A Study of Gas Diffusion Electrodes for the Coupled Reaction of Water Electrolysis and Electrocatalytic Benzene Hydrogenation

Gas diffusion electrodes are applied to the coupled reaction of water electrolysis and electrocatalytic benzene hydrogenation. The effects of the preparation conditions of electrodes, electrolyte acidity, the concentration of benzene and water vapor, and the flow rate of N2 are investigated by evaluating the efficiency of the current. Furthermore, the optimal operational conditions have been ascertained. The results of our experiment show that gas diffusion electrodes have good performance when the content of PTFE is 10% (wt) and that of Nafion is 0.75mg/cm2. The optimal operational conditions are as follows: The temperature of electrolysis is 70℃, acidity 0.5mol/L, the concentration of benzene 26%, the concentration of vapor 10%, the flow rate of N2 80mL/min-240mL/min. The efficiency of the current can reach 35% under optimal operational conditions. Then, a conclusion can be drawn that gas diffusion electrodes can improve the rate of the coupled reaction effectively.

Analysis of delamination in thin film electrodes under galvanostatic and potentiostatic operations with Li-ion diffusion from edge

Progressive delamination driven by Li-ion diffusion in elastic disk-like thin film electrodes of Li-ion batteries is modeled based on the cohesive model. Axisymmetric diffusion model is considered under both galvanostatic and potentiostatic operations. The effect of edge diffusion on the delamination process is evaluated. It is found that the diffusion from edge leads to an earlier delamination initiation. The edge effect is significant for active disks with a small aspect ratio, but negligible for the case of large aspect ratio. The edge diffusion is weaker in the potentiostatic operation than in the galvanostatic operation.

Electrocatalytic CO_(2) reduction to C_(2)H_(4): From lab to fab

The global concerns of energy crisis and climate change,primarily caused by carbon dioxide(CO_(2)),are of utmost importance.Recently,the electrocatalytic CO_(2) reduction reaction(CO_(2)RR) to high value-added multi-carbon(C_(2+)) products driven by renewable electricity has emerged as a highly promising solution to alleviate energy shortages and achieve carbon neutrality.Among these C_(2+) products,ethylene(C_(2)H_(4))holds particular importance in the petrochemical industry.Accordingly,this review aims to establish a connection between the fundamentals of electrocatalytic CO_(2) reduction reaction to ethylene(CO_(2)RRto-C_(2)H_(4)) in laboratory-scale research(lab) and its potential applications in industrial-level fabrication(fab).The review begins by summarizing the fundamental aspects,including the design strategies of high-performance Cu-based electrocatalysts and advanced electrolyzer devices.Subsequently,innovative and value-added techniques are presented to address the inherent challenges encountered during the implementations of CO_(2)RR-to-C_(2)H_(4) in industrial scenarios.Additionally,case studies of the technoeconomic analysis of the CO_(2)RR-to-C_(2)H_(4) process are discussed,taking into factors such as costeffectiveness,scalability,and market potential.The review concludes by outlining the perspectives and challenges associated with scaling up the CO_(2)RR-to-C_(2)H_(4) process.The insights presented in this review are expected to make a valuable contribution in advancing the CO_(2)RR-to-C_(2)H_(4) process from lab to fab.

Electrochemical disinfection using the gas diffusion electrode system

A study on the electrochemical disinfection with H202 generated at the gas diffusion electrode （GDE） from active carbon/poly- tetrafluoroethylene was performed in a non-membrane cell. The effects of Pt load and the pore-forming agent content in GDE, and operating conditions were investigated. The experimental results showed that nearly all bacterial cultures inoculated in the secondary effluent from wastewater treatment plant could be inactivated within 30 min at a current density of 10 mA/cm^2. The disinfection improved with increasing Pt load. Addition of the pore-forming agent NH4HCO3 improved the disinfection, while a drop in the pH value resulted in a rapid rise of germicidal efficacy and the disinfection time was shortened with increasing oxygen flow rate. Adsorption was proved to be ineffective in destroying bacteria, while germicidal efficacy increased with current density. The acceleration rate was different, it initially increased with current density. Then decreased, and finally reached a maximum at a current density of 6.7 mA/cm^2. The disinfection also improved with decreasing total bacterial count. The germicidal efficacy in the cathode compartment was approximately the same as in the anode compartment, indicating that the contribution of direct oxidation and the indirect treatment of bacterial cultures by hydroxyl radical was similar to the oxidative indirect effect of the generated H2O2.

Enhancing ammonia production rates from electrochemical nitrogen reduction by engineering three-phase boundary with phosphorus-activated Cu catalysts

Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems.

CO_(2)electrolysis:Advances and challenges in electrocatalyst engineering and reactor design

Electrochemical reduction of CO_(2)(CO_(2)RR)coupled with renewable electrical energy is an attractive way of upgrading CO_(2)to value-added chemicals and closing the carbon cycle.However,CO_(2)RR electrocatalysts still suffer from high overpotential,and the complex reaction pathways of CO_(2)RR often lead to mixed products.Early research focuses on tuning the binding of reaction intermediates on electrocatalysts,and recent efforts have revealed that the design of electrolysis reactors is equally important for efficient and selective CO_(2)RR.In this review,we present an overview of recent advances and challenges toward achieving high activity and high selectivity in CO_(2)RR at ambient conditions,with a particular focus on the progress of CO_(2)RR electrocatalyst engineering and reactor design.Our discussion begins with three types of electrocatalysts for CO_(2)RR(noble metalbased,none-noble metal-based,and metal-free electrocatalysts),and then we examine systems-level strategies toward engineering specific components of the electrolyzer,including gas diffusion electrodes,electrolytes,and polymer electrolyte membranes.We close with future perspectives on catalyst development,in-situ/operando characterization,and electrolyzer performance evaluation in CO_(2)RR studies.

Advances and challenges of electrolyzers for large-scale CO_(2) electroreduction

CO_(2) electroreduction(CO_(2) ER)to high value-added chemicals is considered as a promising technology to achieve sustainable carbon neutralization.By virtue of the progressive research in recent years aiming at design and understanding of catalytic materials and electrolyte systems,the CO_(2) ER performance(such as current density,selectivity,stability,CO_(2) conversion,etc.)has been continually increased.Unfortunately,there has been relatively little attention paid to the large-scale CO 2 electrolyzers,which stand just as one obstacle,alongside series-parallel integration,challenging the practical application of this infant technology.In this review,the latest progress on the structures of low-temperature CO_(2) electrolyzers and scale-up studies was systematically overviewed.The influence of the CO_(2) electrolyzer configurations,such as the flow channel design,gas diffusion electrode(GDE)and ion exchange membrane(IEM),on the CO_(2) ER performance was further discussed.The review could provide inspiration for the design of large-scale CO_(2) electrolyzers so as to accelerate the industrial application of CO_(2) ER technology.

Gas diffusion in catalyst layer of flow cell for CO_(2) electroreduction toward C_(2+) products

The use of gas diffusion electrode(GDE)based flow cell can realize industrial-scale CO_(2) reduction reactions(CO_(2)RRs).Controlling local CO_(2) and CO intermediate diffusion plays a key role in CO_(2)RR toward multi-carbon(C_(2+))products.In this work,local CO_(2) and CO intermediate diffusion through the catalyst layer(CL)was investigated for improving CO_(2)RR toward C_(2+)products.The gas permeability tests and finite element simulation results indicated CL can balance the CO_(2) gas diffusion and residence time of the CO intermediate,leading to a sufficient CO concentration with a suitable CO_(2)/H_(2)O supply for high C_(2+)products.As a result,an excellent selectivity of C_(2+)products~79%at a high current density of 400 mA·cm^(-2) could be obtained on the optimal 500 nm Cu CL(Cu500).This work provides a new insight into the optimization of CO_(2)/H_(2)O supply and local CO concentration by controlling CL for C_(2+)products in CO_(2)RR flow cell.

A novel bifunctional oxygen electrode architecture enabled by heterostructures self-scaffolding for lithium–oxygen batteries

In recent years, as one of the most promising chemical power sources for future society, lithium–oxygen (Li–O2) battery receives great attention due to its extremely high theoretical energy density of 3505 Wh kg^(–1)[1–4]. In practice, large polarization and consequent low energy efficiency currently still hinder the application of Li–O2batteries, which mainly results from the sluggish electrochemical reaction kinetics of oxygen diffusion electrodes in aprotic electrolytes [5]. On one hand, oxygen reduction reaction (ORR)in aprotic electrolytes is intrinsically sluggish due to the difficult charge transfer, the low solubility of oxygen.

Innovative strategies toward challenges in PV-powered electrochemical CO_(2)reduction

The solar energy-driven electrochemical CO_(2)reduction to value-added fuels or chemicals is considered as an attractive path to store renewable energy in the form of chemical energy to close the carbon cycle.However,CO_(2)reduction suffers from a number of challenges including slow reaction rates,low selectivity,and low energy conversion efficiency.Recently,innovative strategies have been developed to mitigate this challenges.Especially the development of flow cell reactors with a gas diffusion electrode,ionic liquid electrolytes,and new electrocatalysts have dramatically improved the reaction rates and selectivity to desired products.In this perspective,we highlight the key recent developments and challenges in PVpowered electrochemical CO_(2)reduction and propose effective strategies to improve the reaction kinetics,to minimize the electrical energy losses,and to tune the selectivity of the catalysts for desired products,and then suggest future direction of research and development.

Microbial electrosynthesis of acetate from CO_(2)in three-chamber cells with gas diffusion biocathode under moderate saline conditions

The industrial adoption of microbial electrosynthesis(MES)is hindered by high overpotentials deriving from low electrolyte conductivity and inefficient cell designs.In this study,a mixed microbial consortium originating from an anaerobic digester operated under saline conditions(∼13 g L^(−1)NaCl)was adapted for acetate production from bicarbonate in galvanostatic(0.25 mA cm^(−2))H-type cells at 5,10,15,or 20 g L^(−1)NaCl concentration.The acetogenic communities were successfully enriched only at 5 and 10 g L^(−1)NaCl,revealing an inhibitory threshold of about 6 g L^(−1)Na^(+).The enriched planktonic communities were then used as inoculum for 3D printed,three-chamber cells equipped with a gas diffusion biocathode.The cells were fed with CO_(2)gas and operated galvanostatically(0.25 or 1.00 mA cm^(−2)).The highest production rate of 55.4 g m^(−2) d^(−1)(0.89 g L^(−1)d^(−1)),with 82.4%Coulombic efficiency,was obtained at 5 g L^(−1)NaCl concentration and 1 mA cm^(−2)applied current,achieving an average acetate production of 44.7 kg MWh−1.Scanning electron microscopy and 16S rRNA sequencing analysis confirmed the formation of a cathodic biofilm dominated by Acetobacterium sp.Finally,three 3D printed cells were hydraulically connected in series to simulate an MES stack,achieving three-fold production rates than with the single cell at 0.25 mA cm^(−2).This confirms that three-chamber MES cells are an efficient and scalable technology for CO_(2)bio-electro recycling to acetate and that moderate saline conditions(5 g L^(−1)NaCl)can help reduce their power demand while preserving the activity of acetogens.

Preparation of a Pb loaded gas diffusion electrode and its application to C02 electroreduction

A Pb loaded gas diffusion electrode was fabricated and used for the electroreduction of CO2 to formic acid. The Pb/C catalyst was prepared by isometric impregnation. The crystal structure and morphology of the Pb/C catalyst were characterized by X-ray diffraction （XRD） and transmission electron microscope （TEM）. The preparation conditions of the gas diffusion electrode were optimized by adjusting the amounts of polytetrafluoroethylene （PTFE） in the gas diffusion layer and acetylene black in the catalytic layer. The electrochemical performance of the as-prepared gas diffusion electrode was studied by chronoamperometry and cyclic voltammetry. The optimized gas diffusion electrode showed good catalytic performance for the electroreduction of CO2. The current efficiency of formic acid after 1 h of operation reached a maximum of 22% at -2.0 V versus saturated calomel electrode （SCE）.

Evaluation of the technoeconomic feasibility of electrochemical hydrogen peroxide production for decentralized water treatment

This study evaluated the feasibility of electrochemical hydrogen peroxide(H2O2)production with gas diffusion electrode(GDE)for decentralized water treatment.Carbon black-polytetrafluoroethylene GDEs were prepared and tested in a continuous flow electrochemical cell for H2O2 production from oxygen reduction.Results showed that because of the effective oxygen transfer in GDEs,the electrode maintained high apparent current efficiencies(ACEs,>80%)for H_(2)O_(2) production over a wide current density range of 5–400 mA/cm^(2),and H_(2)O_(2) production rates as high as~202 mg/h/cm^(2) could be obtained.Long-term stability test showed that the GDE maintained high ACEs(>85%)and low energy consumption(<10 kWh/kg H2O2)for H_(2)O_(2) production for 42 d(~1000 h).However,the ACEs then decreased to~70%in the following 4 days because water flooding of GDE pores considerably impeded oxygen transport at the late stage of the trial.Based on an electrode lifetime of 46 days,the overall cost for H2O2 production was estimated to be~0.88$/kg H_(2)O_(2),including an electricity cost of 0.61$/kg and an electrode capital cost of 0.27$/kg.With a 9 cm^(2) GDE and 40 mA/cm^(2) current density,~2–4 mg/L of H2O2 could be produced on site for the electro-peroxone treatment of a 1.2 m^(3)/d groundwater flow,which considerably enhanced ibuprofen abatement compared with ozonation alone(~43%–59%vs.7%).These findings suggest that electrochemical H_(2)O_(2) production with GDEs holds great promise for the development of compact treatment technologies for decentralized water treatment at a household and community level.