy revealed the transformation process of CoOOH.Calculations using the density functional theory showed that during OER,doped Mo increased the spin-up density of states and shrank the spin-down bandgap of the 3d orbits in the reconstructed CoOOH under the electrochemical activation process,which simultaneously optimized the adsorption and electron conduction of oxygen-related intermediates on Co sites and lowered the OER overpotentials.Our research provides new insights into the methodical planning of the creation of transition-metal oxyhydroxide OER catalysts.

Interfacial reaction between AZ91D magnesium alloy melt and mild steel under high temperature

The metallurgical quality control of magnesium(Mg)and Mg alloys in melting process is required to ensure a satisfied mechanical and corrosion performance,while the typical used steel crucible introduces impurities and interfacial interaction during melting process.Therefore,a systematic study about impurities diffusion and interfacial interaction between molten Mg and steel is necessary.In the present study,the interfacial reaction between molten AZ91D Mg alloy and mild steel during melting process was investigated with the melting temperatures of 700℃,750℃ and 800℃.The results show that Al(Fe,Mn)intermetallic layer is the intermetallic primarily formed at the interfaces of AZ91D melt and mild steel.Meanwhile,Al_(8)(Mn,Fe)5is indexed between Al(Fe,Mn)and AZ91D.AlFe_(3)C appears between the mild steel and Al(Fe,Mn)at 700℃ and 750℃,but absent at 800℃ due to the increased solubility of carbon in Mg matrix.It is found that the growth of the intermetallic layer is controlled by diffusion mechanism,and Al and Mn are the dominant diffusing species in the whole interfacial reaction process.By measuring the thickness of different layers,the growth constant was calculated.It increases from 1.89(±0.03)×10^(-12)m^(2)·s^(-1)at 700℃ to 3.05(±0.05)×10^(-12)m^(2)·s^(-1)at 750℃,and 5.18(±0.05)×10^(-12)m^(2)·s^(-1)at 800℃.Meanwhile,the content of Fe is linearly increased in AZ91D with the increase of holding time at 700℃ and 750℃,while it shows a significantly increment after holding for 8 h at 800℃,indicating holding temperature is more crucial to determine the Fe content of AZ91D than holding time.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Possibilities for the synthesis of superheavy element Z=121 in fusion reactions

Based on the dinuclear system model,the calculated evaporation residue cross sections matched well with the current experimental results.The synthesis of superheavy elements Z=121 was systematically studied through combinations of stable projectiles with Z=21-30 and targets with half-lives exceeding 50 d.The influence of mass asymmetry and isotopic dependence on the projectile and target nuclei was investigated in detail.The reactions^(254)Es(^(46)Ti,3n)^(297)121 and^(252)Es(^(46)Ti,3n)^(295)121 were found to be experimentally feasible for synthesizing superheavy element Z=121,with maximal evaporation residue cross sections of 6.619 and 4.123 fb at 219.9 and 223.9 MeV,respectively.

Differences in CO_(2)-Water-Rock Chemical Reactions among ’Sweet Spot’ Reservoirs:Implications for Carbon Sequestration

The Lucaogou Formation,located in the Jimsar Sag,Junggar Basin,NW China,has great potential for shale oil resources.In the process of CO_(2)-EOR(CO_(2) enhance oil recovery),mineral dissolution,precipitation and transformation,leading to the local corrosion or blockage of reservoirs,have a significant influence on recovery.In this study,a combination of high-temperature and high-pressure laboratory experiments and coupled temperature/fluid-chemistry multifield numerical simulations are used to investigate CO_(2)-water-rock reactions under various reservoir conditions in the upper and lower ’sweet spots’,to reveal the mechanisms underlying CO_(2)-induced mineral dissolution,precipitation and transformation.In addition,we quantitatively calculated the evolution of porosity over geological timescales;compared and analyzed the variability of CO_(2) transformation in the reservoir under a variety of temperature,lithology and solution conditions;and identified the main factors controlling CO_(2)-water-rock reactions,the types of mineral transformation occurring during long-term CO_(2) sequestration and effective carbon sequestration minerals.The results demonstrate that the main minerals undergoing dissolution under the influence of supercritical CO_(2) are feldspars,while the main minerals undergoing precipitation include carbonate rock minerals,clay minerals and quartz.Feldspar minerals,especially the initially abundant plagioclase in the formation,directly affects total carbon sequestration,feldspar-rich clastic rocks therefore having considerable sequestration potential.

Effects of Maillard reaction and its product AGEs on aging and age-related diseases

Maillard reaction(MR)is a non-enzymatic browning reaction commonly seen in food processing,which occurs between reducing sugars and compounds with amino groups.Despite certain advantages based on Maillard reaction products(MRPs)found in some food for health and storage application have appeared,however,the MR occurring in human physiological environment can produce advanced glycation end products(AGEs)by non-enzymatic modification of macromolecules such as proteins,lipids and nucleic acid,which could change the structure and functional activity of the molecules themselves.In this review,we take AGEs as our main object,on the one hand,discuss physiologic aging,that is,age-dependent covalent cross-linking and modification of proteins such as collagen that occur in eyes and skin containing connective tissue.On the other hand,pathological aging associated with autoimmune and inflammatory diseases,neurodegenerative diseases,diabetes and diabetic nephropathy,cardiovascular diseases and bone degenerative diseases have been mainly proposed.Based on the series of adverse effects of accelerated aging and disease pathologies caused by MRPs,the possible harm caused by some MR can be slowed down or inhibited by artificial drug intervention,dietary pattern and lifestyle control.It also stimulates people's curiosity to continue to explore the potential link between the MR and human aging and health,which should be paid more attention to for the development of life sciences.

Bimetallic In_(2)O_(3)/Bi_(2)O_(3) Catalysts Enable Highly Selective CO_(2) Electroreduction to Formate within Ultra-Broad Potential Windows

CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet the industrial demands.Herein,the nanorod-like bimetallic ln_(2)O_(3)/Bi_(2)O_(3)catalysts were successfully synthesized by pyrolysis of bimetallic InBi-MOF precursors.The abundant oxygen vacancies generated from the lattice mismatch of Bi_(2)O_(3)and ln_(2)O_(3)reduced the activation energy of CO_(2)to*CO_(2)·^(-)and improved the selectivity of*CO_(2)·^(-)to formate simultaneously.Meanwhile,the carbon skeleton derived from the pyrolysis of organic framework of InBi-MOF provided a conductive network to accelerate the electrons transmission.The catalyst exhibited an ultra-broad applied potential window of 1200 mV(from-0.4 to-1.6 V vs RHE),relativistic high Faradaic efficiency of formate(99.92%)and satisfactory stability after 30 h.The in situ FT-IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO_(2)molecules,and oxygen vacancy path is dominant pathway.This work provides a convenient method to construct high-performance bimetallic catalysts for the industrial application of CO_(2)RR.