复合电化学系统的制氢:阴极过程

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摘要

目前,氢具有产热高、燃烧温度高的特点,是一种很有前途的燃料。氢气燃烧过程中不产生温室气体,具有环境安全的特点。制氢的方法有很多种:包括电解水和碳氢化合物转化的传统方法,以及热化学方法。从天然气和焦炭中获得氢的廉价方法伴随着碳氧化物的形成,热化学方法需要高温(高达1000°C)。电解碱金属氢氧化物水溶液制氢的方法是最耗能的。然而,它被认为是欧盟最有前途的国家之一。为了减少氢气生产的能源消耗,作者建议将通常产生氧气的正极替换为平衡电位低于氧气的溶解阳极,例如铁电极。在这种情况下,采用这种组合电化学方法,系统中的分解电压为0.44 V,而传统的水电解为1.23 V。铁在氯化物介质中溶解的过电压为几十毫伏。然而,阳极和阴极之间的电位差ΔU变得小于平衡电位差ΔE0 = 0.44 V。本研究旨在证实电解质的组成和浓度的选择:阴极电解质,以确保减少氢释放的能量消耗;阳极液——防止铁阳极钝化,因为钝化会导致氧气释放。本工作研究了在1 M (= mol/L) NaCl溶液中加入1 M(5、10、15、20 mL)盐酸溶液中氢气释放的阴极过程。电解过程中以铂为阴极。阳极材料是铁,St3级。研究发现,在电解质组成由中性(1 M NaCl)到酸性(1 M HCl)的变化范围内,观察到水的排出机制发生了变化。在中性介质中,放电根据海洛夫斯基机制发生,在酸性介质中,放电根据沃尔默机制发生。阳极液组成和浓度的选择是复杂的,因为需要提供含有氯离子的酸性介质来防止阳极钝化。为了成功地提取铁阳极的溶解产物,溶液的酸度必须至少为3。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Hydrogen production in a combined electrochemical system: Cathode process
Today, hydrogen is recognized as a promising fuel, which is characterized by high heat generation and combustion temperature. It is also characterized by environmental safety due to the fact that no greenhouse gases are formed during the combustion of hydrogen. There are various methods of hydrogen production: traditional methods, which include electrolysis of water and conversion of hydrocarbons, and thermochemical ones. A cheap method of hydrogen obtaining from natural gas and coke is accompanied by the carbon oxides formationю Thermochemical methods are require high temperatures (up to 1000°C). The method for hydrogen production by electrolysis of aqueous solutions of alkali metal hydroxides is the most energy-intensive. However, it is considered one of the most promising in the European Union. To reduce energy consumption for hydrogen production, the authors suggest replacingthe positive electrode, which normally produces oxygen, with a dissolving anode with an equilibrium potential lower than that of oxygen, such as an iron electrode. In this case, with such a combined electrochemical method, the decomposition voltage in the system will be 0.44 V against 1.23 V with traditional water electrolysis. The overvoltage of iron dissolution in a chloride medium is several tens of millivolts. However, the potential difference between the anode and cathode ΔU becomes smaller than the equilibrium potential difference ΔE0 = 0.44 V. This research aims to substantiate the choice of the composition and concentration of electrolytes: catholyte –to ensure conditions for reducing energy consumption for hydrogen release; anolyte – to prevent passivation of the iron anode, which can lead to the oxygen release. This work results in research of the cathodic process of hydrogen release in the following solutions: 1 M (= mol/L) NaCl with the addition of 1 M hydrochloric acid in the amount of 5, 10, 15, 20 mL. Platinum is used as a cathode for the electrolysis process. The anode material is an iron, St3 grade. It has been found that in the range of changes in the composition of the electrolyte from neutral (1 M NaCl) to acidic (1 M HCl), a change in the mechanism of water discharge is observed. In a neutral medium, the discharging occurs according to the Heyrovsky mechanism, and in an acidic medium - according to the Volmer mechanism. The choice of the anolyte composition and concentration is complicated by the need to provide an acidic medium containing chlorine ions to prevent passivation of the anode. The acidity of the solution must be at least 3 for the successful extraction of dissolution products of the iron anode.
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