Extraction of Valuable Metals from Titanium-bearing Blast Furnace Slag by Acid Leaching

To realize the resource utilization of the valuable metals in the titanium-containing blast furnace slag,the process route of “hydrochloric acid leaching-electrolysis-carbonization and carbon dioxide capture-preparation of calcium carbonate” was proposed.In this study,the influences of process conditions on the leaching rates of calcium,magnesium,aluminum,and iron and the phases of the leaching residue were investigated for the leaching process.The experimental results show that the HCl solution could selectively leach the elements from the titanium-containing blast furnace slag.The better leaching conditions are the HCl solution concentration of 4 mol/L,the leaching time of 30 min,the ratio of liquid volume to solid gas of 10 mL/g,and the stirring paddle speed of 300 r/min.Under the conditions,the leaching rates of calcium,magnesium,aluminum,and iron can reach 85.87%,73.41%,81.35%,and 59.08%,and the leaching rate of titanium is 10.71%.The iron and the aluminum are removed from the leachate to obtain iron-aluminum water purification agents,and the magnesium is removed from the leachate to obtain magnesium hydroxide.The leaching residue phase is dominated by perovskite,followed by magnesium silicate and tricalcium aluminate,and the titaniumrich material could be obtained from the leaching residue by desiliconization.

Rational Design of Cost-Effective Metal-Doped ZrO_(2)for Oxygen Evolution Reaction

The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction(OER)due to the“stable-oractive”dilemma.Zirconium dioxide(ZrO_(2)),a versatile and low-cost material that can be stable under OER operating conditions,exhibits inherently poor OER activity from experimental observations.Herein,we doped a series of metal elements to regulate the ZrO_(2)catalytic activity in OER via spin-polarized density functional theory calculations with van der Waals interactions.Microkinetic modeling as a function of the OER activity descriptor(G_(O*)-G_(HO*))displays that 16 metal dopants enable to enhance OER activities over a thermodynamically stable ZrO_(2)surface,among which Fe and Rh(in the form of single-atom dopant)reach the volcano peak(i.e.the optimal activity of OER under the potential of interest),indicating excellent OER performance.Free energy diagram calculations,density of states,and ab initio molecular dynamics simulations further showed that Fe and Rh are the effective dopants for ZrO_(2),leading to low OER overpotential,high conductivity,and good stability.Considering cost-effectiveness,single-atom Fe doped ZrO_(2)emerged as the most promising catalyst for OER.This finding offers a valuable perspective and reference for experimental researchers to design cost-effective catalysts for the industrial-scale OER production.

Mitigated reaction kinetics between lithium metal anodes and electrolytes by alloying lithium metal with low-content magnesium

Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.

The effect of the carbon components on the performance of carbonbased transition metal electrocatalysts for the hydrogen evolution reaction

The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production industry.However,there is a lack of discussion regarding the effect of carbon components on the performance of these electrocatalysts.This review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting materials.It not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.

Secondary reaction mechanism of leaching process of calcium aluminate slag

SiO2 in calcium aluminate slag exists in the form of γ-2CaO·SiO2 which is more stable than β-2CaO·SiO2. However, it is decomposed by sodium carbonate solution during leaching process, leading to the secondary reaction. The extent of secondary reaction and reaction mechanism of calcium aluminate slag were studied using XRD. The results show that the decomposition rate of γ-2CaO·SiO2 increases with the increase in leaching time and sodium carbonate concentration. The main products of secondary reaction are the mixture of hydrogarnet and sodium hydrate alumina-silicate. SiO2 concentration rises firstly and then drops with the increase of leaching temperature. XRD results indicate that the stable product of secondary reaction at low temperature is hydrogarnet. But hydrogarnet is transformed into sodium hydrate alumina-silicate at high temperature.

Methanol Tolerant Non-noble Metal Co-C-N Catalyst for Oxygen Reduction Reaction Using Urea as Nitrogen Source

A non-noble metal oxygen reduction reaction （ORR） catalyst labeled as Co-C-N（800） was synthesized by heat-treating a mixture of urea, cobalt chloride and acetylene black for 2 h at 800 ℃ in an inert nitrogen atmosphere. X-ray diffraction pattern indicates that a metallic β-Co is generated after the heat-treating process. The results from cyclic voltammograms show that the obtained Co-C-N（800） catalyst has good ORR catalytic activity in 0.5 mol/L H2SO4 solution. The catalyst is also good at methanol tolerance and stability in the acidic solution.

Reaction Process of Chromium Slag Reduced by Industrial Waste in Solid Phase

M, a particular industrial waste, was selected to detoxify chromium slag at a high temperature. The carbon remaining in M reduced Cr （ Ⅳ ） of Na2 CrO4 borne in the chromium slag to Cr （ Ⅲ ） in the solid phase reaction, and its thermodynamics and kinetics were studied. The reduction process of Na2CrO4 by carbon produced CO, whiCh＇was endothermic. Under the experimental condition, the apparent activation energy was 4. 41 kJ·mol^-1 , the＇apparent order of reaction for Na2 CrO4 was equal to one, and the partial pressure of CO was only 0.22 Pa at 1 330℃.

Recent developments in metal phosphide and sulfide electrocatalysts for oxygen evolution reaction

Oxygen evolution reaction(OER),as an important half‐reaction involved in water splitting,has been intensely studied since the last century.Transition metal phosphide and sulfide‐based compounds have attracted increasing attention as active OER catalysts due to their excellent physical and chemical characters,and massive efforts have been devoted to improving the phosphide and sulfide‐based materials with better activity and stability in recent years.In this review,the recent progress on phosphide and sulfide‐based OER electrocatalysts in terms of chemical properties,synthetic methodologies,catalytic performances evaluation and improvement strategy is reviewed.The most accepted reaction pathways as well as the thermodynamics and electrochemistry of the OER are firstly introduced in brief,followed by a summary of the recent research and optimization strategy of phosphide and sulfide‐based OER electrocatalysts.Finally,some mechanistic studies of the active phase of phosphide and sulfide‐based compounds are discussed to give insight into the nature of active catalytic sites.It is expected to indicate guidance for further improving the performances of phosphide and sulfide‐based OER electrocatalysts.

Remediation of Steel Slag on Acidic Soil Contaminated by Heavy Metal

The technology of in situ immobilization with amendments is an important measure that remediates the soil contaminated by heavy metals, and selecting economical and effective amendments is the key. The effects and mechanism of steel slag, the silicon-rich alkaline byproduct which can remediate acidic soil contaminated by heavy metal, are mainly introduced in this paper to provide theory reference for future research. Firstly, the paper analyzes current research situation of in situ immobilization with amendments. Then, it introduces the main physicochemical properties of steel slag, and the effect on soil pH value as well as heavy metal activity. Besides, the paper elaborates the promoting effect on silicon-requiring plant and the strengthening mechanism for its resistant capability of heavy metal. According to the analysis, the application of steel slag could be a potential valuable strategy to remediate acidic soil contaminated by heavy metal by modifying the transformation of heavy metals in both soil and plant, so that the translocation of heavy metal in food chain is reduced.

Electrocatalytic activity of non-precious metal catalyst Co-N/C toward oxygen reduction reaction

Metallic cobalt was deposited on acetylene black to synthesize a composite Co/C by chemical reduction method.A platinumfree electrocatalyst Co-N/C（800） for oxygen reduction reaction（ORR） was synthesized by mixing the composite Co/C with urea and heat-treating at 800℃.The results from linear sweep voltammograms indicated that the Co-N/C（800） is active to ORR.Theβ-Co and cobalt oxides are not the active site of the catalyst Co-N/C.However,the existence of cobalt facilitated the modification of nitrogen to carbon black and led to the formation of active site of catalyst Co-N/C（800）.

Catalytic Reduction of CO2 to CO via Reverse Water Gas Shift Reaction:Recent Advances in the Design of Active and Selective Supported Metal Catalysts

The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemicals and fuels.However,this reaction is mildly endothermic and competed by a strongly exothermic CO2 methanation reaction at low temperatures.Therefore,the improvement in the low-temperature activities and selectivity of the RWGS reaction is a key challenge for catalyst designs.We reviewed recent advances in the design strategies of supported metal catalysts for enhancing the activity of CO2 conversion and its selectivity to CO.These strategies include varying support,tuning metal–support interactions,adding reducible transition metal oxide promoters,forming bimetallic alloys,adding alkali metals,and enveloping metal particles.These advances suggest that enhancing CO2 adsorption and facilitating CO desorption are key factors to enhance CO2 conversion and CO selectivity.This short review may provide insights into future RWGS catalyst designs and optimization.

The Mechanism of Ground Granulated Blastfurnace Slag Preventing Alkali Aggregate Reaction

Three different methods were applied to study the alkali content of gelpores in cement. In the closed system, the concentration of K＋, Na＋ and OH - have not reduced with the increase of age. In the open system, the diffusion and transferring of K＋ and Na＋ towards free space leads to the de-crease of total alkali content. In the micro-analysis system, the contents of K＋ and Na＋ in the first hy- drated layer of ground granulated blastfurnace slag （GBFS） are very low, while the contents of calcium and magnesium are relatively high. This phenomenon shows that the mechanism of GBFS preventing alkali aggregate reaction （AAR） is： when GBFS is dissolved by alkali medium, SiO2 and Al2O3 are dissolved into the cement matrix, then around GBFS particles form reaction rings rich in Ca2＋ and Mg^2＋, and the C-S-H gel of positive charges formed in the area repulses K＋ and Na＋, which are forced to transfer to the mortar＇s matrix, pore or mortar sample surface. The transferred K ^＋ and Na^＋ form alkali gel products with other dissolved ions, then become evenly distributed in the mortar sample and react with Ca（OH）2 in pore solutions to form （Na,K）x-2z·zCa·（SiO2）y·（OH）x gel products; and thus changes the AAR gel products＇ structure. The gel products will not expand, and so they can delay expansion destruction.

Recent Advances of Transition Metal Basic Salts for Electrocatalytic Oxygen Evolution Reaction and Overall Water Electrolysis

Electrocatalytic oxygen evolution reaction(OER)has been recognized as the bottleneck of overall water splitting,which is a promising approach for sustainable production of H_(2).Transition metal(TM)hydroxides are the most conventional and classical non-noble metal-based electrocatalysts for OER,while TM basic salts[M^(2+)(OH)_(2-x)(A_(m^(-))_(x/m),A=CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)]consisting of OH−and another anion have drawn extensive research interest due to its higher catalytic activity in the past decade.In this review,we summarize the recent advances of TM basic salts and their application in OER and further overall water splitting.We categorize TM basic salt-based OER pre-catalysts into four types(CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)according to the anion,which is a key factor for their outstanding performance towards OER.We highlight experimental and theoretical methods for understanding the structure evolution during OER and the effect of anion on catalytic performance.To develop bifunctional TM basic salts as catalyst for the practical electrolysis application,we also review the present strategies for enhancing its hydrogen evolution reaction activity and thereby improving its overall water splitting performance.Finally,we conclude this review with a summary and perspective about the remaining challenges and future opportunities of TM basic salts as catalysts for water electrolysis.

General approach for atomically dispersed precious metal catalysts toward hydrogen reaction

As a carbon-free energy carrier,hydrogen has become the pivot for future clean energy,while efficient hydrogen production and combustion still require precious metal-based catalysts.Single-atom catalysts(SACs)with high atomic utilization open up a desirable perspective for the scale applications of precious metals,but the general and facile preparation of various precious metal-based SACs remains challenging.Herein,a general movable printing method has been developed to synthesize various precious metal-based SACs,such as Pd,Pt,Rh,Ir,and Ru,and the features of highly dispersed single atoms with nitrogen coordination have been identified by comprehensive characterizations.More importantly,the synthesized Pt-and Ru-based SACs exhibit much higher activities than their corresponding nanoparticle counterparts for hydrogen oxidation reaction and hydrogen evolution reaction(HER).In addition,the Pd-based SAC delivers an excellent activity for photocatalytic hydrogen evolution.Especially for the superior mass activity of Ru-based SACs toward HER,density functional theory calculations confirmed that the adsorption of the hydrogen atom has a significant effect on the spin state and electronic structure of the catalysts.

Extraction of metals from a zinc smelting slag using two-step procedure combining acid and ethylene diaminetetraacetic acid disodium

A two-step leaching method in combination of acid and ethylene diaminetetraacetic acid disodium （EDTA-Na2） was applied to extract metals such as Cd, Cu, Fe, Pb and Zn from a zinc smelting slag. The results show that the extraction rates of Cd, Cu, Fe and Zn in slag reach 88.3%, 54.1%, 69.6% and 54.7%, respectively, while the extraction rate of Pb is only 0.05% leached with 1.25 mol/L sulfuric acid under the conditions of the ratio of slag to liquid of 100 g/L, 65 ℃ and 120 r/min for 2 h. However, Pb extraction rate from 1.25 mol/L sulfuric acid leached residue reaches as high as 66.5% by using 0.1 mol/L EDTA-Na2 solution. The results indicate that two-step sequential extraction procedure combining 1.25 mol/L sulfuric acid and 0.1 mol/L EDTA-Na2 solution can extensively extract Cd, Cu, Fe, Pb and Zn from zinc smelting slag.

Effect of Al content on the reaction between Fe-10Mn-xAl(x=0.035wt%,0.5wt%,1wt%,and 2wt%)steel and CaO-SiO_(2)-Al_(2)O_(3)-MgO slag

The effect of Al content(0.035 wt%,0.5 wt%,1 wt%,and 2 wt%)on the composition change of steel and slag as well as inclusion transformation of high manganese steel after it has equilibrated with Ca O-Si O_(2)-Al_(2)O_(3)-Mg O slag was studied using the method of slag/steel reaction.The experimental results showed that as the initial content of Al increased from 0.035 wt%to 2 wt%,Al gradually replaced Mn to react with Si O_(2)in slag to avoid the loss of Mn due to the reaction;this process caused both Al_(2)O_(3)in slag and Si in steel to increase while Si O_(2)and Mn O in slag to reduce.In addition,the type of inclusions also evolved as the initial Al content increased.The evolution route of inclusions was Mn O→Mn O-Al_(2)O_(3)-Mg O→Mg O→Mn O-Ca O-Al_(2)O_(3)-Mg O and Mn O-Ca O-Mg O.The shape of inclusions evolved from spherical to irregular,became faceted,and finally transformed to spherical.The average size of inclusions presented a trend that was increasing first and then decreasing.The transformation mechanism of inclusions was explored.As the initial content of Al increased,Mg and Ca were reduced from top slag into molten steel in sequence,which consequently caused the transformation of inclusions.

Alkali Aggregate Reaction in Alkali Slag Cement Mortars

By means of 'Mortar Bar Method',the ratio of cement to aggregate was kept as a constant 1∶2.25,the water cement ratio of the mixture was 0.40,and six prism specimens were prepared for each batch of mixing proportions with dimensions of 10×10×60mm 3 at 38±2℃ and RH≥95%, the influences of content and particle size of active aggregate, sort and content of alkali component and type of slag on the expansion ratios of alkali activated slag cement(ASC) mortars due to alkali aggregate reaction(AAR) were studied. According to atomic absorption spectrometry,the amount of free alkali was measured in ASC mortars at 90d.The results show above factors affect AAR remarkably,but no dangerous AAR will occur in ASC system when the amount of active aggregate is below 15% and the mass fraction of alkali is not more than 5% (Na 2O).Alkali participated in reaction as an independent component, and some hydrates containing alkali cations were produced, free alkalis in ASC system can be reduced enormously.Moreover,slag is an effective inhibitor, the possibility of generating dangerous AAR in ASC system is much lower at same conditions than that in ordinary Portland cement system.

Beneficial use of stainless steel EAF slag as composite cement admixture and its heavy metals leaching risk analysis

This study analyzes the feasibility of using stainless steel electric arc furnace （EAF） slag as composite cement admixture and the risk of leaching-out of heavy metals. The results show that the stainless steel EAF slag, mainly made up of Ca2 SiO4, Ca3 Mg （ SiO4 ） 2, some Cr-containing minerals and in small particle size, is easily ground and has cementitious activity. EAF slag, when used as cement admixture, can be added with a maximum percentage of 32%. It can meet the strength requirements of the standard P · C 32.5 cement. When the mixing percentage is decreased to 25 % , the strength of the cement can be increased to that of P · C 42.5 cement. Other main quality indexes of composite cement, such as the setting time and stability, also satisfy standard requirements. The results also show that most of the heavy metals in the stainless steel EAF slag exist in a stable speciation. The concentration of heavy metals that leach out from the stainless steel EAF slag and the composite cement products is far lower than the standard limit of hazardous wastes. The main heavy metal, chromium, exists as less hazardous trivalent chromium. Therefore, the risk of heavy metals leaching out from the stainless steel EAF slag is low. The internal exposure index （IRa） and the external exposure index （Iγ） of the stainless steel EAF slag are both lower than 1.0, satisfying the standard requirements of the state for the radionuclides of building materials. Therefore, stainless steel EAF slag can be safely used as admixture to produce composite cement.

Laser Ablation Atomic Beam Apparatus with Time-Sliced Velocity Map Imaging for Studying State-to-State Metal Reaction Dynamics

We report a newly constructed laser ablation crossed molecular beam apparatus, equipped with time-sliced velocity map imaging technique, to study state-to-state metal atom reaction dynamics. Supersonic metal atomic beam is generated by laser vaporization of metal rod, and free expansion design without gas flow channel has been employed to obtain a good quality of metal atomic beam. We have chosen the crossed-beam reaction Al＋O2 to test the performance of the new apparatus. Two-rotational-states selected AIO（X^2∑＋, v=0, N and N＋I4） products can be imaged via P（N） and R（N＋14） branches of the Av=l band at the same wavelength, during （1＋1） resonance-enhanced multi-photon ionization through the AIO（D2E＋） intermediate state. In our experiment at 244.145 nm for simultaneous transitions of P（15） and R（29） branch, two rings in slice image were clearly distinguishable, corresponding to the AiO（v=0, N=IS） and AIO（v=0, N=29） states respectively. The energy difference between the two rotational levels is 403 cm^-1. The success of two states resolved in our apparatus suggests a better collisional energy resolution compared with the recent research study [J. Chem. Phys. 140, 214304 （2014）].

Simple synthesis of nitrogen‐doped carbon spheres as a highly efficient metal‐free electrocatalyst for the oxygen reduction reaction

In the present work, nitrogen‐doped carbon spheres were synthesized through a simple hydro‐thermal treatment using glucose and melamine as inexpensive carbon and nitrogen sources, re‐spectively. The ratio of melamine to glucose and annealing temperature were optimized. The final optimal sample exhibited a catalytic activity for the oxygen reduction reaction（ORR） that was supe‐rior than that of commercial 20%Pt/C in 0.1 mol/L KOH. It revealed an onset potential of –22.6 mV and a half‐wave potential of –133.6 mV （vs. Ag/AgCl）, which are 7.2 and 5.9 mV more positive than those of the 20%Pt/C catalyst, respectively, as well as a limiting current density of 4.6 mA/cm^2, which is 0.2 mA/cm^2 higher than that of the 20%Pt/C catalyst. The catalyst also exhibited higher stability and superior durability against methanol than 20%Pt/C. Moreover, ORRs on this catalyst proceed through a more effective 4 e^– path. The above mentioned superiority of the as‐prepared catalyst makes it promising for fuel cells.