Kinetics and thermodynamics modeling of Nd(III) removal from aqueous solution using modified Amberlite XAD7

New adsorbent material was obtained by modification of commercial Amberlite XAD7 with thiourea that represents a non-toxic, cheap and environmentally friendly extractant. Prepared adsorbent was used for removal of neodymium ions from aqueous solutions. Thiourea modified Amberlite involved in this study shows good adsorption capacities (74.3 mg/g) and excellent efficiency during Nd removal process. In order to elucidate the mechanism of the Nd adsorption process kinetic, thermodynamic and equilibrium studies were performed, establishing this way which kinetic model better describes the Nd adsorption process. Moreover the thermodynamic studies prove that the Nd adsorption on thiourea modified Amberlite XAD7 is an endothermic and spontaneous process.     

Covalently functionalized graphene by thiourea for enhancing H2-evolution performance of TiO2 photocatalyst

Graphene as a well-known electron cocatalyst can enhance the hydrogen-production performance of photocatalysts due to its excellent conductivity. For highly efficient graphene-modified TiO₂ photocatalyst, besides the speedy electron transfer via graphene, it is significant to raise the interfacial hydrogen-generation reaction rate on the graphene surface. In this paper, thiourea (TU) can covalently functionalize graphene and act as effective H⁺-adsorbed active sites to improve the hydrogen-production efficiency of graphene-modified TiO₂ (TiO₂/rGO-TU). The TiO₂/rGO-TU sample was successfully prepared by a facile nucleophilic substitution reaction between the thiol (-SH) of thiourea and carboxyl (-COOH) of graphene. The TiO₂/rGO-TU could possess the maximum H₂-generation rate of 241.83 μmol h^?1 g^?1, which was 2.33 and 6.60 times greater than that of TiO₂/rGO and TiO₂, respectively. The enhanced photocatalytic activity of TiO₂/rGO-TU can be ascribed to the synergistic effect of graphene and thiourea, namely, the graphene functions as a cocatalyst to capture the photoexcited electrons of TiO₂ and the thiourea acts as effectual H⁺-adsorbed active sites to promote interfacial hydrogen generation. This study presents a feasible strategy for developing grephene-based photocatalysts for prospective applications in the hydrogen-production field.     

Layer by layer assembly of glucose oxidase and thiourea onto glassy carbon electrode: Fabrication of glucose biosensor

For the first time a novel, simple and facile approach is described to construct highly stable glucose oxidase (GOx) multilayer onto glassy carbon (GC) electrode using thiourea (TU) as a covalent attachment cross-linker. The layer by layer (LBL) attachment process was confirmed by cyclic voltammetry, electrochemical impedance spectroscopy and Fourier transform infrared reflection spectroscopy (FT-IR-RS) techniques. Immobilized GOx shows excellent electrocatalytic activity toward glucose oxidation using ferrocenemethanol as artificial electron transfer mediator and biosensor response was directly correlated to the number of bilayers. The surface coverage of active GOx per bilayer, heterogeneous electron transfer rate constant (k_s) and Michaelis–Menten constant (K_M), of immobilized GOx were 1.50 × 10⁻¹² mol cm⁻², 9.2 ± 0.5 s⁻¹ and 3.42(±0.2) mM, respectively. The biosensor constructed with four-bilayers of TU/GOx showed good stability, high reproducibility, long life-time, fast amperometric response (5 s) with the high sensitivity of 5.73 μA mM⁻¹ cm⁻² and low detection limit of 6 μM at concentration range up to 5.5 mM.     

Performance of nitrogen- and sulfur-containing carbon material derived from thiourea and formaldehyde as electrochemical capacitor

In order to investigate the performance of an electrochemical capacitor consisting of a nitrogen- and sulfur-containing carbon material, the carbon material derived from thiourea and urea was synthesized by a polymerization process of the urea resin. No solid appeared after the polymerization process. When the dried sample after the polymerization process was heated in flowing N2 gas, we obtained carbon material. However, there was no product when only thiourea was heated under the same conditions. The percentages of nitrogen and sulfur in all the samples synthesized from thiourea were roughly 5-20 wt.% and 3-8 wt.% even after washing with hot water, respectively. No specific peak derived from the redox reaction appeared in the CV graphs for the samples. The capacitance value of T-urea800W, which was synthesized by the heat treatment at 800 °C and then wash with hot water, was 138.8 F g⁻¹ at the current density of 50 mA g⁻¹ in a 1 M H₂SO₄ water solution whereas that value of a commercial activated carbon was 107.1 F g⁻¹ under the same conditions. It was presumed from the XPS measurements that the status of the nitrogen and sulfur in the materials are a pyridine-like nitrogen at the edge part of the graphitic structure, a quaternary nitrogen in the graphitic-layered structure, and S⁰, S⁴⁺, and S²⁻, respectively.     

Bitumen chemical modification by thiourea dioxide

This work evaluates a novel bitumen modification through the use of a chemical agent, thiourea dioxide, substance which has been traditionally used as a reducing agent. Thermo-gravimetric analysis demonstrated the formation of new chemical compounds, most probably originated through reactions between products from thiourea dioxide thermal decomposition and some highly polar bitumen molecules. As a result of these reactions, which continues even after 60 days, bitumen permanent deformation resistance at high temperature is enhanced, as indicated by a significant increase in its viscosity and elastic features. On the other hand, thiourea dioxide addition produces changes in the bitumen colloidal nature, which improve its flexibility at low in-service temperatures, and consequently its resistance to thermal cracking under loading. In fact, dynamic bending tests indicated a remarkable decrease in the value of binder glass transition temperature, which was further corroborated by differential scanning calorimetry. As a conclusion, thiourea dioxide can be seen as a promising modifying agent, which can extend the in-service temperature range at which bitumen would present a satisfactory performance.     

Polymer pendant ligand chemistry, 4. Recovery of precious metal ions from strongly acidic solution with a polymer-supported o-phenylenediamine hydrochloride ligand

We report on the synthesis and reactivity of a polymer-supported o-phenylenediamine hydrochloride ligand, PS-PDHC, using macroporous 6% crosslinked polystyrene-divinylbenzene beads. The PS-PDHC ligand was found to be highly selective to AuCl₄⁻ ions in strongly acidic solutions in the presence of other precious metal ions, PdCl₄²⁻, PtCl₄²⁻, RhCl₆³⁻, and RuCl₅²⁻ (selectivity values: 2.5, Au/Pd; 7.5, Au/Pt; 7, Au/Rh; 2.2, Au/Ru) as well as other transition metal ions, Fe ³⁺, Cr³⁺, CU²⁺, Nit+, and Mn²⁺. The sorption capacity, selectivity, kinetics of removal and recovery, and solution isotherms have been determined for AuCl₄⁻ ions in competition with the above-mentioned metal ions. The relative ease of formation of the anionic complex in 0.5 M HCI, AuCl₄⁻ was thought to be the primary reason for its selective ability to bind to the PS-PDHC ligand by an anion-exchange mechanism. Therefore, the effect of the HCI concentration on the kinetics of AuCl₄⁻ ion removal from solution was also investigated to clearly show that raising the pH from 0 to 5 caused a dramatic decrease in rate. The AuCl₄⁻ ion can be recovered quantitatively from the PS-PDHC beads using a 5% thiourea solution in 0.1 M HCl, allowing the polymer-supported ligand to be reused.     

Effect of organic additives on hydrogen permeation into an iron membrane studied by frequency analysis techniques

The effects of thiourea and benzotriazole on the hydrogen permeation into iron were studied using a Devanathan-Stachurski electrochemical double cell equipped with a thin iron membrane. Hydrogen was cathodically generated on the entry side and fully oxidized on the exit side. The spectral analysis of both the electrochemical impedance on the entry side and the permeation transfer function between the ac current signals on the two faces of the membrane were recorded according to a method recently proposed. The modifications of the impedance diagrams and the transfer function diagrams induced by the presence of the organic additives were interpreted at the light of the mechanistic model of the transfer function which was recently derived. It is concluded that both additives inhibit the hydrogen evolution reaction, but thiourea promotes hydrogen penetration by inhibiting the recombination reaction, whereas benzotriazole adsorption inhibits the formation of the H_ads and therefore their penetration into the metal matrix.     

某铜矿酸浸渣硫脲法回收银的特点

本文总结分析了某铜矿酸浸渣采用硫脲溶液浸出，锌粉置换回收银的主要特点，针对其特点提出了处理该类废渣回收银的技术措施。     

Use of thiourea to inhibit the incorporation of hydrogen in Ti and Ti-6Al-4V alloy

Commercially pure titanium and a Ti-6Al-4V alloy covered with a thin thermal oxide film derived from hot rolling were electrolytically hydrogenated in 1N aqueous sulfuric acid solution (H₂SO_4(aq)) to see the influence of thiourea (H₂N-CS-NH₂) on the hydrogen uptake of both metals under atmospheric conditions. The inhibitive effect of thiourea was evaluated through quantitative composition analyses (by using a glow discharge spectrometer, GDS) and qualitative microstructural examinations (by using XRD). Thiourea acts as a hydrogenation inhibitor irrespective of the applied current densities. However, the inhibitive effect is more evident at lower charging current densities for longer operating periods.     

用KIO_3容量法测定镀锌液中的硫脲

镀锌液中加入微量硫脲会产生极好的效果。用聚乙烯酸和淀粉作指示剂，直接用ＫＩＯ３标准溶液滴定，是简便、快速、准确测定镀液中硫脲的理想方法。