Deciphering engineering principle of three-phase interface for advanced gas-involved electrochemical reactions

As an alternative to conventional energy conversion and storage reactions,gas-involved electrochemical reactions,including the carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and hydrogen evolution reaction(HER),have become an emerging research direction and have gained increasing attention due to their advantages of environmental friendliness and sustainability.Various studies have been designed to accelerate sluggish kinetics but with limited results.Most of them promote the reaction by modulating the intrinsic properties of the catalyst,ignoring the synergistic effect of the reaction as a whole.Due to the introduction of gas,traditional liquid-solid two-phase reactions are no longer applicable to future research.Since gas-involved electrochemical reactions mostly occur at the junctions of gaseous reactants,liquid electrolytes and solid catalysts,the focus of future research on reaction kinetics should gradually shift to three-phase reaction interfaces.In this review,we briefly introduce the formation and constraints of the three-phase interface and propose three criteria to judge its merit,namely,the active site,mass diffusion and electron mass transfer.Subsequently,a series of modulation methods and relevant works are discussed in detail from the three improvement directions of‘exposing more active sites,promoting mass diffusion and accelerating electron transfer’.Definitively,we provide farsighted insights into the understanding and research of three-phase interfaces in the future and point out the possible development direction of future regulatory methods,hoping that this review can broaden the future applications of the three-phase interface,including but not limited to gas-involved electrochemical reactions.

Advanced In Situ Characterization Techniques for Direct Observation of Gas-Involved Electrochemical Reactions

Gas-involved electrochemical reactions provide feasible solutions to the worldwide energy crisis and environmental pollution.It has been recognized that various elements of the reaction system,including catalysts,intermediates,and products,will undergo real-time variations during the reaction process,which are of significant meaning to the in-depth understanding of reaction mechanisms,material structure,and active sites.As judicious tools for real-time monitoring of the changes in these complex elements,in situ techniques have been exposed to the spotlight in recent years.This review aims to highlight significant progress of various advanced in situ characterization techniques,such as in situ X-ray based technologies,in situ spectrum technologies,and in situ scanning probe technologies,that enhance our understanding of heterogeneous electrocatalytic carbon dioxide reduction reaction,nitrogen reduction reaction,and hydrogen evolution reaction.We provide a summary of recent advances in the development and applications of these in situ characterization techniques,from the working principle and detection modes to detailed applications in different reactions,along with key questions that need to be addressed.Finally,in view of the unique application and limitation of different in situ characterization techniques,we conclude by putting forward some insights and perspectives on the development direction and emerging combinations in the future.

Effects of stress dependent electrochemical reaction on voltage hysteresis of lithium ion batteries

Intercalation of lithium ions into the electrodes of lithium ion batteries is affected by the stress of active materials, leading to energy dissipation and stress dependent voltage hysteresis. A reaction-diffusion-stress coupling model is established to investigate the stress effects under galvanostatic and potentiostatic operations. It is found from simulations that the stress hysteresis contributes to the voltage hysteresis and leads to the energy dissipation. In addition, the stress induced voltage hysteresis is small in low rate galvanostatic operations but extraordinarily significant in high rate cases. In potentiostatic operations, the stresses and stress induced overpotentials increase to a peak value very soon after the operation commences and decays all the left time. Therefore,a combined charge-discharge operation is suggested, i.e., first the galvanostatic one and then the potentiostatic one. This combined operation can not only avoid the extreme stress during operations so as to prevent electrodes from failure but also reduce the voltage hysteresis and energy dissipation due to stress effects.

Direct Electrochemical Reaction of Horseradish Peroxidase Immobilized on the Surface of Active Carbon Powders

It is reported for the first time that horseradish peroxidase (HRP) immobilized on the active carbon can undergo a direct quasi-reversible electrochemical reaction. In addition, the immobilized HRP showed the stable bioelectrocatalytic activity for the reduction of H2O2.

Effect of electrochemical reactions droplet metal in direct current on oxygen contamination of submerged arc welding

Agglomerated fluxes with different basicity index designed in laboratory were used to study electrochemical reactions between slag and metal in submerged arc welding under both power polarities. The droplet metal oxygen and nitrogen contents were measured using oxygen-nitrogen instrument in order to analyze indirectly metallurgy electrochemical reactions taking place in cathode and anode of welding arc. The results show that just in the period of droplet growth at the tip of consumable electrode the electrochemical oxygen contamination is produced in the case of direct current electrode positive polarity whereas electrochemical oxygen lost in electrode negative polarity. Furthermore, the results indicate that the basicity index of molten slag has great influence upon electrochemical reaction. With basicity index increasing, the effect of oxygen transferring resulted from electrochemistry becomes more evident for reacting dynamics depended on ion characteristics of molten slag. The effect of basicity index on metal-slag electrochemical reaction is contrary to traditional thermo-chemical reaction and therefore it is necessary to be considered as a metallurgy factor.

Synergistic promotion of particulate matter reduction and production performance via adjusting electrochemical reactions in the zinc electrolysis industry

Heavy particulate matter (PM) pollution and high energy consumption are the bottlenecks of hydrometallurgy, especially in the electrolysis process. Therefore, an urgent need is to explore PM reduction methods with production performance co-benefits. This study presents three PM reduction methods based on controlling operating parameters, i.e., lowering electrolyte temperature, H2SO4 concentration, and current density of the cathode. The optimized conditions were also investigated using the response surface methodology to balance the PM reduction effect and Zn production. The results showed that lowering electrolyte temperature is the most efficient, with an 89.0% reduction in the PM generation flux (GFPM). Reducing H2SO4 concentration led to the minimum side effects on the current efficiency of Zn deposition (CEZn) or power consumption (PC). With the premise of non-deteriorating CEZn and PC, GFPM can be reduced by 86.3% at the optimal condition (electrolyte temperature = 295 K, H2SO4 = 110 g/L, current density = 373 A/m^(2)). In addition, the reduction mechanism was elucidated by comprehensively analyzing bubble characteristics, electrochemical reactions, and surface tension. Results showed that lower electrolyte temperature inhibited the oxygen evolution reaction (OER) and compressed gas volume. Lower H2SO4 concentration inhibited the hydrogen evolution reaction (HER) and reduced electrolyte surface tension. Lower current density inhibited both OER and HER by decreasing the reaction current. The inhibited gas evolutions reduced the microbubbles’ number and size, thereby reducing GFPM. These results may provide energy-efficient PM reduction methods and theoretical hints of exploring cleaner PM reduction approaches for industrial electrolysis.

Exploring nitrogen reduction reaction mechanisms in electrocatalytic ammonia synthesis:A comprehensive review

The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia synthesis.While the process is thermodynamically feasible at ambient temperature and pressure,challenges such as the competing hydrogen evolution reaction,low nitrogen solubility in electrolytes,and the activation of inert dinitrogen(N_(2))gas adversely affect the performance of ammonia production.These hurdles result in low Faradaic efficiency and low ammonia production rate,which pose obstacles to the commercialisation of the process.Researchers have been actively designing and proposing various electrocatalysts to address these issues,but challenges still need to be resolved.A key strategy in electrocatalyst design lies in understanding the underlying mechanisms that govern the success or failure of the electrocatalyst in driving the electrochemical reaction.Through mechanistic studies,we gain valuable insights into the factors affecting the reaction,enabling us to propose optimised designs to overcome the barriers.This review aims to provide a comprehensive understanding of the various mechanisms involved in eNRR on the electrocatalyst surface.It delves into the various mechanisms such as dissociative,associative,Mars-van Krevelen,lithium-mediated nitrogen reduction and surface hydrogenation mechanisms of nitrogen reduction.By unravelling the intricacies of eNRR mechanisms and exploring promising avenues,we can pave the way for more efficient and commercially viable ammonia synthesis through this sustainable electrochemical process by designing an efficient electrocatalyst.

In situ observation of the electrochemical behavior of Li–CO_(2)/O_(2)batteries in an environmental transmission electron microscope

Li–CO_(2)/O_(2)batteries,a promising energy storage technology,not only provide ultrahigh discharge capacity but also capture CO_(2)and turn it into renewable energy.Their electrochemical reaction pathways'ambiguity,however,creates a hurdle for their practical application.This study used copper selenide(CuSe)nanosheets as the air cathode medium in an environmental transmission electron microscope to in situ study Li–CO_(2)/O_(2)(mix CO_(2)as well as O_(2)at a volume ratio of 1:1)and Li–O_(2)batteries as well as Li–CO_(2)batteries.Primary discharge reactions take place successively in the Li–CO_(2)/O_(2)–CuSe nanobattery:(I)4Li^(+)+O_(2)+4e^(−)→2Li_(2)O;(II)Li_(2)O+CO_(2)→Li_(2)CO_(3).The charge reaction proceeded via(III)2Li_(2)CO_(3)→4Li^(+)+2CO_(2)+O_(2)+4e^(−).However,Li–O_(2)and Li–CO_(2)nanobatteries showed poor cycling stability,suggesting the difficulty in the direct decomposition of the discharge product.The fluctuations of the Li–CO_(2)/O_(2)battery's electrochemistry were also shown to depend heavily on O_(2).The CuSe‐based Li–CO_(2)/O_(2)battery showed exceptional electrochemical performance.The Li^–CO_(2)/O_(2)battery offered a discharge capacity apex of 15,492 mAh g^(−1) and stable cycling 60 times at 100 mA g^(−1).Our research offers crucial insight into the electrochemical behavior of Li–CO_(2)/O_(2),Li–O_(2),and Li–CO_(2)nanobatteries,which may help the creation of high‐performance Li–CO_(2)/O_(2)batteries for energy storage applications.

Elucidating the Role of Mass Transfer in Electrochemical Redox Reactions on Electrospun Fibers

Mass transfer can tune the surface concentration of reactants and products and subsequently infl uence the catalytic perfor-mance.The morphology of nanomaterials plays an important role in the mass transfer of reaction microdomains,but related studies are lacking.Herein,a facile electrospinning technique utilizing cellulose was employed to fabricate a series of carbon nanofi bers with diff erent diameters,which exhibited excellent electrochemical nitrate reduction reaction and oxygen evolu-tion reaction activities.Furthermore,the microstructure of electrocatalysts could infl uence the gas-liquid-solid interfacial mass transfer,resulting in diff erent electrochemical performances.

Core-shell Ag-Pt nanoparticles:A versatile platform for the synthesis of heterogeneous nanostructures towards catalyzing electrochemical reactions

Heterogeneous nanostructures that are defined as a hybrid structure consisting of two or more nanoscale domains with distinct chemical compositions or physical characteristics have attracted intense efforts in recent years.In this review,we focus on the introduction of a number of heterogeneous nanostructures derived using core-shell Ag-Pt nanoparticles as starting materials,including hollow,dimeric and composite structures and also highlight their application in catalyzing electrochemical reactions,e.g.,methanol oxidation reaction and oxygen reduction reaction.This review not only shows the capability of core-shell Ag-Pt nanoparticles in producing various heterogeneous nanostructures as starting templates,but also highlights the structural design or electronic interaction that endows the heterogeneous nanostructures with enhanced catalytic properties either in methanol oxidation or in oxygen reduction.Further,we also make some perspectives for more heterogeneous nanostructures that may be prepared by using core-shell Ag-Pt particles or their derivatives so as to offer the readers the opportunities and challenges in this field.

Electrochemical reaction mechanism of porous Zn_(2)Ti_(3)O_(8)as a high-performance pseudocapacitive anode for Li-ion batteries

Zn_(2)Ti_(3)O_(8),as a new type of anode material for lithium-ion batteries,is attracting enormous attention because of its low cost and excellent safety.Though decent capacities have been reported,the electrochemical reaction mechanism of Zn_(2)Ti_(3)O_(8)has rarely been studied.In this work,a porous Zn_(2)Ti_(3)O_(8)anode with considerably high capacity(421 mAh/g at 100 mA/g and 209 mAh/g at 5000 mA/g after 1500 cycles)was reported,which is even higher than ever reported titanium-based anodes materials including Li_(4)Ti_(5)O_(12),TiO_(2)and Li_(2)ZnTi_(3)O_(8).Here,for the first time,the accurate theoretical capacity of Zn_(2)Ti_(3)O_(8)was confirmed to be 266.4 mAh/g.It was also found that both intercalation reaction and pseudocapacitance contribute to the actual capacity of Zn_(2)Ti_(3)O_(8),making it possibly higher than the theoretical value.Most importantly,the porous structure of Zn_(2)Ti_(3)O_(8)not only promotes the intercalation reaction,but also induces high pseudocapacitance capacity(225.4 mAh/g),which boosts the reversible capacity.Therefore,it is the outstanding pseudocapacitance capacity of porous Zn_(2)Ti_(3)O_(8)that accounts for high actual capacity exceeding the theoretical one.This work elucidates the superiorities of porous structure and provides an example in designing high-performance electrodes for lithium-ion batteries.

Study of antigen and antibody reaction in electrochemical reactions with ellipsometric spectroscopy

IN the study of antigen and antibody reaction with ellipsometric spectroscopy, most researchers calculated the thickness of antibody film, absorbance and film constant by mathematic models.But by using simple mathematic models, it is very hard to describe accurately the real state of the system. Huang and Ord proposed a new physical measurement (optical tracking rate,Vop), indicating the total change of △, Ψ in study of oxidation and reduction reaction of the iron electrode in alkaline solution. Many experimental results showed that the spectral peaks in Vop～t figure correspond to the turning points on the polarization curve. This work

Bi-Atom Electrocatalyst for Electrochemical Nitrogen Reduction Reactions

The electrochemical nitrogen reduction reaction(NRR)to directly produce NH3 from N_(2) and H_(2)O under ambient conditions has attracted significant attention due to its ecofriendliness.Nevertheless,the electrochemical NRR presents several practical challenges,including sluggish reaction and low selectivity.Here,bi-atom catalysts have been proposed to achieve excellent activity and high selectivity toward the electrochemical NRR by Ma and his co-workers.It could accelerate the kinetics of N_(2)-to-NH_(3) electrochemical conversion and possess better electrochemical NRR selectivity.This work sheds light on the introduction of bi-atom catalysts to enhance the performance of the electrochemical NRR.

Activation of Transition Metal(Fe,Co and Ni)-Oxide Nanoclusters by Nitrogen Defects in Carbon Nanotube for Selective CO_(2) Reduction Reaction

The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.

CHRONOABSORPTOMETRY FOR THE DETERMINATION OF KINETIC PARAMETERS OF ELECTRON TRANSFER REACTIONS USING LONG-OPTICAL-PATH ELECTROCHEMICAL CELL

A single potential step chronoabsorptometric method for the determination of ki- netic parameters of simple quasi-reversible reactions is described.It is verified by determining the kinetic parameters for the electroreduction of ferricyanide.A long-optical-path electro- chemical cell with a plug-in electrode is used.The thickness of solution layer is 0.55 mm

Electrochemical Determination of Rate Constants for Reactions of OH and its Application in the Evaluation of Anti-Oxidant Actions of Rheum

A single-sweep oscillopolarographic procedure is descrital which allows detethenahon of rateconstants for reachons of oH. For a wide range of compounds, the results fit well with rate constantspreviously obtained with other methods. Rate constants for reactions of six kinds of active compoundscontalned in rheum, a tradihonal Chinese herb, have been deteboned by this method. Rcationmechanism ha5 also been discussed.

Zeolite-mediated hybrid Cu^(+)/Cu~0 interface for electrochemical nitrate reduction to ammonia

The electrocatalytic conversion of reactive nitrogen species to ammonia is a promising strategy for efficient NH_(3) synthesis.In this study,we reveal that the hybrid Cu^(+)/Cu~0 interface is catalytically active for electrochemical ammonia synthesis from nitrate reduction.To maintain the hybrid Cu^(+)/Cu~0 state at negative reaction potentials,hydrophilic zeolite is used to modify Cu/Cu_(2)O electrocatalyst,which demonstrates an impressive NH_(3) production rate of 41.65 mg h^(-1) cm^(-2)with ~100% Faradaic efficiency of ammonia synthesis at-0.6 V vs.RHE.In-situ Raman spectroscopy unveil the high activity originates from the zeolite reconstruction at the electrode–electrolyte interface,which protects the valence state of Cu~0/Cu^(+) site under negative potential and promotes electrochemical activity towards NH_(3) synthesis.

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.

Recent advances and strategies in the stabilization of single-atom catalysts for electrochemical applications

Owing to the rapidly increasing consumption of fossil fuels,finding clean and reliable new energy sources is of the utmost importance.Thus,developing highly efficient and low-cost catalysts for electrochemical reactions in energy conversion devices is crucial.Single-atom catalysts(SACs)with maximum metal atom utilization efficiency and superior catalytic performance have attracted significant attention,especially for electrochemical reactions.However,because of the highly unsaturated coordination environment,the stability of SACs can be a challenge for practical applications.In this review,we will summarize the strategies to increase the stability of SACs and synthesizing stable SACs,as well as the application of SACs in electrochemical reactions.Finally,we offer a perspective on the development of advanced SACs through rational design and a deeper understanding of SACs with the help of in situ or operando techniques in electrochemical reactions.

Nitrogen-Doped Hierarchical Heterostructured Aerophobic MoS_(x)/Ni_(3)S_(2)Nanowires by One-pot Synthesis:System Engineering and Synergistic Effect in Electrocatalysis of Hydrogen Evolution Reaction

Non-noble metal electrocatalysis has witnessed rapid and profound performance improvements owing to the emergence of advanced nanosynthetic techniques.Integration of these nanotechniques can lead to synergistic performance enhancement,but such system-engineering strategies are difficult to achieve because of the lack of effective synthesis method.We hereby demonstrate an integrated approach that combines most of the existing nanotechniques in a facile one-pot synthesis.Material characterization reveals that the product shows key features intended by techniques including morphological,structural,doping,heterointerface,and surface wetting engineering.The as-obtained nitrogen-doped hierarchical heterostructured MoS_(x)/Ni_(3)S_(2)nanowires show an overpotential that is only50 mV higher than commercial Pt/C for hydrogen evolution reaction over current densities from 10 to 150 mA cm^(-2).Correlations between the adopted nanotechniques and the electrochemical reaction rates are established by evaluating the impacts of individual techniques on the activation energy,pre-exponential factor,and transfer coefficient.This indepth analysis provides a full account of the synergistic effects and the overall improvement in electrocatalytic performance of hydrogen evolution reaction.This work manifests a generic strategy for multipurpose material design in non-noble metal electrocatalysis.