Deep removal of trace arsenic from acidic SbCl3 solution by in-situ galvanically coupled Cu2Sb/Cu particles.

Arsenic is a harmful associated element in antimony ore, which might bring out the risk of leakage during complex industrial production of high-purity antimony. Herein, we reported a novel and efficient way to remove the trace arsenic impurity from acidic SbCl3 solution by utilizing copper-system bimetallic particles. Specifically, galvanically coupled Cu2Sb/Cu was in-situ synthesized by introducing precursor copper powder to the specific SbCl3 solution. DFT studies revealed that Sb(III) was easily reduced by Cu to form Cu2Sb due to the strong adsorption of Sb(III) on Cu (111) crystal plane. The Cu2Sb/Cu coupling exhibited excellent activity for As(III) reduction, over 99.4% arsenic were removed under optimal conditions and residual arsenic concentration dropped to only 2.7 mg L-1. Crucially, Sb(III) concentration changes could be neglected. Besides, the dearsenization residues were extensively characterized to analyze the evolvement and cause in the reaction process. The results confirmed that the arsenic removal mechanisms by Cu2Sb/Cu particles were multi-affected, including adsorption, displacement, and precipitation. And the strong electrostatic attraction of AsO+ under high HCl conditions was identified as a key step to achieving dearsenization. This research will provide a theoretical guidance for the green synthesis of high-purity antimony and related products.

Speciation characterization of arsenic-bearing phase in arsenic sulfide sludge and the sequential leaching mechanisms.

Arsenic sulfide sludge (ASS) is a kind of deleterious waste which contains various valuable metallic elements, such as Re and Pb, which are always associated with arsenic-bearing phases in ASS. The leaching speed and efficiency of valuable elements may depend on the phase constitution. Here, we proposed a sequential leaching method to thoroughly understand the constitution of arsenic-bearing phase and the distribution of valuable elements in ASS. The results show that five major arsenic-bearing phases exist in ASS: amorphous As2S3, crystalline As4S4, As2O3, and As atoms dissolved into the lattice of PbS and PbSO4 phases. Re is mainly distributed in As2S3 and As4S4 phases. During the leaching process, the dissolution of As2O3 particles and As2O3 layers on the surface of As2S3/As4S4 particles occurs first. Then, the reaction between As2S3/As4S4 particles and copper sulfate happens. The order of leaching sequence is As2O3, amorphous As2S3 and crystalline As4S4. The majority of Re element exists in the solution while almost all Pb element remains in the solid residues, which is beneficial for the separation and purification valuable elements individually. This work not only detailed determines the arsenic-bearing species, but also provides significant theoretical bases for extracting valuable elements from ASS.

CO2 photoelectroreduction with enhanced ethanol selectivity by high valence rhenium-doped copper oxide composite catalysts.

CuO supported catalyst with high valence rhenium doping were specially studied for photoelectrocatalytic reduction of CO2 to small molecular alcohols, which were synthesized by nitrate thermal decomposition method on anatase TiO2 nanotube arrays (TiO2-NTs). Photoelectrochemical measurements indicate that the high valence rhenium doping helps in improving the catalytic activity and selectivity of CuO supported catalysts. For the case of 6 wt% Re-doped CuO/TiO2-NTs calcined at 723 K, the principal products are methanol and ethanol with yield up to 19.9 µmol and 7.5 µmol after 5 h photoelectrocatalysis at external potential of -0.4 V under simulated solar illumination. In contrast, the products catalyzed by undoped CuO/TiO2-NTs are only methanol and formaldehyde. These results indicate that the high valence rhenium doping will promote the alcoholization process and benefit the CC coupling, leading to the selective conversion of CO2 to ethanol. Furthermore, under suitable external potential (-0.5 V) the CO2 conversion product is almost entirely composed of ethanol.

A comparative study of the effects of different TiO2 supports toward CO2 electrochemical reduction on CuO/TiO2 electrode.

CuO-based electrodes possess vast potential in the field of CO2 electrochemical reduction. Meantime, TiO2 supports show the advantages of being non-toxic, low-cost and having high chemical stability, which render it an ideal electrocatalytic support with CuO. However, different morphologies and structures of TiO2 supports can be obtained through various methods, leading to the discrepant electrocatalytic properties of CuO/TiO2. In this paper, three supports, named dense TiO2, TiO2 nanotube and TiO2 nanofiber, were applied to synthesize CuO/TiO2 electrodes by thermal decomposition, and the performances of the electrocatalysts were studied. Results show that the main product of the three electrocatalysts was ethanol, but the electrochemical efficiency and reaction characteristics are obviously different. The liquid product of CuO/Dense TiO2 is pure ethanol, however, the current efficiency is rather low owing to the higher resistance of the TiO2 film. CuO/TiO2 nanotube shows high conductivity and ethanol can be synthesized at low overpotential with high current efficiency, but the gas products cannot be restricted. CuO/TiO2 nanofiber has a larger specific surface area and more active sites, which is beneficial for CO2 reduction, and the hydrogen evolution reaction can be evidently restricted. The yield of ethanol reaches up to 6.4 µmol cm-2 at -1.1 V (vs. SCE) after 5 h.

Three-Dimensional Ordered Macro/Mesoporous Cu/Zn as a Lithiophilic Current Collector for Dendrite-Free Lithium Metal Anode.

Li dendrites are considered as the primary cause for degradation and inevitable short circuit in lithium-metal batteries (LMBs). Although contemporary strategies have shown potential for addressing dendrite growth, none have achieved complete elimination. In this paper, a dendrite-free, three-dimensional, ordered, macro/mesoporous Cu/Zn current collector was prepared using a combination of simple colloidal crystal template and electrochemical method (electrodeposition and pulse plating). When paired with a hierarchically structured mesoporous (20-50 nm) and macroporous (450 nm) anode, this novel current collector achieved stable charge/discharge cycles of over 2000 h and a small plating/stripping potential (≈8 mV) at a current density of 0.2 mA cm-2. Coulombic efficiencies (CE) also reached 94.7% after 400 cycles. This three-dimensional, ordered, macro/mesoporous structure provides a greater specific surface area, reduces local current density, and contains a lithiophilic Zn coating that serves as preferred Li nucleation sites. By combining these factors, dendrite-free Li deposition and superior electrochemical performance improvements in LMBs have been realized.

Effective combination of CuFeO2 with high temperature resistant Nb-doped TiO2 nanotube arrays for CO2 photoelectric reduction.

Herein, we report a simple approach to synthesize CuFeO2/TNNTs photocathodes composed of high-temperature resistance n-type Nb-doped TiO2 nanotube arrays (TNNTs) and p-type CuFeO2 for CO2 reduction. TNNTs were prepared by anodic oxidation on TiNb alloy sheets and CuFeO2/TNNTs were then prepared by coating precursor liquid onto TNNTs followed by heat treatment in argon atmosphere. The microstructures of CuFeO2/TNNTs and TNNTs before and after heat treatment were investigated by SEM and TEM. The phase compositions of CuFeO2/TNNTs were studied by XRD and XPS, and the light absorption performance were tested by UV-vis diffuse reflectance spectrum. Results show that TNNTs exhibit a regular nanotube arrays structure and this structure is well remained after the calcination at 650 °C. In addition, TNNTs show similar semiconductor properties to n-type TiO2, which enables them to be integrated with p-type CuFeO2 to obtain composite photocathodes with a p-n junction. The synthesized CuFeO2/TNNTs photocathode is well crystallized because no other crystalline iron or copper compounds are included in the prepared photocathode. Furthermore, the photocathode shows high light absorption and fast carrier transport due to the appropriate band gap and p-n junction. As a result, high photoelectrocatalytic CO2 reduction performance with high selectivity to ethanol is obtained on this photocathode.

Highly porous copper ferrite foam: A promising adsorbent for efficient removal of As(III) and As(V) from water.

A novel copper ferrite foam fabricated on Fe-Ni foam substrate was synthesized via a simple hydrothermal method to efficiently remove arsenic from aqueous solution. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-Ray diffraction pattern (XRD) and Raman spectra were used to characterize the morphology and surface composition of the copper ferrite foam (CFF). The adsorption behavior of As(III) and As(V) onto this CFF is studied as a function of solution pH, temperature, contact time, and different concentrations. Results shown that this CFF has high adsorption capacity and excellent recyclability. Adsorption isotherms study indicates Langmuir model of adsorption. The maximum adsorption capability of As(III) and As(V) on CuFe2O4 foam is observed about 44.0 mg g-1 and 85.4 mg g-1, respectively. Regeneration experiment indicates that arsenic could be easily desorbed from CFF with 0.10 mol L-1 NaOH and the high adsorption capacity can be maintained for six regeneration cycle.

An internal magnetic field strategy to reuse pulverized active materials for high performance: a magnetic three-dimensional ordered macroporous TiO2/CoPt/α-Fe2O3 nanocomposite anode.

A ferromagnetic three-dimensional ordered macroporous TiO2/CoPt/α-Fe2O3 (3DOMTCF) nanocomposite was synthesized via a sol-gel approach templated by poly(methyl methacrylate) (PMMA) microspheres. After magnetization, it exhibited an extremely high reversible capacity and a long cycle life, which were ascribed to the internal magnetic field for reusing pulverized active materials and its unique structure.

Copper-promoted cementation of antimony in hydrochloric acid system: A green protocol.

A new method of recovering antimony in hydrochloric acid system by cementation with copper powder was proposed and carried out at laboratory scale. Thermodynamic analysis and cyclic voltammetry test were conducted to study the cementation process. This is a novel antimony removal technology and quite meets the requirements of green chemistry. The main cement product Cu2Sb is a promising anodic material for lithium and sodium ion battery. And nearly all consumed copper powder are transformed into CuCl which is an important industrial material. The effect of reaction temperature, stoichiometric ratio of Cu to Sb(III), stirring rate and concentration of HCl on the cementation efficiency of antimony were investigated in detail. Optimized cementation condition is obtained at 60 °C for 120 min and stirring rate of 600 rpm with Cu/Sb(III) stoichiometric ratio of 6 in 3 mol L(-1) HCl. At this time, nearly all antimony can be removed by copper powder and the cementation efficiency is over 99%. The structure and morphologies of the cement products were characterized by X-ray diffraction and scanning electron microscopy, respectively. Results show that the reaction temperature has little influence on the morphology of the cement products which consist of particles with various sizes. The activation energy of the cementation antimony on copper is 37.75 kJ mol(-1), indicating a chemically controlled step. Inductively coupled plasma mass spectrometry results show that no stibine generates during the cementation process.

An AIL/IL-based liquid/liquid extraction system for the purification of His-tagged proteins.

A sorbent based on affinity ionic liquid (AIL), triazacyclononane-ionic liquid, was synthesized, characterized, and applied to the extraction of histidine (His)-tagged proteins from aqueous buffer to ionic liquid (IL) phase. The adsorbed His-tagged proteins could be back-extracted from the IL phase to the aqueous buffer with an imidazole solution. The specific binding of His-tagged proteins with AIL/IL could be affected by a few factors including the ionic strength and coordinated metal ions. In the case of His-tagged enhanced green fluorescent protein (EGFP), the maximum binding capacity of Cu(2+)-AIL/IL reached 2.58 µg/µmol under the optimized adsorption conditions. The eluted His-tagged EGFP kept fluorescent and remained active through the purification process. Moreover, a tandem extraction process successively using Cu(2+)-AIL/IL and Zn(2+)-AIL/IL systems was developed, which was proven very efficient to obtain the ultimate protein with a purity of about 90 %. An effective reclamation method for the AIL/IL extraction system was further established. The sorbent could be easily regenerated by removing metal ions with EDTA and the followed reimmobilization of metal ions. Easy handling of the presented M(2+)-AIL/IL system and highly specific ability to absorb His-tagged proteins make it attractive and potentially applicable in biomolecular separation.