The main goal of the project is to develop, construct, and validate an Intelligent Electrochemical Reactor-based System – i-CLARE – for the removal of harmful contaminants dissolved in water, such as pesticides, antibiotics, dioxins, and plant protection agents, among others.

Sabina Żołędowska, Institute of Biotechnology and Molecular Medicine
Introduction and Invitation Made on land, ends up in the water

Sabina Żołędowska

The primary goal of this project concerns the design and fabrication of the electrochemical water treatment system, with implemented artificial intelligence procedures dedicated to identify and learn the most efficient operating parameters in order to dispose of a given mixture of contaminants. This high-performance electrochemical reactor will be build based on a novel type of electrode material. The proposed approach utilizes the application of reticulated vitreous carbon foams (RVC), with deposited modified metal oxides (MMO) and diamond thin films. The following setup is characterized by high surface area development and satisfactory mechanical and electrochemical properties, designed for high electrocatalytic process efficiency

To accomplish significant and ambitious objectives, a collaboration was initiated in 2020 among four research and development centers: the Institute of Biotechnology and Molecular Medicine, Gdansk University of Technology, SensDx JSC, and the Norwegian Institute for Air Research. he project’s primary focus revolves around a few main topics: Reactor design and construction, selection of a specific type of reticulated vitreous carbon foams (RVC), analytical studies  of harmful contaminants parameters and AI implementation. 

Prof. Tadeusz Ossowski, Institute of Biotechnology and Molecular Medicine
ICLARE project design and effects

Tadeusz Ossowski

The i-Clare reactor is a novel electrochemical reactor designed for the efficient treatment of organic compounds in electrolytes. This paper outlines the comprehensive design and construction process of the i-Clare reactor, encompassing several key aspects. Firstly, the determination of current and voltage parameters was conducted through experiments using an electrolyser with varying electrolyte volumes ranging from 1 to 5 litres, while considering the presence of degraded organic compounds. Furthermore, the selection of suitable corrosion-resistant metallic cathode materials was investigated to ensure optimal performance within the designed reactor. Various materials such as titanium and stainless steel were tested, and cathodes were shaped as perforated sheets or Ledochowski mesh structures. To enable intelligent control and monitoring of the reactor, advanced software utilizing artificial intelligence and machine learning techniques was designed and implemented. This software enhances the overall efficiency and responsiveness of the i-Clare reactor. Hydrodynamic conditions and current efficiency were analyzed based on laboratory single-pass reactors, and the influence of flow on the electro-oxidation process and mechanical properties of the RVC (Retained Volumetric Capacity) electrodes were studied. The current-voltage parameters for the electrolyser were calculated through laboratory studies conducted in electrolyte volumes ranging from 1 to 5 litres. The adjustment of current demand and voltage range was performed experimentally, considering the active surface of modified RVC electrodes, which presented challenges in estimating their actual working surfaces due to their porous nature. The selection and verification of cathode materials and the determination of electroactive surfaces were crucial elements in optimizing the operation parameters of the electrochemical reactor. The findings from this study contribute to advancing the understanding and development of efficient electrochemical reactors for the treatment of organic compounds.

Robert Bogdanowicz / Michał Sobaszek, Gdańsk University of Technology
Electrode materials for electrooxidation ICLARE reactors

Robert Bogdanowicz

This abstract focuses on the deposition of boron-doped diamond (BDD) and metal mixed oxides (MMO) onto porous carbon electrodes/foams. The study aims to explore the synthesis process and investigate the electrochemical properties of these composite materials for various applications. The deposition process involves the incorporation of boron atoms into the diamond lattice, enhancing its electrical conductivity and chemical reactivity. Additionally, metal mixed oxides are introduced to further improve the electrode performance by providing catalytic activity and stability. The porous carbon electrodes/foams serve as a robust and highly conductive substrate for the deposition.  Several variables are examined during the synthesis process, including the concentration of boron dopant, types of metal oxides, deposition techniques, and annealing conditions. These variables are optimized to achieve the desired properties, such as enhanced electrocatalytic activity, high surface area, and good stability. The resulting BDD and MMO composite electrodes/foams demonstrate promising electrochemical performance for various applications, including wastewater treatment. The unique combination of boron-doped diamond and metal mixed oxides offers synergistic effects, leading to improved catalytic activity, selectivity, and durability. Overall, the deposition of boron-doped diamond and metal mixed oxides onto porous carbon electrodes/foams presents a versatile and effective approach to develop advanced electrochemical materials with excellent performance characteristics for diverse applications in the field of energy conversion and environmental remediation.

Mattia Pierpaoli / Paweł Jakóbczyk/ Paweł Ślepski, Gdańsk University of Technology/ Institute of Biotechnology and Molecular Medicine
Monitoring system of ICLARE system

Paweł Jakóbczyk

In the laboratory settings, the development of electrolyzer cell designs and the monitoring of electrolysis efficiency are carried out in parallel. This research aims to not only focus on the primary task of electro-oxidation and electroanalysis of decomposition products but also validate sensory systems and flow-through systems. Additive manufacturing technology, specifically 3D printing, proves to be advantageous in fabricating electrolyzer cells due to its ease in modifying dimensions, adjusting hydrodynamic flow distribution, and facilitating the setup of secondary cells for monitoring physicochemical parameters in a flow-through or bypass mode. Additionally, 3D printing enables a modular design approach by stacking multiple independent electrolyzer cells.

The selection of the monitoring cell design is driven by the need to (1) minimize sampling volume, (2) minimize interference between different sensors, (3) reduce sensor stabilization time to achieve stable and reliable readings, and (4) optimize fluid dynamics to avoid dead volumes and bypasses that may impact the replacement of sampled liquid aliquots. The monitoring cell incorporates sensors for measuring redox potential, O2 electrochemical levels, pH, electrical conductivity, and turbidity. It is connected in series with an optical cell that captures visible spectra (300 – 1100 nm) at each sampling interval (5 minutes) using a deuterium lamp as the light source. Computational Fluid Dynamics (CFD) optimization is employed to analyze the variation of physicochemical parameters over time when a potential difference is applied between the anode and cathode.

This study presents a comprehensive approach to electrolyzer cell design and monitoring, leveraging 3D printing technology and sensor integration. The optimized monitoring cell design, supported by CFD analysis, ensures accurate and efficient measurement of physicochemical parameters during electrolysis processes.

Keywords: electrolyzer cell, monitoring, additive manufacturing, 3D printing, physicochemical parameters, sensors, flow-through systems, computational fluid dynamics

Jacek Ryl, Gdańsk University of Technology
Carbon-based ceramic foams for water remediation: properties vs process efficacy and electrode stabilit

Jacek Ryl

A new type of electrode material was proposed using a carbon-ceramic foam filter modified with photoactive fillers, dedicated for photoelectrochemical wastewater treatment processes. This modification has resulted in an efficient, environmentally friendly, and cost-effective solution. The manufacturing of carbon-ceramic foam filters involves mixing α-Al2O3 ceramic powder with crushed sintering coal, crushed organic coal binder, aqueous silicic acid sol, and sodium lignosulfonate. Additionally, 5% wt. of potassium hexavanadate (KVO) and titanium oxide were added to induce electro-oxidation efficacy. The resulting mass was coated with polymer foams and baked at high temperatures in an oxygen-free atmosphere. 

The developed carbon-ceramic foam filters modified with TiO2 and KVO were tested as anode materials for electrolysis supported by photodegradation in a Xe arc lamp to simulate sunlight. The oxidation of caffeine was promoted by hydroxyl radicals generated via the oxidation of water on the anode surface. The caffeine’s degradation efficiency was analyzed via UV-Vis spectroscopy and differential pulse voltammetry. The repeatability, durability, and ability of modified carbon-ceramic foams were also evaluated. With their remarkable mechanical and chemical stability, these composites are an excellent option for electrochemical applications. Their highly developed surface makes them particularly well-suited as anode materials for wastewater treatment. The application of carbon-ceramic foam filters modified with photoactive fillers showcases a promising and valuable alternative to the use of electrode materials in photoelectrochemical processes

Paweł Rostkowski, NILU, Norway
Challanges in enviromental analytics

Paweł Rostkowski

High-resolution mass spectrometry (HRMS), coupled with liquid or gas chromatography (LC or GC), has revolutionized environmental analyses through suspect and non-targeted screening (NTS) approaches. NTS is a discovery-based method for detecting organic chemicals without prior knowledge of the sample’s composition. In suspect screening, molecular features are compared against databases of chemical suspects to identify potential matches. True NTS involves exploring and postulating unknown compounds.

This approach has been successfully applied in various fields. For example, in environmental monitoring, suspect screening helps identify known contaminants, while true NTS reveals emerging pollutants. In food safety, suspect screening detects known contaminants like pesticides, while true NTS uncovers new and unexpected compounds. Pharmaceutical analysis benefits from suspect screening for known drugs and true NTS for identifying metabolites and degradation products.

In the i-Clare project, a combination of targeted analyses, suspect screening, and true NTS was used to assess the removal efficiency of i-Clare compounds in electrolysis samples. HRMS facilitated accurate identification and characterization of compounds, while chromatographic techniques enabled comprehensive analysis.

Zofia Cebula, Institute of Biotechnology and Molecular Medicine
iClare system as an answer for selected environmental pollutants

The chemical industry has a very high position among the industrial sectors of the Polish economy. The share of the chemical industry in the total industry is 17%. The last decade shows that the chemical sector is one of the fastest-growing areas in the Polish economy. Currently in the world and in Poland, a growing emphasis on environmental protection by increasing awareness in society, developing and implementing new technologies and legal regulations. The Council Directive of the European Union 91/271/EEC regulates the issues of municipal sewage treatment (UWWT) in Europe and is one of the most important driving forces on the market of sewage treatment devices. To select a representative group of compounds for iCare project the team focused on organic compounds. The selection criteria were: 
– the possibility of oxidation and reduction of the selected compound
– ease of analysis and detection by electrochemical and chromatographic methods
– representativeness from different groups of pollutants.

Six model substances were selected: paracetamol, diclofenac, bisphenol A (BPA) , N-phenyl-N’-(1,3-dimethylbutyl)-p-phenylenediamine(6-PPD), triclosan and caffeine. 

To estimate the biosafety and effectiveness of RVC electrodes we planned to perform a bioassay with an array of microbial strains to assess the toxicity of the standard buffer solutions and later on with the use of test substances (samples), before and after the treatment with the i-CLARE system. The toxicity of iCLARE chemicals and products of electrolysis are evaluated before and after the treatment using MARA tests in which sample toxicity is assessed on the basis of the inhibition degree of test organisms’ growth after incubation.

Michał Kruczkowski, Proximo
Algorithms for water treatment and monitoring: Supervised learning and data mining methods supporting electrochemical water treatment

Michał Kruczkowski

Circulation economy of water is one of the most urgent environmental challenges of our society. There are numerous silent killers dissolved in water, including drugs and antibiotics, hormones, dioxides and others. The efficient remediation system for the removal of these harmful contaminants may be successfully carried out by means of electrocatalytic processes, which serve as an eco-friendly procedure in comparison to other treatments. To solve this problem, the approach applying machine learning based on regression models was proposed. Unfortunately, measured datasets were very heterogeneous in the case of building machine learning models due to the facts of asynchronous measurements, many missing values, different pollutants, etc. The ultimate goal of the research was precise prediction of the concentration of selected pollutants in the water. The solution includes data pre-treatment leading to obtaining feature vectors creating datasets for machine learning. The selection of the algorithm best suited for the task, data preprocessing and regression approach are described. The results of cross-validation show scores over 90% for validations datasets proving a high accuracy of the model predictions which is a very good prognosis for future research.

Iwona Kaczmarzyk, Gdańsk University of Technology
Environmentally-friendly oxygen-activated carbon felt anodes to remediation of acetaminophen

Iwona Kaczmarzyk

Carbon felts are interesting carbonaceous material, with highly developed surface areas, and they are highly conductive materials that fit the requirements for both anodes and cathodes in advanced electrocatalytic processes. We present eco-friendly advanced oxidative modification processes (thermal, chemical, and plasma-chemical), which were applied to carbon felt anodes to enhance their efficiency towards electro-oxidation. Presented modifications of the porous anodes results in increased kinetics of acetaminophen degradation in aqueous environments. Moreover, oxygen-activated carbon felts could be adapted to also degradation hazardous pollutant groups such as anti-inflammatory pharmaceuticals.
A pristine carbon felt electrode was capable of decomposing up to 70% of the acetaminophen in a 240 min electrolysis process, while the oxygen-plasma treated electrode achieved a removal yield of 99.9% estimated utilizing HPLC-UV-Vis. The enhancement of the electrochemical oxidation rates towards acetaminophen was attributed to the appearance of surface carbonyl species. Our results indicate that the best-performing plasma-chemical treated CFE follows a heterogeneous mechanism with only approx. 40% removal due to direct electro-oxidation.  The utilized oxidation techniques deliver single-step, eco-friendly, and stable physiochemical reformation of carbon felt surfaces and achieved satisfactory acetaminophen degradation level.

Sabina Żołędowska, Tadeusz Ossowski, Institute of Biotechnology and Molecular Medicine
Outlook and perspectives

The i-CLARE project is focused on the design, examination, and fabrication of a new-generation system for electrochemical water treatment with the application of artificial intelligence. The cooperation between Polish and Norwegian partners runs smoothly and is a source of insightful work management in those two countries. The consortium validated electrode modification methods that are the base of the iCLARE product and established the procedures for the detection of chemicals detection (GUT): – deposition of metal oxides WO3 and V2O5-  deposition of boron-doped diamond/nanowalls structures by CVD process.  The chosen electrodes (porous Ferroterm electrodes) were stress tested for various parameters that might occur inside the iCLARE machine–corosis, the long-term structure of the electrode surface during electrochemical processes, and energetic efficacy using cyclic polarization and electrochemical impedance spectroscopy (before and after electrolysis) and dynamic electrochemical impedance spectroscopy (DEIS). This tool allows real-time monitoring of the changes at the electrode/electrolyte interphase. The final size and reactor form parameters are ongoing during the series of technical repetitions.On the other hand, the toxicity of iCLARE chemicals and products of electrolysis are evaluated before and after the treatment using MARA examination (IBMM) and HPLC-MS-MS (NILU) giving us information about the harmfulness of using electrode material and the efficiency of iClare system in the disposal of pollutants. Implementation of data into the system that uses artificial intelligence and the possibility of practical application is in progress (SensDx).