Effect of Lead Ions on the Kinetics of Gold Deposition from Cyanide Electrolytes

The depolarization of the gold electrodeposition in the presence of lead ions depends on their concentration and the duration of electrode contact with solution preceding a potential scan in an extremum fashion. At constant coverages of the gold surface by lead adatoms , the process rate depends on the overvoltage in accord with the Tafel equation. Effective values of the exchange current i ₀ and transfer coefficient increase with from i ₀ 3 × 10^–5 A cm^–2 and = 0.23 in pure solutions to 3 × 10^–4 A cm^–2 and 0.53 at 0.4. The reaction order by cyanide ions is independent of and equals nearly –0.9. Effects of lead adatoms on the kinetics of cathodic and anodic processes are compared and the obtained data may be brought to conformance given that their mechanisms in pure solutions differ and converge in the presence of lead adatoms.     

Anodic behavior of gold in acid thiourea solutions: A cyclic voltammetry and quartz microgravimetry study

It is shown that at potentials E < 0.5 V (NHE) gold undergoes practically no dissolution in thiourea solutions containing no catalytically active species. The dissolution at a perceptible rate (> 100 μA cm^?2) starts at E ≥ 0.65 V, with the primary process being the oxidation of thiourea, which gives rise a current peak at E ? 1.0 V. The thiourea oxidation at E ≥ 1.1 produces the appearance of catalytically active species, which drastically accelerate the gold dissolution process in the potential region extending from a steady-state value to 0.6 V, where the current efficiency for gold approaches 100% and a peak emerges at E ? 0.55 V. The peak’s height is commensurate with the value of the limiting diffusion current associated with the ligand supply. The species in question make no discernible impact on the thiourea oxidation process. Formamidine disulfide, which forms during the anodic oxidation of thiourea or which is added in solution on purpose, exerts no noticeable catalytic influence on the anodic gold dissolution. The catalytically active species is presumably the S^2? ion, product of decomposition and deep oxidation of thiourea and formamidine disulfide. Indeed, adding sulfide ions in solution has a strong catalytic effect on the gold dissolution, whose character is identical to that of the effect exerted by products of anodic oxidation of thiourea at E ≥ 1.1 V μA cm^?2.     

Kinetic Parameters of the Dissolution of Gold in Thiourea Solutions

The temperature dependence of the rate constants for the dissolution of gold in thiourea solutions was determined. The activation energies calculated suggest that the rate of gold dissolution is diffusion-controlled at 5-22 °C but is kinetically-controlled at 25-60 °C (E _a = 42.83 kJ/mol). Auger spectroscopy was used to study the composition of the surface adsorption layers and a mechanism for the passivation of the reactive surface during the gold dissolution process was proposed.     

Kinetic Parameters of Gold Dissolution in Cyanide Solutions: The Effect of Complex Cyanide Ions of Mercury

The kinetics of the gold dissolution in cyanide solutions is studied at constant values of the coverage () of the gold surface by mercury atoms. The constancy of is ensured by maintaining an identical value of the duration (t) of contact of electrode with solution (after renewing its surface by cutting off a thin surface layer of metal) at a potential of –1.3 V, at which the discharge of mercury ions is limited by their diffusion to the electrode. At t = const kinetic dependences of the gold dissolution process correspond to the Tafel equation. Effective values of exchange current i ₀, transfer coefficient , and reaction order by cyanide ions P are determined. With increasing value of their magnitude increases from values 10^–5 A cm^–2, 0.1, and 0.17 that are characteristic of purely cyanide solutions (composition 0.1 M KCN, 0.1 M KOH, and 0.01 M KAu(CN)₂) to i ₀ 2 × 10^–4 A cm^–2, = 0.46, and P 1 at t = 270 s. These results are compared with the data obtained earlier during similar investigations in solutions containing thallium, lead, and bismuth. Common and individual features in the behavior of mercury-containing electrolytes are revealed. It is shown that the possible mechanism of the acceleration of the gold dissolution process in the presence of catalytically active atoms, which had been proposed in these works, may be used also for explaining the action of mercury atoms on this process.     

On the reason for gold passivation in thiourea electrolytes during its dissolution in the presence of sulfide ions

The effect of the gold surface renewal on the polarization curve is studied at various gold dissolution stages in electrolytes containing 0.1 M thiourea, (1.4–4.0) 10^?5 M sodium sulfide, and 0.5 M sulfuric acid, at 20°C. The behavior of the curves after the cutting-off of a surface layer of gold in the potential region where a current decay is observed (i.e. passivation of the process) and the dependence of the current in the maximum of a polarization curve on the thiourea concentration are explained by “deactivation” of catalytically active adsorbed sulfide ions.     

Cooperative Ligands in Dissolution of Gold

Development of new, environmentally benign dissolution methods for metallic gold is driven by needs in the circular economy. Gold is widely used in consumer electronics, but sustainable and selective dissolution methods for Au are scarce. Herein, we describe a quantitative dissolution of gold in organic solution under mild conditions by using hydrogen peroxide as an oxidant. In the dissolution reaction, two thiol ligands, pyridine-4-thiol and 2-mercaptobenzimidazole, work in a cooperative manner. The mechanistic investigations suggest that two pyridine-4-thiol molecules form a complex with Au⁰ that can be oxidized, whereas the role of inexpensive 2-mercaptobenzimidazole is to stabilize the formed Au^I species through a ligand exchange process. Under optimized conditions, the reaction proceeds vigorously and gold dissolves quantitatively in two hours. The demonstrated ligand-exchange mechanism with two thiols allows to drastically reduce the thiol consumption and may lead to even more effective gold dissolution methods in the future.     

离子色谱法测定硫脲中的钙离子

建立了离子色谱法测定硫脲中钙离子的方法。采用CS12A阳离子交换色谱柱,以甲基磺酸(16mmol/L)作为淋洗液,测定了硫脲样品中的钙离子,通过分析5批不同的样品,分别得到其钙值在270~410μg/g,加标回收率在97.2%~102.3%。方法无需复杂的样品前处理,分析方法干扰小,测定结果令人满意。     

The effect of chemisorbed sulfide ions on the gold electrodeposition from acidic thiocarbamide electrolytes

Introducing sodium sulfide (about 10^?5 M) into acidic thiocarbamide solutions reduces the gold reduction overpotential. The reaction rate passes through a maximum at a potential of 0.1 V. The overpotential depends on the sulfide ion concentration and the time of electrode exposure to solution prior to the beginning of scanning. Transients of potential measured on a renewable gold electrode in thiocarbamide electrolytes containing catalytically active species served as the basis for calculations of the coefficient of trapping of sulfide ions by the growing gold deposit. The kinetics of gold electrodeposition at fixed surface coverages with adsorbed sulfide ions θ is studied. It is shown that at θ = const, the dependence of the reaction rate on the overpotential is described by the Tafel equation. It is shown that with an increase in θ, the effective values of exchange current and transfer coefficient increase from i ₀ ≌ 10^?5 A/cm² and α ≌ 0.25 in pure solutions to α ≌ 0.5 and i ₀ ≌ 10^?4 A/cm² at θ ≥ 0.3 and then remains virtually unchanged. The reaction order decreases in the absolute magnitude, remaining negative. Thus for θ ≌ 0, p _k = ?logi/?logc = ?1, whereas for θ ≥ 0.3, p _k = ?0.3. A possible explanation is proposed for the catalytic effect of the sulfide ion adsorption on the mechanism of the gold reduction from acidic thiocarbamide electrolytes.     

Electrocatalysis by adatoms at the gold and silver dissolution in cyanide solutions

The peculiarities of the effects of upd thallium, lead, bismuth, and mercury on the dissolution rates of gold and silver in cyanide electrolytes are compared. In general, they feature the abrupt acceleration of the dissolution of gold and, to a lesser extend, silver in the chemisorption range of mentioned ions. As the potential increases, the gold dissolution rates passes through a maximum the height of which is comparable with the limiting current of this process associated with limitations in the delivery of cyanide ions to the electrode surface. The current decay after the maximum is due to desorption of catalytically active adatoms. The chemisorption rate of thallium, lead, and bismuth ions at potentials more negative than the current peak is controlled by their diffusion to the gold surface, whereas the chemisorption rate of mercury is controlled by the adsorption kinetics. With the increase in the surface coverage with adatoms θ, the catalytic activity of all considered adatoms passes through a maximum. The sharp increase in the effective transfer coefficient in the presence of these adatoms makes the main contribution into the acceleration of the gold dissolution, while the increase in the exchange current has a smaller effect. The chemisorption of mentioned atoms on gold not only accelerates the dissolution but also changes its mechanism. For gold dissolution, the catalytic activity of upd thallium, lead, and bismuth increases in the following sequence: Tl ? Pb < Bi and the effect is additive in their simultaneous presence. For silver, the increase in the exchange current makes the main contribution into the acceleration of dissolution, whereas the transfer coefficient and the reaction order with respect to the ligand change insignificantly. Explanation of the observed peculiarities is given.     

沉淀溶解法制备纳米硫化锌

以烷基黄原酸锌和硫化钠分别为锌源和硫源，采用烷基黄原酸锌沉淀溶解法制备了粒度可调、粒径分布比较窄的面心硫化锌纳米粒子，利用比表面积(BET)测定、透射电镜(TEM)、粉末X射线衍射(XRD)、傅里叶转换红外光谱(FTIR)等方法对合成的硫化锌纳米粒子进行了表征。结果表明随着烷基黄原酸锌链长的增长，通过添加硫化钠而生成的硫化锌纳米粒子的粒径逐渐减小。本文还对沉淀溶解法制备纳米硫化锌的溶液化学反应机理进行了探讨。     

The effect of potential on the gold dissolution in cyanide solutions in the presence of sulfide ions

The effect of potential on the rate of gold dissolution in the cyanide solutions in the presence of sulfide ions is studied. The dependences of current on the time after the electrode surface renewal were measured under the potentiostatic conditions. The majority of experiments were performed in the solution of the following composition, M: 0.1 KCN, 0.1 KOH, 0.01 KAu(CN)₂, (1.5–2) × 10^?5 Na₂S at 23°C. It is shown that, at the potentials more positive than ?0.1 V (NHE), the rate of gold dissolution starts to increase as soon as the surface is renewed, which is associated with high-rate chemisorption of catalytically active sulfide ions. At E < ?0.1 V, the chemisorption proceeds slowly, and a considerable increase in the current takes much time. Therefore, in the potentiodynamic measurements, at E < ?0.1 V, no catalytic effect of sulfide ions is observed. When the ratio between the concentrations of sulfide and cyanide ions is decreased, the potential, which, by convention, bounds the aforementioned ranges, shifts in the positive direction. Plausible explanations for these regularities are proposed.     

酸性介质中丙烯基硫脲对铜阳极溶出和阴极沉积过程影响的EQCM研究

采用循环伏安(CV)和电化学石英晶体微天平(EQCM)方法研究了酸性介质中铜阳极溶出和阴极沉积过程以及丙烯基硫脲(AT)对该过程的影响. 结果表明, 铜阳极溶出和阴极沉积过程的M/n分别为32.0和34.2 g/mol, 都是两电子过程, 其间未检测到Cu(Ⅰ)中间产物. AT改变了铜阳极溶出和阴极沉积的历程. 在含AT的溶液中, 铜阳极溶出和阴极沉积过程的M/n分别为61.9和65.4 g/mol, 可指认铜阳极溶出产物为CuAT+, 并提出了AT存在下Cu阳极溶出和阴极沉积过程的反应机理; 从电极表面质量定量变化的角度提供了Cu阳极溶出和阴极沉积过程的新数据.     

硫脲型树脂富集—石墨炉原子吸收光谱测定地质水中痕量金

本文研究了硫脲型树脂对金的吸附条件，提出了以水文地球化学探矿为目的现场富集，石墨炉原子吸收光谱测定地质水中痕量金的方法，实验表明：该树脂在［Ｈ＾＋］＞０．２ｍｏｌ／Ｌ的较宽酸度范围内，在最大流速情况下对天然水中痕量金进行富集，测得回收率达９８％以上，大部分共存离子不影响金的富集与测定，方法的检出限为０．０５ｎｇ／Ｌ。     

岩矿样品金元素分析中硫脲解脱流程的改进

硫脲解脱流程作为金矿样品金分析测试重要的前处理环节,在采用传统的水浴锅解脱流程测试过程中,发现存在耗电量大、比色管易进水汽、易结垢、架易腐蚀掉落等缺点。为了改善上述问题,本实验室在金分析过程中对解脱流程尝试做了改进,更换常用的水浴锅为恒温烘箱进行解脱,进而做了对比。同时,本研究对烘箱参数、温度设置、加热时间等做了对比分析,以获得最佳处理物理环境,并对改进前后所获得的测试结果进行了相关性分析,以判别其测试结果的可替代性。结果表明：采用烘箱代替水浴锅解脱,具有升温快,温度可控,耗电低,效率高,安全卫生,质量稳定可靠等优势。烘箱参数推荐设置为P:28、I:200、D:50,烘箱解脱过程中温度应控制95-102℃之间,升温时间15 min之后解脱液即可达到90 ℃以上,解脱时间一般需要35-40 min。通过相关性分析,其相关性系数均在0.99以上,呈近函数高度相关关系,由此认为,在实验室金分析过程中,烘箱代替水浴锅解脱完全可行,烘箱解脱更具有优势,应推广应用。     

Kinetics of the Oxidation of Methyl Phenyl Sulfide by Hydrogen Peroxide in the Presence of Hydrocarbonate Anion

The oxidation of methyl phenyl sulfide in water and water-alcohol mixtures takes place both by a noncatalytic mechanism and with the participation of hydrogen peroxide as catalyst; in the presence of ammonium hydrocarbonate it takes place by a mechanism involving HCO ₄ ⁻ as a more active oxidant than hydrogen peroxide (>100 times). In water-alcohol media (ethylene glycol, isopropyl alcohol, tert-butanol) the rate decreases in the order H₂O > EG > IPA > TBA. The reactivity of organic sulfides varies in the following way: MeSPh ≈ EtSPh << Et₂S. The results were interpreted from the standpoint of a molecular mechanism of oxidation of the sulfide with H₂O₂ and HCO ₄ ⁻ through a polar transition state, containing the HOX molecule (X = H, OH, OR) as acid-base catalyst.__________Translated from Teoreticheskaya i Eksperimental’naya Khimiya, Vol. 41, No. 2, pp. 94–99, March–April, 2005.     

Catalytic Activity of Thallium, Lead, and Bismuth Adatoms in the Gold Dissolution Reaction in Cyanide Solutions: A Comparative Characterization

Quartz microgravimetry is used to determine the ratio between coefficients of mass transfer (1 : 0.54 : 0.48), which characterizes relative values of rates of diffusion of hydroxy complexes of thallium, lead, and bismuth in alkaline solutions. The ratio is used when refining the condition under which on a renewable electrode in solutions containing these ions at the concentration c _i the electrode coverage by relevant adatoms _i with increasing duration of contact of the electrode with solution reaches constant values: (c _Tl t) = (0.54c _Pb t) = (0.48c _Bi t). Measured are i,t curves on a renewable gold electrode at E = const in solutions containing 0.1 M KCN, 0.1 M KOH, 0.01 M KAu(CN)₂, and 8 × 10^–6 M compounds of thallium or 1.5 × 10^–5 M, lead, or 1.6 × 10^–5 M, bismuth. Shown is that at (, E) = const the currents of dissolution of gold in these solutions increase in the series Tl < Pb < Bi, which evidences an increase in this series of the catalytic activity of adatoms of these metals. Shown is that at = const the catalytic action of adatoms of thallium and bismuth has an approximately additive character. The obtained data are analyzed with allowance made for the explanation offered earlier for the catalytic effect of adatoms on the anodic dissolution of gold based on the hypothesis about the shift of the potential of the free zero charge in the negative direction after substituting a metal atom for chemisorbed cyanide ions.     

低成本硫化物固态电解质Li6-xPS5-xClx的制备与性能研究

硫化物固体电解质以其室温电导率高,热稳定性好,电化学窗口宽等特点,在高功率及室温固态电池方面优势突出,是极具潜力的固态电解质材料. 但制备其所需的高纯度Li₂S原料高昂的价格使其实际应用受到掣肘,故本文使用单质锂金属（99.9%）、升华硫、氯化锂和五硫化二磷等低成本原料,采用球磨法和高温热处理制备得到了Li_6-xPS_5-xCl_x（x = 0.5）固态电解质粉末,通过X射线衍射（XRD）、拉曼（Raman）、扫描电子显微镜（SEM）及能谱仪（EDS）对Li_6-xPS_5-xCl_x（x = 0.5）固态电解质进行了表征,并使用交流阻抗法测试了其电导率,电导率可达8.29×10 ^-4 S·cm ^-1,将Li_6-xPS_5-xCl_x（x = 0.5）固态电解质粉末进行冷压制片,制成Li对Li半电池后显示了良好的循环性能.     

Kinetics and mechanism of gold dissolution in thiourea solutions: Effect of sulfide ions

Chronoamperograms for gold in solutions containing 0.1 M thiourea, 0.5 M H₂SO₄, and catalytically active sulfide ions at the concentration c ₁ from 1 × 10^?5 to 4 × 10^?5 M are obtained at different potentials with the aid of an automated setup intended for renewing the electrode surface directly in the solution by cutting off a thin surface layer of the metal. It is shown that the results of measurements of the current practically coincide at a constant value of the product c ₁ t, where t is the time period elapsed after the renewal of the electrode surface. Such a coincidence testifies to a diffusion nature of processes that hamper accumulation of sulfide ions at the gold surface. This fact permitted the use of a procedure developed previously for the calculation of polarization curves at constant values of surface coverage θ by catalytically active ions. At θ = const, the voltammetric curves for gold in sulfide-containing thiourea solutions are shown to correspond to the Tafel equation. With the surface coverage increasing, the effective values of the exchange current i ₀, transfer coefficient α, and anodic reaction order with respect to thiourea P _a increase from the values i }~ 10^?5 A cm^?2, α }~ 0.12, and P _a = 0.2, which are characteristic of pure solutions, to 2 × 10^?4 A cm^?2, α }~ 0.5, and P _a = 1.1 (at θ }~ 0.5). An interpretation to the established regularities is given.     

Inhibition of Amyloid Fibril Growth and Dissolution of Amyloid Fibrils by Curcumin–Gold Nanoparticles

Inhibition of amyloid fibrillation and clearance of amyloid fibrils/plaques are essential for the prevention and treatment of various neurodegenerative disorders involving protein aggregation. Herein, we report curcumin‐functionalized gold nanoparticles (Au‐curcumin) of hydrodynamic diameter 10–25 nm, which serve to inhibit amyloid fibrillation and disintegrate/dissolve amyloid fibrils. In nanoparticle form, curcumin is water‐soluble and can efficiently interact with amyloid protein/peptide, offering enhanced performance in inhibiting amyloid fibrillation and dissolving amyloid fibrils. Our results imply that nanoparticle‐based artificial molecular chaperones may offer a promising therapeutic approach to combat neurodegenerative disease.