Square‐wave Voltammetry of Two‐step Surface Electrode Mechanisms Coupled with Chemical Reactions – A Theoretical Overview

Square‐wave voltammetry (SWV) of so‐called “surface redox reactions” is seen as a simple and efficient tool to quantify large number of drugs, physiologically active substances and other important chemicals. It also provides elegant methods to get access to relevant kinetic and thermodynamic parameters related to many lipophilic compounds. Moreover, with this technique we can study activity of various enzymes by exploring the “protein‐film voltammetry” set up. In this work, we focus on theoretical SWV features of four complex surface electrode mechanisms, in which the electron exchange between the working electrode and the studied redox substrate takes place in two successive steps. While we present large number of calculated square‐wave voltammograms, we give hints to recognize particular two‐step surface mechanism, but also to distinguish it from other similar mechanisms. We present plenty of relevant aspects of surface two‐step surface EE, two‐step surface ECE and surface catalytic EEC’ mechanisms. Moreover, we present for the first time a series of theoretical results related to two‐step surface EECrev mechanism (i. e. two‐step surface reaction coupled to follow‐up reversible chemical step). The simulated voltammetric patterns presented in this work can bring relevant aspects to resolve some experimental situations met in voltammetry of many redox enzymes and other important substances whose electrochemical transformation occurs in two‐steps.     

Anodic oxide growth on Zr in neutral aqueous solution

Anodization and subsequent cathodic reactions on a thin-film sample of Zr were studied with in-situ neutron reflectometry (NR) and electrochemical impedance spectroscopy (EIS). The NR results during anodization showed the originally 485 Å thick Zr film generally behaved similar to a bulk electrode in neutral solution. The anodization ratio measured at applied potentials increased in steps of 0.5 V was somewhat higher than the value determined by coulometry, while the Pilling Bedworth ratio is in good agreement with published data. Thickening of the oxide layer, accelerated immediately after each potential increase, gradually decreased over several hours, but remained nonzero even after ～12 h. The thickened oxide eventually cracked when its thickness reached ～120 Å, causing loss of passivation. Surprisingly, neither the anodization ratio nor the Pilling Bedworth ratio showed any discontinuity at the time of oxide cracking, and the EIS behaviour remained qualitatively as before. This observation is taken as the evidence that the cracked and intact regions of the electrode behave more or less independently as parallel electrodes. When the potential was eventually switched to cathodic polarity, NR shows, as expected, that the effects of oxide cracking were irreversible. However, the electrode resistance recovered partially suggesting the cracks were rapidly plugged with newly formed oxide.     

Effect of polyethylene glycol on corrosion of fresh macroporous silicon in 1.0 M NaOH and application in determination of porosity and thickness by gravimetric measurement

Abstract

This work presents on improvement in gravimetric measurement for determining the porosity and thickness of microporous silicon. Herein, the corrosion of fresh macroporous silicon (f-MPSi) in 1.0?M NaOH with different concentrations of polyethylene glycol (PEG 200/400/600) was studied by weight loss measurement and scanning electron microscopy (SEM). The results showed that the corrosion rate decreased with increasing polyethylene glycol concentration, and increased with an increase in temperature. Polyethylene glycol can inhibit the corrosion of f-MPSi in NaOH solution. Moreover, 1.0?M NaOH/PEG 600 (10%) can be used as the optimized solution to remove f-MPSi for measuring its porosity and thickness by gravimetric measurement.     

乙醇对纳米多孔氧化铝薄膜热释光的影响

以乙醇-草酸混合溶液为电解液,用二次阳极氧化法制备纳米多孔Al_2O_3∶C薄膜。在制备过程中,碳的掺杂浓度可控。实验结果表明,随着碳浓度的增加,热释光强度逐渐增大;随着退火温度的升高,320℃左右的主热释光峰的强度先升高后降低。在退火温度为500℃时,主热释光峰的强度达到最大。纯草酸溶液制备的Al_2O_3薄膜的热释光剂量响应曲线在10~50 Gy是线性的,在50~100 Gy呈超线性;而乙醇-草酸混合溶液制备的Al_2O_3∶C薄膜在10~100 Gy基本呈线性。     

基于伽利略结构的二级激光扩束系统的设计

针对高倍率扩束系统设计要求(即轴上和轴外像差都得到较好的校正),从三级像差理论出发,设计了一种新型的40^×高倍率激光扩束系统。该系统是基于简单的伽利略结构并通过二级扩束系统来实现的,系统包括4片透镜,通过引入2个二次非球面、 2个反射镜或1个棱镜来折叠光路。利用CODE V光学设计软件给出了该系统的光学结构参数和外形结构图,并进行了像质评价。结果表明：该系统结构简单,设计难度小,成本较低,像质好,性能优良,是一种可以被广泛采用的高倍率激光扩束系统。     

硬质合金CVD金刚石涂层工具衬底前处理技术研究

本研究采用KOH:K3[Fe(CN)6]:H2O和H2SO4:H2O2两种溶液浸蚀硬质合金衬底,分别选择刻蚀WC和Co.并在浸蚀过的硬质合金衬底上,用强电流直流伸展电弧等离子体CVD法沉积金刚石涂层.研究表明,两步混合处理法不仅可以有效的去除硬质合金基体表面的钴,而且,还可显著粗化硬质合金衬底.因此,提高了金刚石薄膜的质量和涂层的附着力.     

添加表面活性剂两步沉淀法制备甲醇催化剂

采用添加表面活性剂两步沉淀法制备了具有高表面铜相对浓度的超细甲醇合成催化剂。以组成为H2/CO/CO2/N2=66/27/3/4(体积比）的原料气对催化剂进行了活性评价。结果表明,该催化剂比传统并流沉淀法制备的铜基催化剂活性提高47.9%,比两步沉淀法和添加表面活性剂并流沉淀法制备的铜基催化剂活性分别提高9.3%和16.8%。利用SEM、XRD及XPS方法对催化剂的结构、形貌和表面金属组成进行了表征。     

负载铂催化剂中沸石载体酸性对甲烷两步转化的影响

考察了具有相同金属分散度的Pt/NaY、Pt/HNaY、 Pt/HY、Pt/NaBeta和Pt/HBeta催化剂中沸石载体的酸性对在低温下（≤250 ℃）甲烷两步等温转化反应以及由甲烷解离吸附产生的表面碳物种分布的影响。由甲烷等温两步转化生成的C2+烃类产物的总量随着载体酸性的增加而明显增加;C2～C6产物的分布也发生了变化。由表面碳物种的程序升温加氢结果表明,在各种催化剂上碳物种的形式是相似的,其总量和具有活性的Cα物种的量均因载体酸性增加而增加,反应性也增大。这种因沸石载体酸性变化而引起的载体效应是由金属和载体的相互作用造成负载在酸性载体上铂粒子的贫电子性而引起,即由金属粒子电子性质的变化而引起的催化性质的变化。     

ZnO-SnO_2透明导电薄膜的制备及性能研究

采用二步成胶工艺制备ZnO-SnO_2透明导电薄膜,应用X射线衍射、原子力显微镜、紫外-可见分光光度计、薄膜分析仪及四探针仪等对薄膜的结构、表面微观形貌、透过率和导电性能进行表征.结果表明,锌锡摩尔比为9/12,退火温度为500 ℃时,薄膜的透过率达90%,电阻率为3.15×10~(-3) Ω·cm.与其它工艺相比,二步成胶工艺所制备出的ZnO-SnO_2透明导电薄膜性能优异.     

阳极氧化法制备TiO_2纳米管及其光催化性能

纳米TiO_2对诸多环境污染物有显著的光催化降解作用,光催化已发展成为新型环境污染治理技术.本文采用阳极氧化法制备出TiO_2纳米管,对比了四种电解液组成(A氟化铵+硫酸铵+水;B氟化铵+硫酸铵+乙酸+水;C氟化铵+硫酸铵+甘油+水;D氢氟酸+二甲基亚砜(DMOS)+乙醇)对催化剂表面形貌及光催化性能的影响.结果表明,电解液A和C都制备出了形貌清晰的TiO_2纳米管,管径约为60～74 nm.样品经400℃煅烧,TiO_2晶型主要为锐钛矿相;经500℃煅烧,出现少量金红石相;经700℃煅烧,晶型全部为金红石相.具有良好形貌的TiO_2纳米管同时具有良好的紫外光吸收能力.当亚甲基蓝初始浓度为10mg·L~(-1),经500℃煅烧的TiO_2纳米管光催化活性最佳,光照30 min亚甲基蓝的降解率达89.98%.亚甲基蓝光催化降解反应符合一级反应动力学,反应速率常数为0.079 30.