Effects and mechanisms of fluorite on the co-reduction of blast furnace dust and seaside titanomagnetite

The co-reduction roasting and grinding-magnetic separation of seaside titanomagnetite and blast furnace dust was investigated with and without fluorite addition at a reduction roasting temperature of 1250°C for 60 min, a grinding fineness of-43 μm accounting for 69.02 wt% of the total, and a low-intensity magnetic field strength of 151 kA/m. The mineral composition, microstructure, and state of the roasted products were analyzed, and the concentrations of CO and CO_2 were analyzed in the co-reduction roasting. Better results were achieved with a small fluorite dosage(≤4 wt%) in the process of co-reduction. In addition, F^- was found to reduce the melting point and viscosity of the slag phase because of the high content of aluminate and silicate minerals in the blast furnace dust. The low moisture content of the blast furnace dust and calcic minerals inhibited the hydrolysis of CaF_2 and the loss of F^-. Compared with the blast furnace dust from Chengdeng, the blast furnace dusts from Jiugang and Jinxin inhibited the diffusion of F-when used as reducing agents, leading to weaker effects of fluorite.

Petroleum coke as reductant in co-reduction of low-grade laterite ore and red mud to prepare ferronickel: Reductant and reduction effects

Petroleum coke is industrial solid wastes and its disposal and storage has been a great challenge to the environment. In this study, petroleum coke was utilized as a novel co-reduction reductant of low-grade laterite ore and red mud. A ferronickel product of 1.98wt% nickel and 87.98wt% iron was obtained with 20wt% petroleum coke, when the roasting temperature and time was 1250°C and 60 min, respectively. The corresponding recoveries of nickel and total iron were 99.54wt% and 95.59wt%, respectively. Scanning electron microscopy-energy dis- persive spectrometry (SEM-EDS) analysis showed metallic nickel and iron mainly existed in the form of ferronickel particles which distrib- uted uniformly at a size of approximately 30 μm with high purity. This study demonstrated that petroleum coke is a promising reductant in the co-reduction of laterite ore and red mud. Compared to other alternatives, petroleum coke is advantageous with reduced production cost and high applicability in anthracite-deficient areas.

Efficient C-N coupling in electrocatalytic urea generation on copper carbonate hydroxide electrocatalysts

Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.

Concave Cu-Pd bimetallic nanocrystals： Ligand-based Co-reduction and mechanistic study

The synthesis of highly uniform alloy nanocrystals with a concave feature is desirable for applications in catalysis but is an arduous task. This article proposes an initiative protocol for the fabrication of novel Cu-Pd alloy nanocrystals, wherein the volume of decylamine （DA） in the reaction system was found to greatly influence the formation of different morphologies, including the tetrahedron （TH）, concave tetrahedron （CTH）, rhombohedral-tetrapod （RTP）, and tetrapod （TP）. The alloy structure of the products arises from the coordination interaction between the DA and metal ions, which affects the reduction potential of Cu and Pd species, and thus yields co-reduction. Other reaction parameters, such as the type of ligand, amount of reductant, and temperature, were also altered to study the growth mechanism, yielding consistent conclusions in the diffusion-controlled regime. As a catalyst, 48-nm Cu-Pd concave tetrahedral nanocrystals were highly active for the hydrogenation of 3-nitrostyrene and exhibited 〉99.9% chemoselectivity to C=C instead of-NO2.

Electrochemical Preparation of Mg-Li-Al-Er Alloys by Co-reduction in Molten Chloride

The electrochemical behavior of Mg, Li, AI and Er were investigated by electrochemical techniques in LiCI- KCI-MgCI2-AICI3-ErCI3 melts at 823 K. The cyclic voltammetry and chronopotentiometry indicated that the co-reduction of Mg, Li, AI and Er occurs at current densities more negative than -0.89 A.cm-2. Er（lll） under-potential deposited on pre-reduced AI electrode formed AI-RE alloys. X-ray diffraction （XRD） results indicated that Mg17Al12, Al2Er, Al2Er3 and Al4Li9 phases were prepared by galvanostatic electrolysis. ICP analyses of samples showed that lithium and aluminum contents of Mg-Li-AI-Er alloys could be controlled by concentration of AICI3 and cathodic current density.

Electrochemical Co-reduction of Bi(Ⅲ)and Y(Ⅲ)and Extracting Yttrium from Molten LiCl-KCl Using Liquid Bi as Cathode

The electrochemical reaction of Bi(Ⅲ)and co-reduction behaviour of Bi(Ⅲ)and Y(Ⅲ)ions were researched in molten LiCl-KCl on a ttmgsten(W)electrode employing a range of electrochemical teclmiques.Cyclic voltammetric and square-wave voltanunetric results revealed that the reduction of Bi(Ⅲ)was a one-step process,with the exchange of three electrons on a W electrode,and diffusion-controlled.The electrochemical curves showed two reduction peaks pertaining to the formation of Bi-Y alloy compounds,because of the co-reduction of Bi(Ⅲ)and Y(Ⅲ) by metallic Y deposited on the pre-deposited Bi-coated W electrode and reacting with Bi metal in molten LiCl-KCl. Furthermore,galvanostatic electrolysis was conducted using liquid Bi as cathode to extract yttrium at different current intensities,and the extractive products were analyzed by SEM,EDS and XRD.The results indicated that BiY intermetallic compotmd was formed in the molten LiCl-KCl-YCl3 system.

Electrochemical co-reduction of holmium and magnesium ions in eutectic LiCl-KCl salts

The electrochemical co-reduction of Ho(Ⅲ)and Mg(Ⅱ)ions was investigated on Mo electrode in eutectic LiCl–KCl salts at temperature of 773 K using various electrochemical techniques.Cyclic voltammogram(CV)and square wave voltammogram exhibit three reduction peaks corresponding to the reduction of Ho(Ⅲ)on pre-deposited Mg electrode,whose potentials are more positive than that of Ho on Mo electrode because of the formation of Mg-Ho intermetallic compounds by co-reduction of Ho(Ⅲ)and Mg(Ⅱ)ions.Meanwhile,chronopotentiometry and open-circuit chronopotentiometry were used to explore the electrochemical formation of Mg–Ho intermetallics.Mg–Ho alloys were produced by galvanostatic electrolysis at the current of 1.5 A for different electrolysis durations.Ho_(5)Mg_(24),HoMg_(2) and HoMg intermetallic compounds were acquired and characterized by X-ray diffraction(XRD)and scanning electron microscopy(SEM)coupled with energy-dispersive spectroscopy(EDS).The results indicate that Mg–Ho intermetallic compounds,Ho_(5)Mg_(24),HoMg_(2) and HoMg,could be prepared by molten salts electrolysis.

Electrochemical co-reduction of Y(Ⅲ)and Al(Ⅲ)in a fluoride molten salt system and electrolytic preparation of Y-Al intermediate alloys

In this study,a molten salt co-reduction method was proposed for preparing Y-Al intermediate alloys and the electrochemical co-reduction behaviors of Y(Ⅲ)and Al(Ⅲ)and the reaction mechanism of intermetallic compound formation were investigated by transient electrochemical techniques.The results show that the reduction of Y(Ⅲ)at the Mo electrode is a reversible electrochemical process with a single-step transfer of three electrons,which is controlled by the mass transfer rate.The diffusion coefficient of Y(Ⅲ)in the fluoride salt at a temperature of 1323 K is 5.0238×10^(-3)cm^(2)/s.Moreover,the thermodynamic properties associated with the formation of Y-Al intermetallic compounds were estimated using a steady-state electrochemical method.Y-Al intermediate alloy containing 92 wt%yttrium was prepared by constant current electrolysis at 1323 K in the LiF-YF_(3)-AIF_(3)-Y_(2)O_(3)(6 wt%)-Al_(2)O_(3)(1 wt%)system at a cathodic current density of 8 A/cm^(2)for 2 h.The Y-Al intermediate alloy is mainly composed ofα-Y2Al and Y phases.The development and application of this innovative technology have solved major technical problems,such as a long production process,high energy consumption,and serious segregation of alloy elements at this stage.

Defect engineered electrocatalysts for C-N coupling reactions toward urea synthesis

Urea is extensively used in agriculture and chemical industry,and it is produced on an industrial scale from CO_(2)and Haber-Bosch NH_(3)under relatively high temperature and high pressure conditions,which demands high energy input and generates masses of carbon footprint.The conversion of CO_(2)and N sources(such as NO_(2)^(−),NO_(3)^(−),and N_(2))through electrocatalytic reactions under ambient conditions is a promising alternative to realize efficient urea synthesis.Of note,the design of electrocatalyst is one of the key factors that can improve the efficiency and selectivity of C-N coupling reactions.Defect engineer-ing is an intriguing strategy for regulating the electronic structure and charge density of electrocatalysts,which endows electrocatalysts with excellent physicochemical properties and optimized adsorption en-ergy of the reaction intermediates to reduce the kinetic barriers.In this minireview,recent advances of defect engineered electrocatalysts in urea electrosynthesis from CO_(2)and various N reactants are firstly introduced.Mechanistic discussions of C-N coupling in these advances are presented,with the aim of directing future investigations on improving the urea yield.Finally,the prospects and challenges of de-fect engineered electrocatalysts for urea synthesis are discussed.This overview is expected to provide in-depth understanding of structure-reactivity relationship and shed light on future electrocatalytic C-N coupling reactions.

Microfluidic-enabled ambient-temperature synthesis of ultrasmall bimetallic nanoparticles

The production of bimetallic nanoparticles with ultrasmall sizes is the constant pursuit in chemistry and materials science because of their promising applications in catalysis,electronics and sensing.Here we report ambient-temperature preparation of bimetallic NPs with tunable size and composition using microfluidic-controlled co-reduction of two metal precursors on silicon surface.Instead of free diffusion of metal ions in bulk system,microfluidic flow could well control the local ions concentration,thus leading to homogenous and controllable reduction rate among different nucleation sites.By controlling precursor concentration,flow rate and reaction time,we rationally design a series of bimetallic NPs including Ag-Cu,Ag-Pd,Cu-Pt,Cu-Pd and Pt-Pd NPs with ultrasmall sizes(~3.0 nm),tight size distributions(relative standard deviation(RSD)<21%),clean surface,and homogenous elemental compositions among particles(standard deviation(SD)of weight ratios<3.5%).This approach provides a facile,green and scalable method toward the synthesis of diverse bimetallic NPs with excellent activity.

Preparation of highly dispersed superfine W-20 wt% Cu composite powder with excellent sintering property by highly concentrated wet ball-milled process

The ball milling process and the CuWO-WOprecursors were investigated, and a new highly concentrated wet ball-milled process(HWM) was designed. W-20 wt% Cu composite powders with excellent sintering property were synthesized by highly concentrated wet ballmilled process and co-reduction. The powders were characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), field electron transmission electron microscopy(FESEM) and laser-diffraction diameter tester.The results indicate that particle size of W03-CuO powder mixtures decreases to 390 nm rapidly with the milling time increasing to 5 h. The CuWOprecursors promote the microstructural homogeneity of W and Cu. W-Cu composite powders have a highly dispersed and well sintering property. The particle size of W-Cu powders milled by HWM for 5 h is about 680 nm. High-resolution transmission electron microscopy(HRTEM) result suggests that W phase and Cu phase are mixed at nanometer scale. The above W-Cu composite powders reach the relative density of about 99.3%.

Electrochemical formation of La-Al intermetallic compounds in fluoride melts

The electrochemical formation of La-Al alloys in LiF-CaF_(2)molten salt on a molybdenum electrode at 1123 K was investigated by electrochemical techniques,such as cyclic voltammetry,square-wave voltammetry and open-circuit chronopotentiometry.The formation signals of four types of Al-La intermetallic compounds were observed.The Al-La alloy was obtained through galvanostatic electrolysis at 2.5 A·cm^(-2)for 3 h.The phase composition and microstructure of the electrolytic products were analysed by X-ray diffraction(XRD)and scanning electron microscopy with energy-dispersive spectroscopy(EDS).XRD results show that the phase compositions of the alloys are Al_(11)La_(3)and Al,and EDS results reveal 26.7 at%La in the alloy.