Molecular Insights into the Stability of Titanium in Electrolytes Containing Chlorine and Fluorine Ions.

Titanium and its alloys are protected by a compact and stable passive film, which confers resistance to corrosion by the primary halogen chloride (Cl-) while being less effective against fluoride (F-). Although researchers have recognized different macroscopic corrosion effects of these halide ions on titanium, the underlying mechanisms remain largely unexplored. In this work, the bonding of Cl-/F- with stable passive films was studied in neutral and acidic (pH = 2.3) conditions. The synergistic effect between the interfacial hydrogen bond (HB) structure and halogens on titanium corrosion was first revealed using first-principles calculation and Raman spectroscopy. F- forms more stable halogen-Ti bonds than Cl-, resulting in titanium degradation. The proton combined with F- exhibits a specific synergistic effect, causing corrosion of the passive film. The water hydrogen bond transformation index (HBTI) at the titanium/aqueous interface was 1.88 in an acidic solution containing F-, significantly higher than that in neutral/acid solutions containing Cl- (1.80/1.81) and a neutral solution containing F- (1.81). This work clarifies the structure-activity relationship between HBTI and the destruction of titanium passive films. We propose that the microstructure of the interfacial HB is an undeniable factor in the corrosion of titanium.

Insight into oxygen reduction activity and pathway on pure titanium using scanning electrochemical microscopy and theoretical calculations.

HYPOTHESIS: Unlike noble metals, the oxygen reduction reaction (ORR) behavior on Ti is more complicated due to its spontaneously formed oxide film. This film results in sluggish ORR kinetics and tends to be reduced within ORR potential region, causing the weak and multi-reaction coupled current. Though Ti is being used in chemical and biological fields, its ORR research is still underexplored. EXPERIMENTS: We innovatively employed the modified reactive tip generation-substrate collection (RTG/SC) mode of scanning electrochemical microscopy (SECM) with high efficiency of 97.2 % to quantitatively study the effects of film characteristics, solution environment (pH, anion, dissolved oxygen), and applied potential on the ORR activity and selectivity of Ti. Then, density functional theory (DFT) and molecular dynamics (MD) analyses were employed to elucidate its ORR behavior. FINDINGS: On highly reduced Ti, film properties dominate ORR behavior with promoted 4e- selectivity. Rapid film regeneration in alkaline/O2-saturated conditions inhibits ORR activity. Besides, ORR is sensitive to anion species in neutral solutions while showing enhanced 4e- reduction in alkaline media. All the improved 4e- selectivities originate from the hydrogen bond/electrostatic stabilization effect, while the decayed ORR activity by Cl- arises from the suppressed O2 adsorption. This work provides theoretical support and possible guidance for ORR research on oxide-covered metals.

Spectroscopic and Simulation Insights into the Corrosion Mechanism of Sulfite on Titanium.

Ion adsorption and hydrogen bond (HB) network reconstruction in electric double layer (EDL) have a profound impact on the interface properties. The microstructure in the bulk phase of 1.00-21.30 wt.% Na2SO3 aqueous solutions are investigated by X-ray scattering, confocal Raman spectroscopy, and classical molecular dynamics. The electronic properties of SO32- adsorption and the geometric structure of the HB network in the EDL at the titanium TiO2(101) surface are studied by density functional theory (DFT) and classical molecular dynamics. The SO32- strongly weakens the fully hydrogen-bonded water (FHW) and transforms it into partial hydrogen-bonded water (PHW). The HB transformation index (HBTI = PHW/FHW) shows a linear relationship with the mass fraction of Na2SO3. The TiOb-parallel adsorption configuration of SO32- enhances the ionicity of the Ob-Ti6 bond, resulting in the formation of oxygen vacancies at the titanium passive film surface. Besides, SO32- and Na+ are enriched and thermodynamic supersaturated in the inner Helmholtz layer (IHL), and the ions are diluted in the outer Helmholtz layer (OHL). The diffusion coefficient of SO32- and water molecules in EDL decreases seriously, which is easy to causes salt scaling on the surface of titanium passive film. This work provides evidence for the destruction of titanium passive film by SO32-.

An Fe-V@NiO heterostructure electrocatalyst towards the oxygen evolution reaction.

The development of a nonprecious and Earth-abundant electrocatalyst with high electrocatalytic activity for the oxygen evolution reaction (OER) is an emerging hot issue and remains a grand challenge. In the present work, we proposed a facile strategy to construct ultrathin NiO nanosheets decorated with Fe-V nanoparticles on nickel foam (Fe-V@NiO/NF) for use as an OER electrocatalyst. Due to the 3D rational configuration, the Fe-V@NiO/NF with a heterostructure shows excellent electrocatalytic activity towards the OER. Interestingly, it is found that in situ oxidation by galvanostatic electrolysis in alkaline solution is beneficial to enhance the OER performance. After 10 h of electrolysis, a current density of 50 mA cm-2 is achieved at a low overpotential of 271.1 mV. This is because during the in situ oxidation process, iron and vanadium ions insert into the NiO lattice and lead to the generation of highly active α-FeOOH and an amorphous (oxy)-hydroxide layer. Additionally, the charge transfer resistance dramatically reduces with the prolonging of oxidation time.

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.

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.