Electrode Reactor Research Articles

Surface Area-Enhanced Cerium and Sulfur-Modified Hierarchical Bismuth Oxide Nanosheets for Electrochemical Carbon Dioxide Reduction to Formate.

Electrochemical carbon dioxide reduction reaction (ECO2RR) is a promising approach to synthesize fuels and value-added chemical feedstocks while reducing atmospheric CO2 levels. Here, high surface area cerium and sulfur-doped hierarchical bismuth oxide nanosheets (Ce@S-Bi2O3) are develpoed by a solvothermal method. The resulting Ce@S-Bi2O3 electrocatalyst shows a maximum formate Faradaic efficiency (FE) of 92.5% and a current density of 42.09mA cm-2 at -1.16V versus RHE using a traditional H-cell system. Furthermore, using a three-chamber gas diffusion electrode (GDE) reactor, a maximum formate FE of 85% is achieved in a wide range of applied potentials (-0.86 to -1.36V vs RHE) using Ce@S-Bi2O3. The density functional theory (DFT) results show that doping of Ce and S in Bi2O3 enhances formate production by weakening the OH* and H* species. Moreover, DFT calculations reveal that *OCHO is a dominant pathway on Ce@S-Bi2O3 that leads to efficient formate production. This study opens up new avenues for designing metal and element-doped electrocatalysts to improve the catalytic activity and selectivity for ECO2RR.

Current regulates electron donors for heterotrophic and autotrophic microorganisms to enhance sulfate reduction in three-dimensional electrode biofilm reactors

The variability in industrial production often generates wastewater with an unstable carbon-to-sulfur ratio, challenging the concurrent removal of sulfate and organic compounds. Three-dimensional biofilm electrode reactor (3D-BER) technology offers a promising solution, compatible with both autotrophic and heterotrophic sulfate reduction. In this study, four up-flow 3D-BERs with gradient current levels were operated for nearly 400 days to treat simulated high-concentration sulfate wastewater. The effects of current intensity, hydraulic retention time (HRT), and influent carbon-to-sulfur ratio on sulfate and organic removal were investigated. The composition and functions of microbial communities were analyzed by metagenomic sequencing. The synergistic mechanism between heterotrophic and autotrophic sulfate reduction was examined by delineating their individual contributions to sulfate removal. Under optimized conditions (HRT 60 h, influent carbon-to-sulfur ratio of 1.7, and current intensity of 50 mA), the highest removal efficiencies for SO42- and COD reached 70.47 % and 85.58 %, respectively. Elevated current intensity increased the abundances of Desulfuromonadaceae, Desulfovibrionaceae and Methanobacteriaceae, while decreasing Anaerolineaceae and Geobacteraceae. Key genes involved in carbon fixation and hydrogen-relied sulfate reduction showed lower abundances at high current levels, whereas genes for direct electron uptake from the electrode were more abundant. Batch experiments demonstrated a synergistic effect between autotrophic and heterotrophic sulfate reduction, most pronounced at 50 mA. Our work successfully regulates electron donors for microbial reduction of high-concentration sulfate in 3D-BERs by manipulating current intensity, providing new insights into the application of bioelectrochemical technology for complex industrial wastewater treatment.

Non-rigid metal–oxygen bonding empowered nitrate reduction on ruthenium catalysts

Electrocatalytic nitrate reduction (NitRR) offers exciting potential for mass production of ammonia (NH3) from renewables. However, the rigidity of metal−ligand bonds in most electrocatalysts renders them unable to survive the structural transformations required for NitRR. Herein, we establish a type of non-rigid metal−oxygen bonds by employing graphene oxide (GO) sheets as a 'micron-scale' ligand for transition metals (TM). Because of being confined to the interfaces between GO and TM, the oxygenated groups in GO can associate with and dissociate from the TM in response to reaction dynamics. As a proof-of-concept demonstration, an electrocatalyst was developed by dispersing nanoscale ruthenium (Ru) on graphene oxide (GO) and utilizing two-dimensional MXene to compensate for the low electrical conductivity of GO. This electrocatalyst exhibits a maximum NH3 yield of over 5 mg cm−2 h−1, with almost 100 % current-to-NH3 efficiency, far outperforming the performance of most reported Ru-based materials. What's even more remarkable is the achievement of a record-breaking performance: a 200-hour stable electrolysis with a NH3 yield of 40.2 mg cm−2 h−1, using a membrane electrode reactor. Our experimental and theoretical investigations further reveal the non-rigidity of the Ru–O bonds and how they self-regulate to adapt to diverse intermediates involved in NitRR. This work provides an approach to fabricate a high-performance electrocatalyst featuring reversible and non-rigid metal−oxygen bonds, opening new possibilities for practical nitrate electrolysis.

Rotating cylinder electrode in reactive CO2 capture: Identifying active C species via transport, VLE models and kinetics

AbstractThis article explores technical challenges and potential methodologies for understanding electrochemical Reactive CO Capture (RCC) mechanisms. RCC offers potential energy cost advantages by directly converting captured CO into fuels and chemicals, unlike traditional carbon capture and utilization (CCU) processes that require sequential capture, concentration, and compression. However, direct conversion of captured CO introduces complexity due to additional equilibrium buffer reactions, making it challenging to identify active species for reduction in electrochemical studies. This article discusses methods to integrate transport, thermodynamics, and kinetics concepts to identify active carbon sources in RCC. Vapor‐Liquid Equilibrium (VLE) and transport models are validated against experimental results obtained in a gastight rotating cylinder electrode reactor and are shown as useful tools for studying RCC in heterogeneous electrocatalysts across different capture agents, solvents, and temperatures. This article establishes an experimental framework for advancing research in electrochemical RCC.

Electrochemical treatment of 4-chlorophenol by three-dimensional electrode reactors packed with plastic particles electrodes

The three-dimensional electrode reactors (TDER) filled with surface-modified plastic particles electrodes, was much more effective on electrolyzing 4-chlorophenol wastewater than by conventional electrolysis. The experimental results indicated that about 96.8 % of 4-chorophenol was degraded effectively, it was possibly decomposed into aromatic organic compounds and small-molecular organic acids by hydroxyl radicals generated on the surfaces of electrodes, and the biodegradability of treated 4-chlorophenol wastewater was also much more improved than that of the untreated, which would be more easily biologically degraded by the subsequent conventional activated sludge process. Furthermore, the 4-chorophenol wastewater could be co-degraded with high-concentration nitrate effectively, both 2-chlorophenol and 2,4-dichorophenol wastewaters were also similarly decomposed.

Multi-win situation of wastewater purification, carbon emission reduction and resource utilization: Conversion of refractory organics and nitrate to urea and ammonia in a flow-through electrochemical integrated system

The advanced oxidation process is an efficient technology for the degradation and detoxification of refractory organics to ensure water safety. However, most researches focus on improving pollutant degradation but overlook carbon emission and resource utilization. In this study, a flow-through electrochemical integrated system was constructed to simultaneously realize bisphenol A (BPA) oxidation into small non-toxic organics and CO2, and generated CO2 coupled with nitrate-containing wastewater conversion to urea and ammonia on a porous cathode (Zr-Fe/CN). The synergistic effect between anodic BPA oxidation with cathodic CO2 and NO3−reduction improves the electron utilization efficiency and thus increasing the BPA degradation, urea yield rate (UYR) and NH3 yield rate (NYR) by 13.4 % 18.4 % and 8.3 %, respectively. Furthermore, the flow-through operation mode significantly increased the mass transfer efficiency and quickly carried generated CO2 from the anode into the cathode to improve CO2 utilization efficiency. Compared to the parallel plate electrode reactor, the BPA degradation efficiency, UYR and NYR in the flow-through reactor increased from 59.46 % to 84.49 % (the initial concentration of BPA was 40 mg/L), 9.94 mmol h−1g−1 to 19.55 mmol h−1g−1, and 80.31 mmol h−1g−1 to 106.06 mmol h−1g−1 within 60 min, respectively. Moreover, the total carbon conversion efficiency (from BPA to urea) increased from 20.2 % to 42.4 % and the total Faraday efficiency (FE) increased from 78.6 % to 96.3 %. This work provides a multi-win strategy of harmless, resource-based and carbon emission reduction for wastewater treatment.

Microbial communities and denitrification mechanisms of pyrite autotrophic denitrification coupled with three-dimensional biofilm electrode reactor.

Denitrification is of great significance for low C/N wastewater treatment. In this study, pyrite autotrophic denitrification (PAD) was coupled with a three-dimensional biofilm electrode reactor (BER) to enhance denitrification. The effect of current on denitrification was extensively studied. The nitrate removal of the PAD-BER increased by 14.90% and 74.64% compared to the BER and the PAD, respectively. In addition, the electron utilization, extracellular polymeric substances secretion, and denitrification enzyme activity (NaR and NiR) were enhanced in the PAD-BER. The microbial communities study displayed that Dokdonella, Hydrogenophaga, Nitrospira, and Terrimonas became the main genera for denitrification. Compared with the PAD and the BER, the abundance of the key denitrification genes narG, nirK, nirS, and nosZ were all boosted in the PAD-BER. This study indicated that the enhanced autotrophic denitrifiers and denitrification genes were responsible for the improved denitrification in the PAD-BER. PRACTITIONER POINTS: PAD-BER displayed higher nitrate removal, EPS, NAR, and NIR activity. The three types of denitrification (HD, HAD, and PAD) and their contribution percentage in the PAD-BER were analyzed. HAD was dominant among the three denitrification processes in PAD-BER. Microbial community composition and key denitrification genes were tested to reveal the denitrification mechanisms.

Cobalt recovery from spent lithium-ion batteries using a rotating cylindrical electrode reactor

Abstract The cobalt electrodeposition from a leaching containing cathode-powdery of spent laptop lithium-ion batteries (LIBs) of different commercial brands, collected from local laptop repair shops, was investigated. Citric acid (0.14 M) and hydrazine (0.1 M) were employed as complexing and reducing agents in the leaching during 24 h. Cobalt, manganese and nickel concentrations in the leachate, obtained by the flame method in an atomic absorption spectrometer, are reported. A rotating cylindrical electrode reactor which consists of a rotating open bottom as cathode and a static outer cylindrical as anode was employed. The numerical flow patterns and cathode velocities that induce the presence of Taylor vortices inside and/or outside the cathode were investigated. RANS equations with the standard k−ε turbulence model and enhanced wall treatment was used. Electrical power measurements were performed to validate simulations. Cyclic voltammetry experiments with synthetic solutions were applied to determine the reduction potential of cobalt (found in −1.2 V vs SCE). Subsequently, electrolysis experiments were carried out at predetermined cathode speeds (50, 75, and 125 rpm), imposing a working cathodic potential of −1.2 V versus SCE during 12 h. Experimental results indicate that the best cobalt recovery rates and current efficiency coincide with the presence of Taylor vortices both inside and outside the cathode, i.e., at 50 rpm. The peak performance in cobalt recovery and current efficiency was recorded at 49 % and 47.3 %, respectively. Finally, the deposits obtained from each electrolysis test were removed from the cathode and analyzed via energy dispersive spectroscopy. The range of purity of Co obtained in the electrodeposit film were between 56.75 % and 74.8 %.

Efficient degradation of halogenated disinfection by products in a three-dimensional electrode reactor with MnO2/NiMn-LDH/C as particle electrodes: Performance prediction and mechanism exploration

In this work, an in situ novel MnO2/NiMn-LDH/C composite material was designed and used as a particle electrode in a three-dimensional electrochemical continuous flow system, which degraded dichloroacetamide (DCAcAm) because a suitable nickel-manganese metal ratio leads to the construction of MnO2 and NiMn-LDH, and the addition of carbon contributes to the formation of a hierarchical structure. The effects of different conditions were explored by single factor experiments and response surface design experiments. A high removal rate of 89 % was obtained under optimal conditions (current density of 12 mA/cm2, flow rate of 0.5 mL/min, electrolyte concentration of 0.175 mol/L, and a pollutant concentration of 10.5 g/L). According to density functional theory (DFT) calculations, electron paramagnetic resonance (EPR) measurements and free radical quenching experiments, the corresponding electrocatalytic mechanism and reaction pathways were clarified. The application of response surfaces was utilized to predict degradation performance. The results of the recycling experiments show the good stability of this electrode. Finally, the actual chlorin wastewater degradation experiment results showed that the COD and TOC of this wastewater decreased by 76.03 % and 72.41 %, respectively, after 90 min of electrocatalytic degradation. This study offers a novel theoretical framework and technical support for the control of HAcAms.

Design of Experiments-Based Optimization of an Electrochemical Decarboxylative Alkylation Using a Spinning Cylinder Electrode Reactor

Design of Experiments-Based Optimization of an Electrochemical Decarboxylative Alkylation Using a Spinning Cylinder Electrode Reactor

Enhanced denitrification by graphene oxide-modified cathode for the secondary effluent of wastewater treatment plants in three-dimensional biofilm electrode reactors.

In this study, a novel three-dimensional biofilm electrode reactor (3D-BER) with a graphene oxide (GO)-modified cathode was developed to enhance the denitrification performance of secondary effluent from wastewater treatment plants (SEWTPs). The effects of different hydraulic retention times (HRTs) and currents on the 3D-BER were explored. The results indicated that at the optimal HRT of 4 h and current of 350 mA/m2, the 3D-BER with GO-modified cathode had a higher denitrification rate (2.40 ± 0.1 mg TN/L/h) and less accumulation of intermediate products, especially with 3.34% total nitrogen (TN) molar conversion to N2O. The GO-modified cathode offered a large biocompatible specific surface area and enhanced the conductivity, which favored microbial growth and increased electron transfer efficiency and extracellular enzyme activities. Moreover, the activity of nitrite reductase increased more than that of nitrate reductase to accelerate nitrite reduction, thus facilitating the denitrification process. The proposed 3D-BER provided an effective solution to elevate tertiary denitrification in the SEWTP.

The effects of inner electrode shape on the performance of dielectric barrier discharge reactor for oxidative removal of NO and SO2

Seagoing vessels are responsible for more than 90% of global freight traffic, but meanwhile, emission pollutants (NO x and SO x ) of seagoing vessels also cause serious air pollution. Nonthermal plasma (NTP) combined with wet scrubbing technology is considered to be a promising technology. In order to improve the oxidation efficiency and energy efficiency of the NTP reactor, the screw and rod inner electrodes of dielectric barrier discharge (DBD) reactor were investigated. To analyze the mechanism, the optical emission spectra (OES) of NTP were measured and numerical calculation was applied. The experiment results show that the NO oxidation removal efficiency of screw electrode is lower than that of rod electrode. However, the SO2 removal efficiency of screw electrode is higher. According to the OES experiment and numerical calculation, the electric field intensity of the screw electrode surface is much higher than that of the rod electrode surface, and it is easier to generate N radicals to form NO. For the same energy density condition, the OH radical generation efficiency of the screw electrode reactor is similar to that of the rod electrode, but the gas temperature in the discharge gap is higher. Therefore, the SO2 oxidation efficiency of the thread electrode is higher. This study provides guidance for the optimization of oxidation efficiency and energy consumption of DBD reactor.

Dual-course dielectric barrier discharge with a novel hollow micro-holes electrode to efficiently mitigate NOx

The effect of a novel hollow annular micro-hole electrode on the DBD de-NOx performance was investigated. The experimental results show that the hollow electrode allows the feed gas to take full advantage of the redundant heat of the electrode, thus reducing the energy consumption of the system. Subsequently, the micro-hole structure can improve the uniformity of feed gas in the plasma channel and prolong the residence time of the feed gas in the plasma channel. The reactor can also raise the temperature of the feed gas and enhance the plasma electric field. The optimum NOx removal efficiency of about 82.6% is achieved at 16 annular micro-holes. Compared to the rod electrode reactor, the novel electrode reactor shows 19.7% reduction in energy consumption and 13.2% enhancement in de-NOx efficiency. The calculations of de-NOx mechanism show that the NO2 concentration decays significantly as the feed gas residence time increases, accompanied by a slight increase in N2O concentration. The NO2 concentration marginally increases while N2O concentration slightly decreases as the increase of feed gas temperature. DBD de-NOx presents the mode of accelerated reduction of NO, essential removal of NO2, and gradual consumption of N2O with the reduced electric field increases.

The effect of cold plasma seed treatments on nodulation and plant growth in pea (Pisum sativum) and lentil (Lens culinaris)

AbstractCold plasma enhances various biological processes in plants. This study assessed the impact of cold plasma seed treatments on nodulation, root, and shoot growth in pea and lentil under controlled environmental conditions. Seeds were treated with cold plasma generated by a dielectric barrier discharge (DBD) and a pin electrode reactor (PER), with three different exposure durations (3, 6, and 12 min). At 4 weeks, notable enhancements were observed in nodule number and dry weight, root dry weight, length, volume, surface area, and shoot dry weight. The 3‐ and 6‐min exposure using the DBD and the 3‐min exposure using the PER system demonstrated the most significant increases or upward trends in these traits, highlighting the intricate nature of seed–plasma interactions.

Electrochemical reclamation of oil sands process water: Two and three-dimensional electrode configuration systems structured with different anode materials

Several studies have indicated the potential of the electrochemical advanced oxidation process in oil sands process water (OSPW) reclamation; however, the variations in different electrode configuration systems and anode materials remain elusive. This study assembled a two-dimensional electrode system (2-DES) and a packed bed electrode reactor (PBER) for OSPW reclamation, of which boron-doped diamond (BDD) (non-active anode), dimensionally stable anodes (DSA-RuO2 and DSA-IrO2) and graphite (active anodes) were selected as the anode materials, while in PBER, spherical activated carbon (SAC) was added as the third electrode. Within the 2-DES, BDD achieved over 60% removal of chemical oxygen demand (COD) due to its excellent •OH generation ability, while DSAs generated the most active chlorine and were quickly consumed by organic matter during the first 30 minutes. However, mass transfer limitation restricted the 2-DES treatment efficiency regardless of the anode materials employed, particularly resulting in limited removal of naphthenic acids (NAs). Compared to 2-DES, PBER significantly improved the OSPW treatment under identical electrolysis conditions, achieving over 91% COD and 99% NAs removal using DSA-IrO2 + SAC. Because of the contribution of the third electrode in PBER, the performance differences between various anode materials were less substantial than in the case of 2-DES. Packed SAC enhanced the mass transfer performance and generation of radical oxidants during OSPW electrolysis, improving the OSPW electrochemical treatment process. Additionally, SAC adsorbed most free chlorine from the liquid phase, avoiding the formation of halogenated organic compounds in reclaimed OSPW.

Denitrification reaction performance in three-dimensional biofilm electrode reactors using self-releasing carbon biofilm electrodes

Agricultural waste, corncobs, and sponge iron were used to develop a self-releasing carbon biofilm electrode (SRC-BE) and utilized for denitrification experiments in three-dimensional biofilm electrode reactors (3D-BERs). Fe2+ was released to enhance the extracellular electron transfer. Following an alkali treatment, SRC-BE were introduced into 3D-BERs of the electrode group (EG), with iron serving as the anode-cathode plate in the EG. Under a current density of 0.1 mA/cm2, hydraulic retention time of 2 h, and dissolved oxygen control at 0.5–1.0 mg/L, the removal rates were as follows: the highest removal rates were 71.09 % for total nitrogen, 40.26 % for NH4+-N, and 84.34 % for NO3−-N, with a stable 96.87 % removal rate for total phosphate. The effluent chemical oxygen demand in the EG remained stable at approximately 12 mg/L during the stable phase, thus reducing the risk of secondary pollution. The enrichment of electroactive microorganisms and functional genes related to C and N also verified their denitrification efficacy.

Enhanced degradation of nitrogen-containing disinfection by-products via radical attack in ZnAl particle electrode system: Mechanism and density functional theory calculations

Disinfection by-products (DBPs), in water receive attention because of their toxicity, mutagenicity and carcinogenicity. In this study, Nitrosopyrrolidine (NPYR) in water is electrocatalytically degraded by using ZnAl layered double hydroxide/activated carbon (ZnAl-LDH/AC) as a particle electrode in a three-dimensional electrode reactor (3DER). The results of SEM, TEM and XRD showed the successful synthesis of ZnAl-LDH, in which Zn2Al1-LDH had regular morphology and better crystallinity. The results of electrochemical characterization tests indirectly showed that Zn2Al1-LDH/AC had the largest OPE, the smallest mass transfer resistance, and higher mass transfer rate, and better electrocatalytic performance. The pollutant concentration had the greatest effect on the removal rate of NPYR in the one-way experiment, and the interaction effect between different influencing factors is determined by response surface optimization experiments. The optimal operating conditions showed a pollutant removal rate of 83.78%. A response surface prediction model is constructed. Hydroxyl radicals and superoxide radicals are demonstrated to be the main contributors to indirect oxidation by free radical quenching experiments and EPR. DFT calculations combined with GC-MS and LC-MS results deduced two possible degradation pathways. Toxicity prediction of NPYR and its intermediates is performed using software. Based on the above study, a mechanism for the degradation of NPYR by 3DER is proposed.

Removal of N-nitrosopyrrolidine from GAC by a three-dimensional electrochemical reactor: degradation mechanism and degradation path.

Nitrogen-containing disinfection by-products (N-DBPs) produced in the process of drinking water disinfection are widely concerning due to the high cytotoxicity and genotoxicity. It is due to the difficulty of natural degradation of N-DBPs in water and the fact that conventional treatment systems do not effectively treat N-DBPs in drinking water. In this study, N-nitrosopyrrolidine (NPYR) in water was electrocatalytically degraded by a three-dimensional electrode reactor (3DER). This system applied graphite plates as anode and cathode. The granular activated carbon (GAC) was used as third electrode. The degradation of NPYR using a continuous flow three-dimensional electrode reactor was investigated by examining the effects of flow rate, current density, electrolyte concentration, and pollutant concentration on the degradation efficiency, energy consumption, and reaction kinetics of GAC particle electrodes. The results showed that the optimal operating conditions were flow rate = 0.45mL/min, current density = 6mA/cm2, Na2SO4 concentration = 0.28mol/L, and NPYR concentration = 20mg/L. Under optimal conditions, the degradation of NPYR exceeded 58.84%. The main contributor of indirect oxidation was deduced from free radical quenching experiments. NPYR concentration was measured by GC-MS with DB-5 capillary column, operating in full scan monitoring mode for appropriate quantification of NPYR and intermediates. Based on the identification of reaction intermediates, a possible pathway for the electrochemical oxidation of NPYR on GAC particle electrodes was proposed.

Electrode Surface Heating with Organic Films Improves CO2 Reduction Kinetics on Copper.

Management of the electrode surface temperature is an understudied aspect of (photo)electrode reactor design for complex reactions, such as CO2 reduction. In this work, we study the impact of local electrode heating on electrochemical reduction of CO2 reduction. Using the ferri/ferrocyanide open circuit voltage as a reporter of the effective reaction temperature, we reveal how the interplay of surface heating and convective cooling presents an opportunity for cooptimizing mass transport and thermal assistance of electrochemical reactions, where we focus on reduction of CO2 to carbon-coupled (C2+) products. The introduction of an organic coating on the electrode surface facilitates well-behaved electrode kinetics with near-ambient bulk electrolyte temperature. This approach helps to probe the fundamentals of thermal effects in electrochemical reactions, as demonstrated through Bayesian inference of Tafel kinetic parameters from a suite of high throughput experiments, which reveal a decrease in overpotential for C2+ products by 0.1 V on polycrystalline copper via 60 °C surface heating.

Intensive Treatment of Organic Wastewater by Three-Dimensional Electrode System within Mn-Loaded Steel Slag as Catalytic Particle Electrodes.

Developing a green, low-carbon, and circular economic system is the key to achieving carbon neutrality. This study investigated the organics removal efficiency in a three-dimensional electrode reactor (3DER) constructed from repurposed industrial solid waste, i.e., Mn-loaded steel slag, as the catalytic particle electrodes (CPE). The CPE, a micron-grade material consisting primarily of transition metals, including Fe and Mn, exhibited excellent electric conductivity, catalytic ability, and recyclability. High rhodamine B (RhB) removal efficiency in the 3DER was observed through a physical modelling experiment. The optimal operating condition was determined through a single-factor experiment in which 5.0 g·L-1 CPE and 3 mM peroxymonosulfate (PMS) were added to a 200 mL solution of 10 mM RhB under a current intensity of 0.5 A and a 1.5 to 2.0 cm distance between the 2D electrodes. When the initial pH value of the simulated solution was 3 to 9, the RhB removal rate exceeded 96% after 20 min reaction. In addition, the main reactive oxidation species in the 3DER were determined. The results illustrated that HO• and SO4•- both existed, but that the contribution of SO4•- to RhB removal was much lower than that of HO• in the 3DER. In summary, this research provides information on the potential of the 3DER for removing refractory organics from water.