Regarding the treatment of (waste)water, electrochemical processes have various advantages over other methods. They are robust, easy to operate and flexible in case of fluctuating wastewater streams. In addition, a relatively broad spectrum of organic and inorganic impurities can be removed. This contribution provides an overview of electrochemical reactors for water, process water, and wastewater treatment, which are already in technical‐scale operation or subject of research. Some essential basics of electrochemical processes for the treatment of water are presented and examples for applications are given. This is followed by a description of the reactors.

Electrochemical advanced oxidation processes (EAOP^®) are promising technologies for the decentralized treatment of water and will be important elements in achieving a circular economy. To overcome the drawback of the high operational expenses of EAOP^® systems, two novel reactors based on a next-generation boron-doped diamond (BDD) anode and a stainless steel cathode or a hydrogen-peroxide-generating gas diffusion electrode (GDE) are presented. This reactor design ensures the long-term stability of BDD anodes. The application potential of the novel reactors is evaluated with artificial wastewater containing phenol (COD of 2000 mg L⁻¹); the reactors are compared to each other and to ozone and peroxone systems. The investigations show that the BDD anode can be optimized for a service life of up to 18 years, reducing the costs for EAOP^® significantly. The process comparison shows a degradation efficiency for the BDD–GDE system of up to 135% in comparison to the BDD–stainless steel electrode combination, showing only 75%, 14%, and 8% of the energy consumption of the BDD–stainless steel, ozonation, and peroxonation systems, respectively. Treatment efficiencies of nearly 100% are achieved with both novel electrolysis reactors. Due to the current density adaptation and the GDE integration, which result in energy savings as well as the improvements that significantly extend the lifetime of the BDD electrode, less resources and raw materials are consumed for the power generation and electrode manufacturing processes.

Microbial fuel cells are a promising technology for future wastewater treatment, as it allows cleaning and power generation simultaneously. The bottleneck of microbial fuel cells is often its cathodes because they determine the power output. Gas diffusion electrodes might overcome this bottleneck due to their low production costs and high oxygen reduction rates. However, biofilm formation on the gas diffusion electrodes reduces their performance over time. In this work, a new reactor design of the microbial fuel cell using rotating gas diffusion electrodes is presented. The biofilm growth on the electrode during operation was observed and its effect on the performance of the microbial fuel cell was examined. In addition, different antifouling strategies were investigated over a period of 80 days. It was found that already after 7 days of operation a complete biofilm had grown on an untreated gas diffusion electrode. However, this does not seem to affect the performance of the cells in the beginning. Differences in the performance of the reactors with and without an antifouling strategy only become apparent from day 15 onwards. The use of UV radiation and antibacterial membranes leads to the best results with maximum power densities of approx. 200 mW m⁻² while the untreated microbial fuel cell only achieves a maximum power density of approx. 20 mW m⁻².

This contribution describes the effect of the quality of the catalyst coating of cathodes for wastewater treatment by microbial fuel cells (MFC). The increase in coating quality led to a strong increase in MFC performance in terms of peak power density and long-term stability. This more uniform coating was realized by an airbrush coating method for applying a self-developed polymeric solution containing different catalysts (MnO₂, MoS₂, Co₃O₄). In addition to the possible automation of the presented coating, this method did not require a calcination step. A cathode coated with catalysts, for instance, MnO₂/MoS₂ (weight ratio 2:1), by airbrush method reached a peak and long-term power density of 320 and 200–240 mW/m², respectively, in a two-chamber MFC. The long-term performance was approximately three times higher than a cathode with the same catalyst system but coated with the former paintbrush method on a smaller cathode surface area. This extraordinary increase in MFC performance confirmed the high impact of catalyst coating quality, which could be stronger than variations in catalyst concentration and composition, as well as in cathode surface area.

A system of boron-doped diamond (BDD) anode combined with a gas diffusion electrode (GDE) as a cathode is an attractive kind of electrolysis system to treat wastewater to remove organic pollutants. Depending on the operating parameters and water matrix, the kinetics of the electrochemical reaction must be defined to calculate the reaction rate constant, which enables designing the treatment reactor in a continuous process. In this work, synthetic wastewater simulating the vacuum toilet sewage on trains was treated via a BDD-GDE reactor, where the kinetics was presented as the abatement of chemical oxygen demand (COD) over time. By investigating three different initial COD concentrations (C_0,1 ≈ 2 × C_0,2 ≈ 4 × C_0,3), the kinetics was presented and the observed reaction rate constant k_obs. was derived at different current densities (20, 50, 100 mA/cm²). Accordingly, a mathematical model has derived k_obs. as a function of the cell potential $E_{cell}$. Ranging from 1 × 10⁻⁵ to 7.4 × 10⁻⁵ s⁻¹, the k_obs. is readily calculated when $E_{cell}$ varies in a range of 2.5–21 V. Furthermore, it was experimentally stated that the highest economic removal of COD was achieved at 20 mA/cm² demanding the lowest specific charge (~7 Ah/g_COD) and acquiring the highest current efficiency (up to ~48%).

The use of gas diffusion electrodes (GDEs) in microbial fuel cells (MFCs) can improve their cell performance, but tends to cause fouling. In order to allow long-term stable operation, the search for antifouling methods is necessary. Therefore, an antibacterial coating with ammonium compounds is investigated. Within the first 30 days of operation, the maximum measured power density of a GDE with antibacterial ionomer was 606 mW m⁻². The GDE without an antifouling treatment could only reach a maximum of 284 mW m⁻². Furthermore, there was an optimum in the loading amount with ionomer below 2.6 mg cm⁻². Further investigations showed that additional aeration of the GDEs by a fan had a negative effect on their performance. Despite the higher performance, the antibacterial coating could not prevent biofilm growth at the surface of the GDE. The thickness of the biofilm was only reduced by 14–16%. However, the weight of the biofilm on the treated GDEs was 62–80% less than on a GDE without an antifouling treatment. Consequently, the coating cannot completely prevent fouling, but possibly leads to a lower density of the biofilm or prevents clogging of the pores inside the electrodes and improves their long-term stability.