The effects of power ultrasound (24 kHz) on the electrochemical reduction of CO2 on polycrystalline copper electrodes

The electrochemical CO₂ reduction reaction (CO2RR) on polycrystalline copper (Cu) electrode was performed in a CO₂-saturated 0.10 M Na₂CO₃ aqueous solution at 278 K in the absence and presence of low-frequency high-power ultrasound (f = 24 kHz, P_T ~ 1.23 kW/dm³) in a specially and well-characterized sonoelectrochemical reactor. It was found that in the presence of ultrasound, the cathodic current (I_c) for CO₂ reduction increased significantly when compared to that in the absence of ultrasound (silent conditions). It was observed that ultrasound increased the faradaic efficiency of carbon monoxide (CO), methane (CH₄) and ethylene (C₂H₄) formation and decreased the faradaic efficiency of molecular hydrogen (H₂). Under ultrasonication, a ca. 40% increase in faradaic efficiency was obtained for methane formation through the CO2RR. In addition, and interestingly, water-soluble CO₂ reduction products such as formic acid and ethanol were found under ultrasonic conditions whereas under silent conditions, these expected electrochemical CO2RR products were absent. It was also found that power ultrasound increases the formation of smaller hydrocarbons through the CO2RR and may initiate new chemical reaction pathways through the sonolytic di-hydrogen splitting yielding other products, and simultaneously reducing the overall molecular hydrogen gas formation.     

NiWO3 Nanoparticles Grown on Graphitic Carbon Nitride (g‐C3N4) Supported Toray Carbon as an Efficient Bifunctional Electrocatalyst for Oxygen and Hydrogen Evolution Reactions

Catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are at the heart of water oxidation reactions. Despite continuous efforts, the development of OER/HER electrocatalysts with high activity at low cost remains a big challenge. Herein, a composite material consisting of TC@WO₃@g‐C₃N₄@Ni‐NiO complex matrix as a bifunctional electrocatalyst for the OER and HER is described. Though the catalyst has modest activity for HER, it exhibits high OER activity thereby making it a better nonprecious electrocatalyst for both OER and HER and is further improved by g‐C₃N₄. The catalytic activity arises from the synergetic effects between WO₃, Ni‐NiO, and g‐C₃N₄. A Ni‐NiO alloy and WO₃ nanoparticles decorated on the g‐C₃N₄ surface supported toray carbon (TC) matrix (TC@WO₃@g‐C₃N₄@Ni‐NiO) by a facile route that show an excellent and durable bifunctional catalytic activity for OER and HER in the alkaline medium are developed. This carbon nitride with binary metal/metal‐oxide matrix supported with TC exhibit an overpotential of 0.385 and 0.535 V versus RHE at a current density of 10 mA cm^?2 (Tafel slopes of 0.057 and 0.246 V dec^?1 for OER and HER, respectively), in 0.1 m NaOH . The catalyst is tested in water electrolysis for 17 h.     

NiSb纳米颗粒的热液路线制备及电催化析氢性能研究

本文发展了一种简单经济的过渡金属锑化物热液合成路线,在160 oC的温和条件下,由商业易得的乙酰丙酮基镍和三苯基铋在油胺介质中还原制备出NiSb纳米颗粒. 反应中,还原剂甲硼烷-叔丁基胺络合物的使用能够有效促进金属源的快速还原,用以促进NiSb纳米颗粒的生成. 结构表征显示,所制备的NiSb产物为六方相(空间群P6₃/mmc)颗粒状纳米晶,其粒径约为10 nm. 该合成方法可拓展用于CoSb和Ag₃Sb等纳米颗粒的温和制备. 电催化析氢性能研究显示,NiSb纳米颗粒具有良好的电化学析氢反应性能. 结果显示,当阴极电流密度达到50 mA/cm²和10 mA/cm²时所需要的过电位分别为531和437 mV. 同时,NiSb纳米颗粒还具有较小的电荷转移阻抗和优良的循环稳定性能.     

不同pH酸性溶液中铂电极上氢析出和二氧化碳还原的电化学研究

本文利用循环伏安法和电化学原位红外光谱的联用,研究了Pt(111)和Pt膜电极在CO₂饱和的酸性溶液中氢析出和CO₂还原的竞争. 发现：(i)在pH>2的溶液中,主要反应是氢析出,界面pH值随着氢析出突然增加;(ii)通过红外光谱检测,CO_ad是CO₂还原过程中唯一的吸附中间体;(iii)CO_ad生成速率随着欠电位沉积氢(UPD-H)覆盖的增加而增大,并在氢析出的起始电位达到最大值;(iv)在氢析出时,CO_ad的减少与CO₂吸附和还原所必需的的中间产物(H_ad)有限的可用位点和停留时间相关.     

Pt(111)电极上O2与OHad的吸脱附及氧还原反应动力学 (cited: 1)

研究了Pt(111)电极在0.1 mol/L HClO₄溶液中O₂吸附与OH_ad脱附及氧还原反应的动力学．研究发现OH_ad的可逆吸脱附速率很快;在氧还原的动力学或动力学与传质混合控制区,恒电位下氧还原的电流随反应时间缓慢衰减,在转速较大,扫速较慢的情形下正向扫描过程中氧还原的电流总是明显低于逆向扫描的电流;Pt/0.1 mol/L HClO₄从无O₂切换到O_{2相似文献}   

Ultrasound (US), Ultraviolet light (UV) and combination (US + UV) assisted semiconductor catalysed degradation of organic pollutants in water: Oscillation in the concentration of hydrogen peroxide formed in situ

Application of Advanced Oxidation Processes (AOP) such as sono, photo and sonophoto catalysis in the purification of polluted water under ambient conditions involve the formation and participation of Reactive Oxygen Species (ROS) like OH, HO₂, O₂⁻, H₂O₂ etc. Among these, H₂O₂ is the most stable and is also a precursor for the reactive free radicals. Current investigations on the ZnO mediated sono, photo and sonophoto catalytic degradation of phenol pollutant in water reveal that H₂O₂ formed in situ cannot be quantitatively correlated with the degradation of the pollutant. The concentration of H₂O₂ formed does not increase corresponding to phenol degradation and reaches a plateau or varies in a wave-like fashion (oscillation) with well defined crests and troughs, indicating concurrent formation and decomposition. The concentration at which decomposition overtakes formation or formation overtakes decomposition is sensitive to the reaction conditions. Direct photolysis of H₂O₂ in the absence of catalyst or the presence of pre-equilibrated (with the adsorption of H₂O₂) catalyst in the absence of light does not lead to the oscillation. The phenomenon is more pronounced in sonocatalysis, the intensity of oscillation being in the order sonocatalysis > photocatalysis ⩾ sonophotocatalysis while the degradation of phenol follows the order sonophotocatalysis > photocatalysis > sonocatalysis > sonolysis > photolysis. In the case of sonocatalysis, the oscillation continues for some more time after discontinuing the US irradiation indicating that the reactive free radicals as well as the trapped electrons and holes which interact with H₂O₂ have longer life time (memory effect).     

Spectroscopic studies on the interaction and sonodynamic damage of neutral red (NR) to bovine serum albumin (BSA)

In this paper, the interaction of neutral red (NR) with bovine serum albumin (BSA) and the sonodynamic damage to BSA under ultrasonic irradiation was studied by means of ultraviolet-visible (UV-vis) and fluorescence spectra. The quenching constant (K_SV=5.749×10⁴ L/mol), binding constant (K_A=3.19×10⁴ L/mol) and binding site number (n=0.9462) were measured. The binding distance (r=2.47 nm) between NR and BSA was obtained according to Föster’s non-radiative energy transfer theory. The damage process of BSA molecules was detected by the hyperchromic effect of UV-vis spectra and quenching of intrinsic fluorescence spectra. In addition, the influencing factors such as ultrasonic irradiation time and NR concentration on the damage to BSA molecules were also considered. The results showed that the damage degree is enhanced with the increase of ultrasonic irradiation time and NR concentration. The possible mechanism of sonodynamic damage to BSA molecules was mainly mediated by singlet oxygen (¹O₂). Otherwise, the binding and damaging sites to BSA molecules were also estimated by synchronous fluorescence. The results indicated that the NR is more vicinal to tryptophan (Trp) residue than to tyrosine (Tyr) residue and the damage site is also mainly at Trp residues. The research result will bring a certain significance to use sonosensitive drugs in the fields of tumor treatment.     

Effects of UV-irradiation on the thermo-mechanical properties of optical grade poly(methyl methacrylate)

We studied the evolution of the thermo-mechanical properties of poly(methyl methacrylate) (PMMA) materials exposed to ultra-violet (UV) light. To do so we measured important mechanical parameters including the fracture strength, the stress-strain relation, and Young's modulus as a function of the UV-irradiation dose. We concluded that the mechanical properties of PMMA are affected by UV light. The ductility disappears and the strength and strain at rupture strongly decrease (over 30%). The evolution of the Young's modulus is discussed as a function of the cross-linking degree of the materials. Moreover we observed the occurrence of surface damage, which in its turn enhances the degradation of these mechanical parameters.     

Effects and mechanism of ultrasound pretreatment of protein on the Maillard reaction of protein-hydrolysate from grass carp (Ctenopharyngodon idella)

The effects of two types (energy-divergent/gathered) of ultrasound pretreatment of protein on the Maillard reaction of protein-hydrolysate from grass carp (Ctenopharyngodon idella) were studied. The test and analysis of Fourier transform infrared spectroscopy, surface hydrophobicity and atomic force microscopy of protein, peptide concentration, molecular weight distribution and free amino acid content of protein-hydrolysate were performed to reveal the mechanism. Also, the sensory characteristics of Maillard reaction products were evaluated. Results showed that Maillard reaction products presented higher absorbance value at 294 and 420 nm after pretreated by two types of ultrasound compared to that of control. The grafting degree value of products pretreated by energy-divergent ultrasound increased by 13.87%. Both of these two types of ultrasound pretreatment showed higher (p < 0.05) value of grafting degree compared to that of positive control (thermal denaturation). The random coil content and surface hydrophobicity of protein improved significantly (p < 0.05), and the depth distribution of protein molecules narrowed down after pretreated by ultrasound, especially energy-divergent type ultrasound. The change of protein structure increased small molecular peptide/amino acid content in protein-hydrolysate, so that it promoted the Maillard reaction process of protein-hydrolysate and glucose. The mouthfulness and overall acceptance of Maillard reaction products increased after pretreated by two types of ultrasound. Results indicated that ultrasound, especially energy-divergent type ultrasound pretreatment of protein was an effective method to promote Maillard reaction evolution of protein-hydrolysate from grass carp protein and improved the flavor of Maillard reaction products.     

The adsorption geometry of the (2 × 1)-2O oxygen phase formed on the Co(10 0) surface

The bond geometry of the (2 × 1)-2O-p2mg overlayer on Co(10 0) was determined by analyzing low-energy electron diffraction (LEED) intensity data. Oxygen occupies the three-fold coordinated hcp site along the densely packed rows on the unreconstructed surface. The O atoms are attached to two atoms in the first Co layer and to one Co atom in the second layer. The strong interaction between O and Co is indicated by the bond lengths of 1.83 ± 0.10 Å and 1.99 ± 0.10 Å to the top-layer Co and the Co atoms in the second layer, respectively. The most striking result of our work is that oxygen adsorption causes a marked expansion (by 25%) of the first Co layer spacing (0.90 Å) with respect to the bulk value of 0.72 Å. This strong expansion might offer diffusion channels for O atoms to penetrate further into the subsurface region.     

恒星氦燃烧关键反应12C(α,γ)16O天体物理S因子及其反应率

恒星氦燃烧阶段3α反应和12C（α,γ）16O反应相互竞争,两者的反应率共同决定了氦燃烧结束后12C与16O的丰度比,该比值是大质量恒星后继演化以及伴随的元素核合成过程的初始条件。目前,氦燃烧12C（α,γ）16O反应起始T₉=0.2处,天体物理模型要求的反应率的精确度要低于10%,然而尚未有实验或理论给出满足要求的结果。最为直接和可靠地获取12C（α,γ）16O反应率的方法,就是尽可能往低能区测量其天体物理S因子,然后通过理论外推到感兴趣的能区。为此基于经典的R-矩阵理论,建立了适用于低能核反应的多道、多能级的约化R-矩阵理论来拟合几乎所有可用的16O系统的实验数据。配合使用协方差统计和误差传播理论,拟合外推得到了客观的、内部自恰的和唯一性好的12C（α,γ）16O反应天体物理S因子。总的外推S因子STOT（0.3 MeV）=162.7±7.3 keV·b,理论上首次给出达到恒星演化与元素核合成模型的最低要求的S因子。基于计算给出的全能区的S因子,数值积分给出了温度位于0.04 6 T₉ 6 10的12C（α,γ）16O天体物理反应率。在T₉=0.2处,推荐的反应率为（7.83 ±0.35）×10-15 cm3mol-1s-1。During stellar helium burning, the rates of 3α and the 12C(α,γ)16O reaction, in competition with one another, determine the relative abundances of 12C and 16O in a massive star. The abundance ratio is the beginning condition of the following nucleosynthesis and star evolution of massive stars, which are extremely sensitive to the rate of 12C(α,γ)16O reaction at T₉=0.2. The most direct and trustworthy way to obtain the reaction rate of the 12C(α,γ)16O reaction is to measure the S factor for that reaction to as low energy as possible, and to extrapolate to energies of astrophysical interest. Based on a new multilevel and multichannel reduced R-matrix theory for applications in nuclear astrophysics, we have obtained an accurate and self-consistent astrophysical S factor of 12C(α,γ)16O, by a global fitting for almost all available experimental data of 16O system, with the coordination of covariance statistics and error-propagation theory. The extrapolated S factor of 12C(α,γ)16O was obtained with a recommended value STOT (0.3 MeV)=162.7±7.3 keV·b. And the reaction rates of 12C(α,γ)16O for stellar temperatures between 0.04 6 T₉ 6 10 are provided. At T₉=0.2, the reaction rate is (7.83 ±0.35)×10-15 cm3mol-1s-1, where stellar helium burning occurs.     

达旦黄与牛血清白蛋白结合的热力学研究

采用荧光光谱法和紫外-可见吸收光谱法研究了达旦黄(TY)与牛血清白蛋白(BSA)结合反应的特征。实验发现：TY对BSA有较强的荧光猝灭作用,根据荧光猝灭数据,由Stern-Volmer方程和Line weaver-Burk双倒数方程得到了反应的结合常数和热力学参数,并由此推出了结合反应的主要作用力类型。在此基础上依据Frster非辐射能量转移机理,探讨了TY与BSA相互结合时,给体-受体间的距离和能量转移效率。从而证实了该结合作用为单一静态猝灭过程,并阐明了其猝灭机制是通过能量转移产生的。     

CLi+5超碱团簇的结构及储氢性能的理论研究

利用密度泛函理论( B3LYP) 方法,在 6 - 311 + + G ( d,p) 基组水平上,对超碱团簇 CLi₅及其阳离子体系 CLi₅⁺的几何结构和稳定性等物理化学性质进行理论计算,并进一步研究它们的储氢性能． 分析可知,CLi₅⁺超碱离子团簇结构相比中性 CLi₅团簇结构动力学稳定性要高,表面吸氢能力更强． 氢分子在 CLi₅⁺表面能以介于物理吸附与化学吸附之间的形式吸附,每个 Li 原子最多可以有效吸附三个 H₂,平均吸附能处于 1. 065 ～ 2. 732 k Cal/mol 范围内,储氢质量分数可达 39. 30 wt % ,表明 CLi₅⁺超碱离子团簇可以作为一种理想的储氢材料．     

Effect of lattice strain on the oxygen vacancy formation and hydrogen adsorption at CeO2(111) surface

Using first-principles calculation, the effect of lattice strain on the oxygen vacancy formation at CeO₂(111) surface has been investigated. The tensile strain facilitates the oxygen vacancy formation at the surface and the compressive strain hinders the process. This is in part due to the strengthening or weakening of the surface Ce–O bond under the lattice strain. On the other hand, a more open surface with a larger lattice constant can better accommodate the larger Ce³⁺ and thus facilitate the structural relaxation of the reduced surface. The studies on the strain effect on the atomic hydrogen adsorption at the defect-free CeO₂(111) surface show that the adsorption strength monotonously increases with the increase of the lattice strain, further confirming the tunable surface chemical activity by lattice strain.     

Miscibility and Hydrogen Bonding Interactions in Blends of Poly(hydroxyether ketone) and Poly(4-vinyl pyridine)

The influence of silica nanoparticles on the tensile properties of poly(ethylene terephthalate)(PET) fibers was investigated. The results showed that mechanical properties of PET fibers were improved through nano‐silica incorporation. Two maxima of the modulus‐strain curves of PET/silica nanocomposites (PETS) fibers are always higher than those of pure PET (PET0) fibers. The results of microstructure investigations suggested that the amorphous orientation factor of PETS fibers is higher than that of PET0 fibers. It is suggested that the increase of amorphous orientation factor contributed to the improvement of tensile properties of PET fibers. Considering the difference in modulus‐strain curves of PET0 and PETS fibers, it is believed that the addition of nanoparticles not only improved the amorphous orientation factor but also changed the load units of PET fibers when strained, which also resulted in the improvement of tensile properties.     

Dynamic observations of the formation of thin Cu layers on clean and hydrogen-terminated Si(1 1 1) surfaces

The growth of Cu on the clean and hydrogen-terminated Si(1 1 1) surfaces is studied in situ by low-energy electron microscopy (LEEM). The dependence of the growth of the “5×5” layer on the clean Si(1 1 1) 7×7 surface upon the deposition temperature is investigated by combining LEEM with LEED. After completion of the “5×5” layer not only the regular-shaped three-dimensional islands reported before are observed but also irregular shaped more two-dimensional islands. On the hydrogen-terminated Si(1 1 1) surface the formation of the “5×5” structure is suppressed and nano-scale islands form preferentially at the step edges and domain boundaries. This is attributed to the enhancement of the surface migration of Cu atoms by the elimination of the surface dangling bonds.     

pH值对滇池水体溶解性有机质(DOM)光降解作用的影响

运用紫外光谱、三维荧光光谱技术结合平行因子分析法（PARAFAC）探讨了pH值对滇池水体环境中溶解性有机质（DOM）光化学降解特性（紫外光谱特征、荧光组分及其荧光强度）的影响。掌握了不同pH值条件下DOM光化学降解特性及其差异性,可为DOM的生物地球化学循环基础数据提供有利支撑,同时对富营养化湖泊水质改善和有效控制具有重要的启示作用。结果表明,在光降解发生过程中（0～30 d）,DOM被识别出具有三个主要荧光组分,分别为长波类富里酸组分C1（325,425 nm）,类蛋白类组分C2（295, 390 nm）和具有高芳香度特性的类腐殖质组分C3（260/350,360/450 nm）;pH值的变化对DOM光降解过程中的紫外光谱和三维荧光光谱特征均产生重要影响;当pH值从4.0增加到9.0,DOM的紫外吸光系数随pH值增大而增大,总荧光强度随pH值增加而逐渐下降;类蛋白组分C2从降解的第8天开始,其荧光强度也表现出随pH值增加逐渐下降的趋势,这表明高pH值能够促进水体DOM的光降解作用。鉴于pH值能够对DOM光降解过程及其紫外光谱和三维荧光光谱特征产生重要影响,研究认为,对比不同来源DOM（自然水体、DOM提取物等）的紫外光谱、三维荧光光谱和平行因子分析结果时,应监测并报告DOM溶液的pH值,pH值应尽量保持一致,以保证结果的可比性。     

Oxygen adsorption and oxidation reactions on Au(2 1 1) surfaces: Exposures using O2 at high pressures and ozone (O3) in UHV

Nanosized gold particles supported on reducible metal oxides have been reported to show high catalytic activity toward CO oxidation at low temperature. This has generated great scientific and technological interest, and there have been many proposals to explain this unusual activity. One intriguing explanation that can be tested is that of Nørskov and coworkers [Catal. Lett. 64 (2000) 101] who suggested that the “unusually large catalytic activity of highly-dispersed Au particles may in part be due to high step densities on the small particles and/or strain effects due to the mismatch at the Au-support interface”. In particular, their calculations indicated that the Au(2 1 1) stepped surface would be much more reactive towards O₂ dissociative adsorption and CO adsorption than the Au(1 1 1) surface. We have now studied the adsorption of O₂ and O₃ (ozone) on an Au(2 1 1) stepped surface. We find that molecular oxygen (O₂) was not activated to dissociate and produce oxygen adatoms on the stepped Au(2 1 1) surface even under high-pressure (700 Torr) conditions with the sample at 300-450 K. Step sites do bind oxygen adatoms more tightly than do terrace sites, and this was probed by using temperature programmed desorption (TPD) of O₂ following ozone (O₃) exposures to produce oxygen adatoms up to a saturation coverage of θ_O = 0.90 ML. In the low-coverage regime (θ_O ? 0.15 ML), the O₂ TPD peak at 540 K, which does not shift with coverage, is attributed to oxygen adatoms that are bound at the steps on the Au(2 1 1) surface. At higher coverages, an additional lower temperature desorption peak that shifts from 515 to 530 K at saturation coverage is attributed to oxygen adsorbed on the (1 1 1) terrace sites of the Au(2 1 1) surface. Although the desorption kinetics are likely to be quite complex, a simple Redhead analysis gives an estimate of the desorption activation energy, E_d, for the step-adsorbed oxygen of 34 kcal/mol and that for oxygen at the terraces near saturation coverage of 33 kcal/mol, values that are similar to others reported on Au surfaces. Low Energy Electron Diffraction (LEED) indicates an oxygen-induced step doubling on the Au(2 1 1) surface at low-coverages (θ_O = 0.08-0.17 ML) and extensive disruption of the 2D ordering at the surface for saturation coverages of oxygen (θ_O ? 0.9 ML). Overall, our results indicate that unstrained step sites on Au(2 1 1) surfaces of dispersed Au nanoparticles do not account for the novel reactivity of supported Au catalysts for CO oxidation.     

新试剂2-(4-安替比林偶氮)-5-二乙氨基苯胺与钯显色反应的研究及应用

在ｐＨ＝５．０ＨＡｃ－ＮａＡｃ缓冲介质中,吐温－８０存在下,２－（４－安替比林偶氮）－５－二乙氨基苯胺（ＡＤＥＡ）与钯生成２∶１红色络合物,λｍａｘ＝５３０ｎｍ,ε＝６．１５×１０４Ｌ·ｍｏｌ－１·ｃｍ－１,钯的含量在０—２０μｇ／２５ｍＬ内符合比耳定律,本方法用于钯催化剂中痕量钯的测定,结果令人满意。     

Ultrasound-assisted heterogeneous activation of persulfate by nano zero-valent iron (nZVI) for the propranolol degradation in water

This study investigated the degradation of propranolol (PRO), a beta (β)-blockers, by nano zero-valent iron (nZVI) activated persulfate (PS) under ultrasonic irradiation. Effects of several critical factors were evaluated, inclusive of PS concentration, nZVI dosage, ultrasound power, initial pH, common anions, and chelating agent on PRO degradation kinetics. Higher PS concentration, nZVI dosage and ultrasound power as well as acidic pH favored the PRO degradation. Conversely, anions and chelating agent took on the inhibitory effect towards PRO degradation to different extents. Furthermore, the variations of morphology and surface composition of nZVI before and after the reaction were characterized by TEM, XRD and XPS. Finally, on the basis of identified degradation intermediates by LC/MS/MS analysis, this work tentatively proposed the degradation pathways. These encouraging results suggest that US/nZVI/PS process is a promising strategy for the treatment of PRO-induced water pollutant.