Comparative study of hydrogen peroxide electro-generation on gas-diffusion electrodes in undivided and membrane cells

The generation of hydrogen peroxide by means of the cathodic reduction of oxygen at gas-diffusion electrodes with a near 100% current efficiency was achieved in concentrations sufficient for the mineralization of refractory organics in Fenton treatment. A decrease in current efficiency over time at high temperatures and high current densities was observed. The polarization study carried out in potentiostatic, potentiodynamic and galvanostatic modes in 0.5 M Na₂SO₄ solution at pH 3 showed that the destruction of hydrogen peroxide at the cathode of the electrochemical reactor, as well as its chemical decomposition in the bulk solution, takes place at a significantly lower rate than the oxidation of H₂O₂ at the Ti–IrO₂ anode. Preparative electrolysis in the membrane reactor showed much higher current efficiencies for H₂O₂ electro-generation in comparison with tests carried out in an undivided cell. The performance of different proton-exchange membrane in this process was studied and a membrane cell with a heterogeneous MK-40 type PEM was found to be suitable. An optimized cell design, the appropriate selection of electrodes, supporting electrolytes, and a membrane resulted in a lower voltage in the membrane cell in comparison with the undivided cell.     

Electrocatalysis of oxygen evolution/reductionon LaNiO3 prepared by a novel malic acid-aided method

A kinetic study of the electroformation and electroreduction of oxygen in KOH solutions has been carried out on a LaNiO3 electrode obtained through a malic acid precursor route. The new electrocatalyst was found to show greatly enhanced activity for both oxygen evolution and reduction. The apparent electrocatalytic activity of this electrode for oxygen reduction was more than 10 times higher than those reported for similar electrodes obtained by other methods. It was, however, observed to be less active electrocatalytically for oxygen evolution as compared to the active LaNiO3 electrode obtained by the Bockris–Otagawa coprecipitation method. The electrochemical reaction order with respect to OH– concentration was found to be approximately 1 in the case of oxygen evolution while that for oxygen reduction, was approximately –1. The Tafel slope values for the reactions were 2.3RT/F and 2×2.3RT/3F, respectively.     

Effect of silver catalyst on the activity and mechanism of a gas diffusion type oxygen cathode for chlor-alkali electrolysis

Application of a gas-diffusion type oxygen cathode will contribute to energy saving in chlor-alkali electrolysis. For this purpose the development of gas-diffusion electrodes with high performance and durability is essential. We have investigated the performance for oxygen reduction and the mechanism of its on gas-diffusion electrodes with and without Ag catalyst in order to develop such oxygen cathodes with high performance and durability. It has been found that an electrode with no catalyst, that is, carbon support only in the reaction layer, shows electrochemical activity for oxygen reduction in 32 wt % NaOH at 80 °C and 1 atm O₂, but loading of 2 mg cm^–2 Ag of particle size 300 nm, not only improves the activity by about 100 mV but promotes the four-electron reduction to produce OH^–, while H₂O₂ is the predominant reaction intermediate in the absence of the Ag catalyst. The production of H₂O₂ has been demonstrated by conducting CV measurements to detect H₂O₂ in the anodic scan after a cathodic sweep up to 0.3 V vs RHE. It has been shown that the gas-diffusion type oxygen cathode with Ag catalyst has the high performance and durability necessary for chlor-alkali electrolysis.     

过氧化氢合成的研究进展

过氧化氢（H2O2）是一种重要的化工产品,且需求量不断增加。综述了近几年来过氧化氢的研究进展,系统地介绍了燃料电池法,O2、CO、H2O催化合成法、贵金属直接催化合成法和H2／O2介质阻挡放电等离子体法等合成过氧化氢的方法。提出了当前需要解决的问题并对今后的研究工作进行了展望。     

Electrochemical reduction of 2-ethyl-9,10-anthraquinone (EAQ) and mediated formation of hydrogen peroxide in a two-phase medium Part II: Production of alkaline hydrogen peroxide by the intermediate electroreduction of EAQ in a flow-by porous electrode in two-phase liquid–liquid flow

Hydrogen peroxide production by the intermediate electroreduction of the 2-ethyl–9,10-anthraquinone (EAQ) was carried out in a flow-by cell and a two-phase electrolyte formed by a mixture of tributylphosphate (TBP) and diethylbenzene (DEB) as the organic phase, and a solution of NaOH as the aqueous phase. The cathode used was a reticulated vitreous carbon (RVC) foam. We have examined the following process variables: electrolysis current (0.3–3.1A), catholyte flow rate (470–1630mlmin–1), EAQ concentration in the organic phase (0.21–0.42m), organic/aqueous phase volume ratio (1/9–4/6) and grade of porosity of the RVC (20–45ppi). The electrolyses can be carried out in the presence or absence of oxygen gas. The first method is the so-called one-step electrolysis and the second method is the two-step electrolysis. In the second method, the disodium salt of the hydroquinone (EAQNa2) is electrochemically formed in the absence of oxygen. The second step consists of the chemical reaction of this salt with oxygen to form hydrogen peroxide. We obtained a hydrogen peroxide concentration of 0.8m after 10Ah with an electrolysis current of 1.55A and a current efficiency of 70%.     

The “In-cell” and “Ex-cell” Fenton treatment of phenol, 4-chlorophenol and aniline

A comparative study of phenol, 4-chlorophenol and aniline degradation with the electro-generation of H₂O₂ at gas-diffusion electrodes was carried out under three different conditions: electro-Fenton^® treatment in an undivided cell; electro-Fenton treatment in the catholyte of a membrane cell divided by a proton-exchange membrane (in-cell electro-Fenton membrane process); and a treatment of polluted solution in the cathode space of a membrane cell with the generation of H₂O₂, followed by the addition of Fe(II) salt in the other reactor (ex-cell electro-Fenton process).An optimized cell design with no gap between the membrane and the anode, along with the appropriate choice of supporting electrolytes, ensured a voltage reduction with a membrane cell in comparison with that of an undivided cell. The accumulation of hydrogen peroxide in concentrations sufficient for the almost complete destruction (90–98%) of aromatic organic pollutants was achieved in all cases but the ex-cell process with the preparative electrolysis in the pilot scale membrane reactor separated by the proton-exchange membrane MK-40 showed higher treatment efficiency and lower specific energy consumption in comparison with known technologies. Damage of the gas-diffusion layer was observed in some tests which could be caused by alkaline conditions in the pores of the gas-diffusion cathode (GDE). The pH indicator paper showed a color specific for alkaline media in contact with the GDE treated in the solution with pH 3 in the bulk. A possible explanation could be that even in acid media, hydrogen peroxide generation in pores of the gas diffusion layer proceeds with formation of HO ₂ ^? which is common for alkaline media and consecutive protonation occurs at the interface with the acid solution.     

离子选择电极法测定过氧化氢中的硝酸盐含量

开发了用离子选择电极法测定过氧化氢中硝酸盐含量的实验方法。从试样分解条件、pH值与回收率关系试验、定量方法等进行了探讨。精密度试验表明5次测定结果标准偏差为4.61%;回收率在96~100%。跟比色法结果对照,两者数据相近。本方法操作简便、快捷。     

模板法制备介孔SiO2及其孔径调节研究进展

介孔材料具有独特的孔道结构、较大的比表面积、孔径可调、维度有序等特点,在光化学、生物模拟、催化、分离、功能材料等方面具有广阔的应用前景。基于此,本文对模板法制备介孔材料的最新研究进展、影响介孔材料孔径调节与形貌变化的主要因素,如模板剂的种类、有机助剂与反应条件等进行了归纳总结,并对其今后的发展趋势进行了展望。     

模板法制备介孔SiO2及其孔径调节研究进展

介孔材料具有独特的孔道结构、较大的比表面积、孔径可调、维度有序等特点,在光化学、生物模拟、催化、分离、功能材料等方面具有广阔的应用前景。基于此,本文对模板法制备介孔材料的最新研究进展、影响介孔材料孔径调节与形貌变化的主要因素,如模板剂的种类、有机助剂与反应条件等进行了归纳总结,并对其今后的发展趋势进行了展望。     

惰性气体对氢氧等离子体直接合成过氧化氢的影响

在H₂/O₂体系中添加惰性气体(Ar、He、N₂)进行常压介质阻挡放电,合成了H₂O₂水溶液。系统研究了不同惰性气体对体系击穿电压及H₂O₂合成能效的影响。结果表明,添加气体对击穿电压、O₂转化率、H₂O₂选择性、H₂O₂收率及能量效率能产生较大影响。其中Ar的引入不仅降低了击穿电压,还提高了合成H₂O₂的能量效率;当Ar添加量为56.6 ml·min^-1时,击穿电压由11.8 kV降为10.2 kV;合成H₂O₂的能量效率提高51%,由3.45 g·(kW·h)^-1提高至5.20 g·(kW·h)^-1(以100%H₂O₂计)。发射光谱表征发现,在H₂-O₂-Ar放电体系中存在以亚稳态为末态的辐射Ar(696.5、794.8、811.5 nm),表明亚稳态Ar物种的潘宁电离作用可能是降低击穿电压的主要因素。由示波器测量的放电电流波形图可知,Ar的加入增大了体系电子密度,使得相同功率下O₂转化速率大幅提高,从而使合成H₂O₂能量效率显著提高。     

RRDE study of oxygen reduction on Pt nanoparticles inside Nafion®: H2O2 production in PEMFC cathode conditions

Dihydrogen peroxide production on platinum particles supported on carbon inside a proton exchange membrane (Nafion^®), that is, under the working conditions of PEMFC cathodes, is rather small at the usual oxygen reduction potentials. As on bulk platinum, a four-electron mechanism appears to be the main pathway, with particle size and carbon substrate effects on the H₂O₂ production. A large increase in the H₂O₂ contribution takes place at low potentials, that is, at the working potentials of PEMFC anodes.     

Electrosynthesis of hydrogen peroxide by partial reduction of oxygen in alkaline media. Part II: Wall-jet ring disc electrode for electroreduction of dissolved oxygen on graphite and glassy carbon

A wall-jet ring disc electrode was constructed by adapting a wall-jet flow through electrochemical cell. Commercially available spectral graphite and glassy carbon were used as working disc electrodes and the ring electrode was made of stainless steel. The efficiency and rate constants, measured in a planar parallel flow hydrodynamic regime, indicated the partial electroreduction of dissolved oxygen as a quasi-reversible two-electron process for both electrode materials tested.     

氢氧直接合成法制过氧化氢技术进展

氢气和氧气直接合成过氧化氢是典型的原子经济性反应，因过程简单、产品清洁、生产成本低而成为催化领域研究开发的一个热点。总结了该法近年来在催化剂活性组分的选取及载体方面的进展；详细介绍了溶剂的选取和反应机理；讨论了各种反应器的安全性。指出今后的研究重点是提高氢气利用率、开发新型的反应器、提高过程的安全性。     

H2 and H2/CO oxidation mechanism on Pt/C, Ru/C and Pt–Ru/C electrocatalysts

The oxidation kinetics of H₂ and H₂ + 100 ppm CO were investigated on Pt, Ru and Pt–Ru electrocatalysts supported on a high-surface area carbon powder. The atomic ratios of Pt to Ru were 3, 1 and 0.33. XRD, TEM, EDS and XPS were used to characterize the electrocatalysts. When alloyed with ruthenium, a decrease in mean particle size and a modification of the platinum electronic structure were identified. Impedance measurements in H₂SO₄, at open circuit potential, indicated different mechanisms for hydrogen oxidation on Pt/C (Tafel–Volmer path) and Pt–Ru/C (Heyrowsky–Volmer path). These mechanisms also occur in the presence of CO. Best performances, both in H₂ and H₂ + CO, were achieved by the catalyst with the ratio Pt/Ru = 1. This is due to a compromise between the number of free sites and the presence of adsorbed water on the catalyst. For CO tolerance, an intrinsic mechanism not involving CO electroxidation was proposed. This mechanism derives from changes in the electronic structure of platinum when alloyed with ruthenium.     

Catalytic epoxidation with electrochemically in situ generated hydrogen peroxide

The epoxidation of allyl alcohol with in situ generated hydrogen peroxide was performed in an electrochemical cell with a trickle-bed electrode, composed of carbon black, graphite, PTFE and titanium silicalite-1 (TS-1) as heterogeneous epoxidation catalyst. Mass transport in interaction with the catalytic activity limits the epoxidation rate. The conversion of allyl alcohol increases with increase in the content of epoxidation catalyst in the electrode. In contrast, the specific reaction rate decreases due to the reduced accessibility of active sites in the catalyst.     

石墨烯负载纳米银的制备及其对H2O2的电化学检测

采用改进的Hummers法制备了氧化石墨烯（GO）,然后以水合肼作为还原剂,并控制反应的pH=10来制备还原氧化石墨烯（RGO）。采用化学还原法,以石墨烯为载体,以乙酰丙酮银为前体,以硼氢化锂四氢呋喃溶液为还原剂将银离子还原,制备了石墨烯负载纳米银复合材料。通过X 射线粉末衍射（XRD）、傅里叶变换红外光谱（FTIR）和透射电子显微镜（TEM）等表征方法证明了石墨烯上负载的银纳米颗粒结晶良好、尺寸均一、分布均匀,其中银纳米颗粒直径约为8nm。通过循环伏安和计时电流技术对石墨烯负载纳米银复合材料进行电化学测试,结果表明,石墨烯负载纳米银复合材料对过氧化氢的还原具有良好的电催化活性。以此复合纳米结构构建的过氧化氢传感器测试过氧化氢浓度的线性范围为0.1～62.3mmol/L（R=0.990）,检出限为0.017mmol/L（S/N=3）,响应时间小于2s。     

Macrokinetic analysis of polarisation characteristics of gas-diffusion electrodes in contact with liquid electrolytes, Part II: Oxygen reduction as example for a higher order reaction

Classical partial oxidation processes often suffer from low selectivities. Promising alternatives are electrochemical processes where the oxidation takes place at a packed-bed anode while an oxygen-consuming gas–liquid membrane is used as cathode. As a basis for the reliable design of such a process, the performance of oxygen-consuming gas-diffusion electrodes (GDE) is investigated experimentally and is analysed based on a rigorous model accounting for the reaction microkinetics and all relevant mass and charge transport phenomena. The results indicate that oxygen is transported in the gas-filled pores by Knudsen diffusion and that the cathodic oxygen reduction follows a parallel reaction scheme forming hydrogen peroxide at the carbon black support and water at the applied platinum catalyst particles.     

硫酸锌生产除铁工艺及其比较

研究了硫酸锌生产中用氧气或空气氧化法配合过氧化氢深度氧化除铁,其适宜的工艺条件为：氧气或空气氧化,pH值4－5,反应温度85－95℃,氧化时间2－3h,过氧化氢氧化,pH值3－4,反应温度80－85℃,氧化时间3－4h,过氧化氢的量控制为2－3g/L ,溶液中铁含量可控制在0．01g/L以下,同时与其他除铁工艺进行了比较,得出本艺具有操作条件容易控制,除铁效果较好等优点。