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Keywords = zero-gap electrochemical cell

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23 pages, 7325 KB  
Article
3D Multilayered DDM-Modified Nickel Foam Electrode for Advanced Alkaline Water Electrolysis
by Elitsa Petkucheva, Galin Borisov, Jordan Iliev, Elefteria Lefterova and Evelina Slavcheva
Molecules 2026, 31(1), 69; https://doi.org/10.3390/molecules31010069 - 24 Dec 2025
Viewed by 467
Abstract
Advanced alkaline water electrolysis (AWE) in “zero-gap” configuration is a promising approach for low-temperature hydrogen production, but its efficiency strongly depends on the design and surface chemistry of nickel-based electrodes. Here, we present a simple dip-and-drying method (DDM) to modify commercial nickel foam [...] Read more.
Advanced alkaline water electrolysis (AWE) in “zero-gap” configuration is a promising approach for low-temperature hydrogen production, but its efficiency strongly depends on the design and surface chemistry of nickel-based electrodes. Here, we present a simple dip-and-drying method (DDM) to modify commercial nickel foam with a Ni–FeOOH/PTFE microporous catalytic layer and evaluate its electrochemical performance in 1 M KOH and in a laboratory zero-gap cell with a Zirfon® Perl 500 UTP diaphragm, through circulating 25 wt.% KOH. The FeSO4-assisted DDM treatment generates mixed Ni–Fe oxyhydroxide surface species, while PTFE imparts control hydrophobicity, enhancing both catalytic activity and gas-release behavior. Annealing the electrode (DDM-NF-CAT-A) results in a cell voltage of 2.45 V at 1 A·cm−2 and 80 °C, demonstrating moderate performance comparable to other Ni-based electrodes prepared via low-complexity methods, though below that of optimized state-of-the-art zero-gap systems. Short-term durability tests (80 h at 0.5 A·cm−2) indicate stable operation, but long-term industrial performance was not assessed. These findings illustrate the potential of the DDM approach as a simple, low-cost route to structured nickel foam electrodes and provide a foundation for further optimization of catalyst loading, microstructure, and long-term stability for practical AWE applications. Full article
(This article belongs to the Special Issue 30th Anniversary of Molecules—Recent Advances in Electrochemistry)
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15 pages, 2259 KB  
Article
Enhanced Hydrogen Production in Zero-Gap Electrolysis Cell Using Optimized SS316 Metal-Based Electrodes
by Elitsa Petkucheva, Jordan Iliev, Galin Borisov and Evelina Slavcheva
Hydrogen 2025, 6(4), 113; https://doi.org/10.3390/hydrogen6040113 - 2 Dec 2025
Cited by 1 | Viewed by 591
Abstract
This work demonstrates for the first time a cost-effective modification of stainless-steel electrodes with an Fe3+ precursor via the deep-and-dry method (DDM) at processing temperatures between 20 °C and 80 °C, enabling their simultaneous applicability for both OER and HER in zero-gap [...] Read more.
This work demonstrates for the first time a cost-effective modification of stainless-steel electrodes with an Fe3+ precursor via the deep-and-dry method (DDM) at processing temperatures between 20 °C and 80 °C, enabling their simultaneous applicability for both OER and HER in zero-gap electrolyzers. The approach offers a durable and economical alternative to conventional nickel-based electrodes. Morphological and compositional analyses by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) demonstrated a pronounced temperature-dependent evolution of surface features. At 20 °C, the coatings exhibited high porosity and incomplete coverage, whereas treatment at 60 °C yielded a compact, uniform, and continuous layer with suppressed Fe/Ni exposure and enhanced oxygen incorporation. Electrochemical characterization in 25% KOH by cyclic voltammetry and polarization measurements confirmed reversible redox behavior and comparable electrochemically active surface areas across all samples, with the 60 °C electrodes achieving the highest catalytic activity. In electrolysis cell tests (zero gap), the optimized electrodes delivered low cell voltages, current densities up to 1.35 A cm−2, and power outputs approaching 3.5 W cm−2. These results establish processing temperature as a decisive factor for tailoring the morphology, composition, and performance of DDM-fabricated electrodes, underscoring the promise of 60 °C-treated electrodes for efficient hydrogen production. Full article
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19 pages, 6246 KB  
Article
Modified Cu-Sn Catalysts Enhance CO2RR Towards Syngas Generation
by Daniel Herranz, Antonio Maroto, Martina Rodriguez, Juan Ramón Avilés Moreno and Pilar Ocón
Materials 2025, 18(17), 4070; https://doi.org/10.3390/ma18174070 - 30 Aug 2025
Viewed by 872
Abstract
The electrochemical reduction in CO2 (CO2RR) to syngas and value-added hydrocarbons offers a promising route for sustainable CO2 utilization. This work develops tuneable Cu-Sn bimetallic catalysts via electrodeposition, optimized for CO2RR in a zero-gap flow cell fed with CO2-saturated [...] Read more.
The electrochemical reduction in CO2 (CO2RR) to syngas and value-added hydrocarbons offers a promising route for sustainable CO2 utilization. This work develops tuneable Cu-Sn bimetallic catalysts via electrodeposition, optimized for CO2RR in a zero-gap flow cell fed with CO2-saturated KHCO3 solution, a configuration closer to industrial scalability than conventional H-cells. By varying electrodeposition parameters (pH, surfactant DTAB, and metal precursors), we engineered catalysts with distinct selectivity profiles: Cu-Sn(B), modified with DTAB, achieved 50% Faradaic efficiency (FE) to CO at −2.2 V and −50 mA·cm−2, outperforming Ag-based systems that require higher overpotentials. Meanwhile, Cu-Sn(A) favoured C2H4 (35% FE at −100 mA·cm−2), and Cu-Sn(C) shifted selectivity to CH4 (26% FE), demonstrating product tunability. The catalysts’ performance stems from synergistic Cu-Sn interactions and DTAB-induced morphological control, as revealed by SEM/EDX and electrochemical analysis. Notably, all systems operated at lower voltages than literature benchmarks while maintaining moderate CO2 utilization (32–49% outlet). This study highlights the potential of electrodeposited Cu-Sn catalysts for energy-efficient CO2RR, bridging the gap between fundamental research and industrial application in syngas and hydrocarbon production. Full article
(This article belongs to the Special Issue Advances in Catalytic Materials and Their Applications)
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25 pages, 4500 KB  
Article
Cost-Effective Bimetallic Catalysts for Green H2 Production in Anion Exchange Membrane Water Electrolyzers
by Sabrina Campagna Zignani, Marta Fazio, Mariarosaria Pascale, Chiara Alessandrello, Claudia Triolo, Maria Grazia Musolino and Saveria Santangelo
Nanomaterials 2025, 15(13), 1042; https://doi.org/10.3390/nano15131042 - 4 Jul 2025
Cited by 1 | Viewed by 1223
Abstract
Green hydrogen production from water electrolysis (WE) is one of the most promising technologies to realize a decarbonized future and efficiently utilize intermittent renewable energy. Among the various WE technologies, the emerging anion exchange membrane (AEMWE) technology shows the greatest potential for producing [...] Read more.
Green hydrogen production from water electrolysis (WE) is one of the most promising technologies to realize a decarbonized future and efficiently utilize intermittent renewable energy. Among the various WE technologies, the emerging anion exchange membrane (AEMWE) technology shows the greatest potential for producing green hydrogen at a competitive price. To achieve this goal, simple methods for the large-scale synthesis of efficient and low-cost electrocatalysts are needed. This paper proposes a very simple and scalable process for the synthesis of nanostructured NiCo- and NiFe-based electrode materials for a zero-gap AEMWE full cell. For the preparation of the cell anode, oxides with different Ni molar fractions (0.50 or 0.85) are synthesized by the sol–gel method, followed by calcination in air at different temperatures (400 or 800 °C). To fabricate the cell cathode, the oxides are reduced in a H2/Ar atmosphere. Electrochemical testing reveals that phase purity and average crystal size significantly influence cell performance. Highly pure and finely grained electrocatalysts yield higher current densities at lower overpotentials. The best performing membrane electrode assembly exhibits a current density of 1 A cm−2 at 2.15 V during a steady-state 150 h long stability test with 1 M KOH recirculating through the cell, the lowest series resistance at any cell potential (1.8 or 2.0 V), and the highest current density at the cut-off voltage (2.2 V) both at the beginning (1 A cm−2) and end of tests (1.78 A cm−2). The presented results pave the way to obtain, via simple and scalable techniques, cost-effective catalysts for the production of green hydrogen aimed at a wider market penetration by AEMWE. Full article
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11 pages, 1035 KB  
Article
Electrodialysis Using Zero-Gap Electrodes Producing Concentrated Product Without Significant Solution Resistance Losses
by W. Henry Freer, Charles Perks, Charles Codner and Paul A. Kohl
Membranes 2025, 15(6), 186; https://doi.org/10.3390/membranes15060186 - 19 Jun 2025
Cited by 1 | Viewed by 1326
Abstract
Electrochemical separations use an ionic current to drive the flow of ions across an ion exchange membrane to produce dilute and concentrated streams. The economics of these systems is challenging because passing an ionic current through a dilute solution often requires a small [...] Read more.
Electrochemical separations use an ionic current to drive the flow of ions across an ion exchange membrane to produce dilute and concentrated streams. The economics of these systems is challenging because passing an ionic current through a dilute solution often requires a small cell gap to lower the ionic resistance and the use of a low current density to minimize the voltage drop across the dilute product stream. Lower salt concentration in the product stream improves the fraction of the salt recovered but increases the electricity cost due to high ohmic losses. The electricity cost is managed by lowering the current density which greatly increases the balance of the plant. The cell configuration demonstrated in this study eliminates the need to pass an ionic current through the diluted product stream. Ionic current passes only through the concentrated product stream, which allows use of high current density and smaller balance of the plant. The cell has three chambers with an anion and cation membrane separating the cathode and anode, respectively, from the concentrated product solution. The device uses zero-gap membrane electrode assemblies to improve the cell voltage and system performance. As ions concentrate in the center compartment, the solution resistance decreases, and the product is recovered with a lower voltage penalty compared to traditional electrodialysis. This lower voltage drop allows for faster feed flow rates and higher current density. Additionally, the larger cell gap for the product provides opportunities for systems with solids suspended in solution. It was found that the ion collection efficiency increased with current due to enhanced convective mass transfer in the feed streams. Full article
(This article belongs to the Section Membrane Applications for Energy)
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12 pages, 3215 KB  
Article
Advanced Alkaline Water Electrolysis Stack with Non-Noble Catalysts and Hybrid Electrical Connections of the Single Cells
by Galin Borisov, Vasil Bachvarov, Rashko Rashkov and Evelina Slavcheva
Catalysts 2024, 14(3), 179; https://doi.org/10.3390/catal14030179 - 4 Mar 2024
Cited by 6 | Viewed by 5933
Abstract
In this research, a thin layer of multi-metallic non-precious catalyst is prepared by electroplating from an electrolyte bath containing Ni, Co, and Fe sulfates over pressed commercial nickel foam electrode. The composition of the deposited catalytic film and its morphology are characterized by [...] Read more.
In this research, a thin layer of multi-metallic non-precious catalyst is prepared by electroplating from an electrolyte bath containing Ni, Co, and Fe sulfates over pressed commercial nickel foam electrode. The composition of the deposited catalytic film and its morphology are characterized by scanning electron microscopy (SEM) with energy dispersion X-ray (EDX) techniques. The efficiency of the prepared binder-free electrodes for electrochemical water splitting is investigated in a self-designed short water electrolysis stack with zero-gap configuration of the integrated single cells and hybrid electrical connections. The separator used is a commercial Zirfon Perl 500 membrane, doped with 25% KOH. The performance of the catalyst, the single cells, and the developed electrolyzer stack are examined by steady state polarization curves and stationery galvanostatic stability tests in the temperature range 20 °C to 80 °C. The NiFeCoP multi-metallic alloy demonstrates superior catalytic efficiency compared to the pure nickel foam electrodes and reliable stability with time. The single cells in the stack show identical performance and the cumulative stack parameters strictly follow the theoretical considerations. The applied hybrid electrical connections enable scaling of both the stack voltage and the passing current, which in turn ensures flexibility with regard to the input power and the hydrogen production capacity. Full article
(This article belongs to the Section Electrocatalysis)
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10 pages, 1172 KB  
Article
Optimizing the Performance of Low-Loaded Electrodes for CO2-to-CO Conversion Directly from Capture Medium: A Comprehensive Parameter Analysis
by Alessio Mezza, Mattia Bartoli, Angelica Chiodoni, Juqin Zeng, Candido F. Pirri and Adriano Sacco
Nanomaterials 2023, 13(16), 2314; https://doi.org/10.3390/nano13162314 - 12 Aug 2023
Cited by 5 | Viewed by 2106
Abstract
Gas-fed reactors for CO2 reduction processes are a solid technology to mitigate CO2 accumulation in the atmosphere. However, since it is necessary to feed them with a pure CO2 stream, a highly energy-demanding process is required to separate CO2 [...] Read more.
Gas-fed reactors for CO2 reduction processes are a solid technology to mitigate CO2 accumulation in the atmosphere. However, since it is necessary to feed them with a pure CO2 stream, a highly energy-demanding process is required to separate CO2 from the flue gasses. Recently introduced bicarbonate zero-gap flow reactors are a valid solution to integrate carbon capture and valorization, with them being able to convert the CO2 capture medium (i.e., the bicarbonate solution) into added-value chemicals, such as CO, thus avoiding this expensive separation process. We report here a study on the influence of the electrode structure on the performance of a bicarbonate reactor in terms of Faradaic efficiency, activity, and CO2 utilization. In particular, the effect of catalyst mass loading and electrode permeability on bicarbonate electrolysis was investigated by exploiting three commercial carbon supports, and the results obtained were deepened via electrochemical impedance spectroscopy, which is introduced for the first time in the field of bicarbonate electrolyzers. As an outcome of the study, a novel low-loaded silver-based electrode fabricated via the sputtering deposition technique is proposed. The silver mass loading was optimized by increasing it from 116 μg/cm2 to 565 μg/cm2, thereby obtaining an important enhancement in selectivity (from 55% to 77%) and activity, while a further rise to 1.13 mg/cm2 did not provide significant improvements. The tremendous effect of the electrode permeability on activity and proficiency in releasing CO2 from the bicarbonate solution was shown. Hence, an increase in electrode permeability doubled the activity and boosted the production of in situ CO2 by 40%. The optimized Ag-electrode provided Faradaic efficiencies for CO close to 80% at a cell voltage of 3 V and under ambient conditions, with silver loading of 565 μg/cm2, the lowest value ever reported in the literature so far. Full article
(This article belongs to the Special Issue Advances in Nano-Electrochemical Materials and Devices)
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18 pages, 2501 KB  
Article
A New Method Based on a Zero Gap Electrolysis Cell for Producing Bleach: Concept Validation
by Rihab Belhadj Ammar, Takoua Ounissi, Lassaad Baklouti, Christian Larchet, Lasâad Dammak, Arthur Mofakhami and Emna Selmane Belhadj Hmida
Membranes 2022, 12(6), 602; https://doi.org/10.3390/membranes12060602 - 10 Jun 2022
Cited by 3 | Viewed by 5412
Abstract
Commercial bleach (3.6 wt% active chlorine) is prepared by diluting highly concentrated industrial solutions of sodium hypochlorite (about 13 wt% active chlorine) obtained mainly by bubbling chlorine gas into dilute caustic soda. The chlorine and soda used are often obtained by electrolyzing a [...] Read more.
Commercial bleach (3.6 wt% active chlorine) is prepared by diluting highly concentrated industrial solutions of sodium hypochlorite (about 13 wt% active chlorine) obtained mainly by bubbling chlorine gas into dilute caustic soda. The chlorine and soda used are often obtained by electrolyzing a sodium chloride solution in two-compartment cells (chlorine-soda processes). On a smaller scale, small units used for swimming pool water treatment, for example, allow the production of low-concentration bleach (0.3 to 1 wt% active chlorine) by use of a direct electrolysis of sodium chloride brine. The oxidation and degradation reaction of hypochlorite ion (ClO) at the anode is the major limiting element of this two-compartment process. In this study, we have developed a new process to obtain higher levels of active chlorine up to 3.6%, or 12° chlorometric degree. For this purpose, we tested a device consisting of a zero-gap electrolysis cell, with three compartments separated by a pair of membranes that can be porous or ion-exchange. The idea is to generate in the anode compartment hypochlorous acid (HClO) at high levels by continuously adjusting its pH to a value between 4.5 and 5.5. In the cathodic compartment, caustic soda is obtained, while the central compartment is supplied with brine. The hypochlorous acid solution is then neutralized with a concentrated solution of NaOH to obtain bleach. In this work, we studied several membrane couples that allowed us to optimize the operating conditions and to obtain bleach with contents close to 1.8 wt% of active chlorine. The results obtained according to the properties of the membranes, their durability, and the imposed electrochemical conditions were discussed. Full article
(This article belongs to the Special Issue Ion-Exchange Membranes and Processes (Volume III))
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12 pages, 5598 KB  
Article
Bifunctional CuO-Ag/KB Catalyst for the Electrochemical Reduction of CO2 in an Alkaline Solid-State Electrolysis Cell
by Sabrina Campagna Zignani, Massimiliano Lo Faro, Alessandra Palella, Lorenzo Spadaro, Stefano Trocino, Carmelo Lo Vecchio and Antonino Salvatore Aricò
Catalysts 2022, 12(3), 293; https://doi.org/10.3390/catal12030293 - 4 Mar 2022
Cited by 5 | Viewed by 3366
Abstract
The conversion of carbon dioxide into value-added products is progressively gaining momentum. Several strategies have been used to develop technologies that reduce the net emissions of CO2. The utilisation of CO2 could either contribute to carbon recycling. In this paper, [...] Read more.
The conversion of carbon dioxide into value-added products is progressively gaining momentum. Several strategies have been used to develop technologies that reduce the net emissions of CO2. The utilisation of CO2 could either contribute to carbon recycling. In this paper, the transformation of CO2 was investigated in a coelectrolysis cell constituted of a solid polymer electrolyte, a carbon-supported CuO-Ag composite cathode and NiFeOx anode. Noncritical raw materials were synthesised according to the oxalate method and investigated in an alkaline environment. Low-carbon alcohols were obtained with a specific selectivity for ethanol and methanol over the CuO-Ag/KB cathode. The reaction rates at 1.6 V and 1.8 V cell voltages have been determined in steady-state experiments using NaHCO3 supporting electrolyte recirculated at the anode. Full article
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11 pages, 3392 KB  
Article
An Innovative 500 W Alkaline Water Electrolyser System for the Production of Ultra-Pure Hydrogen and Oxygen Gases
by Boguslaw Pierozynski, Tomasz Mikolajczyk, Boguslaw Wojciechowski and Mateusz Luba
Energies 2021, 14(3), 526; https://doi.org/10.3390/en14030526 - 20 Jan 2021
Cited by 5 | Viewed by 4561
Abstract
This paper communicates on an innovative, laboratory size alkaline water electrolyser (AWE) system, capable of efficiently producing ultra-pure hydrogen and oxygen gases. The system is composed of a zero-gap, bipolar-electrode stack, equipped with a polymer-based membrane, along with two drying columns for effective [...] Read more.
This paper communicates on an innovative, laboratory size alkaline water electrolyser (AWE) system, capable of efficiently producing ultra-pure hydrogen and oxygen gases. The system is composed of a zero-gap, bipolar-electrode stack, equipped with a polymer-based membrane, along with two drying columns for effective purification of H2 and O2 gaseous products. An optimal electrochemical efficiency of the electrolyser stack is provided through the employment of catalytically activated, extended surface-area nickel foam electrodes. Laboratory electrochemical examinations of the electrolyser included a series of galvanostatic AWE and alternating current (a.c.) impedance (single cell) experiments. Complementary examinations covered catalyst’s surface topography analysis by combined SEM (Scanning Electron Microscopy) and EDX (Energy Dispersive X-ray Spectroscopy) techniques along with chromatographic evaluation of the purity of hydrogen and oxygen products. Full article
(This article belongs to the Section A5: Hydrogen Energy)
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19 pages, 3971 KB  
Article
Simple and Precise Approach for Determination of Ohmic Contribution of Diaphragms in Alkaline Water Electrolysis
by Jesús Rodríguez, Simonetta Palmas, Margarita Sánchez-Molina, Ernesto Amores, Laura Mais and Roberto Campana
Membranes 2019, 9(10), 129; https://doi.org/10.3390/membranes9100129 - 4 Oct 2019
Cited by 80 | Viewed by 14689
Abstract
A simple and low-cost alternating current (AC)-based method, without electrolyte correction, is proposed (Electrochemical Impedance Spectroscopy (EIS)-Zero Gap Cell) for the determination of ohmic contribution of diaphragms. The effectiveness of the proposed methodology was evaluated by using a commercial Alkaline Water Electrolysis (AWE) [...] Read more.
A simple and low-cost alternating current (AC)-based method, without electrolyte correction, is proposed (Electrochemical Impedance Spectroscopy (EIS)-Zero Gap Cell) for the determination of ohmic contribution of diaphragms. The effectiveness of the proposed methodology was evaluated by using a commercial Alkaline Water Electrolysis (AWE) diaphragm (Zirfon®). Furthermore, the results were compared with two conventional electrochemical methodologies for calculating the separator resistance, based on direct current (DC), and AC measurements, respectively. Compared with the previous techniques, the proposed approach reported more accurate and precise values of resistance for new and aged samples. Compared with the manufacturer reference, the obtained error values for new samples were 0.33%, 5.64%, and 41.7%, respectively for EIS-Zero gap cell, AC and DC methods, confirming the validity and convenience of the proposed technique. Full article
(This article belongs to the Special Issue Membranes for Electrolysis, Fuel Cells and Batteries)
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