Oxygen evolution reaction dynamics, faradaic charge. In energy storage, these include regenerative fuel cells see entry fuel cells, principles and thermodynamics, electrolyzers, metalair batteries, and solardriven watersplitting devices. They showed that when p atoms are introduced into the interior surface sites of graphene, the doped p atoms always move out of the planar surface, because of their large atomic radius in comparison with n atoms, and the pdoped or p,ncodoped. Determining the facile routes for oxygen evolution. Oxygen evolution reaction an overview sciencedirect topics. Oxygen reduction and evolution kinetics the role of licoo. Pressurepromoted irregular comop2 nanoparticles activated by. Herein, we report a template free and rapid highpressure synthesis protocol to fabricate irregular comop 2 nanoparticles for oer catalysts. Nov 19, 2018 oxygen evolution reaction oer plays a vital role in many renewable energy conversion and storage processes. Development of highly active bifunctional electrocatalyst using co. We investigated the roles of covalent bonding, separation of surface oxygen, and electrolyte ph on the oxygen evolution reaction oer on transition metal oxides by comparing catalytic onset potentials and activities of cacoo3 and srcoo3. However, doped sites for the different atoms are highly uncontrollable under.
Stereodefined codoping of spn and s atoms in fewlayer. A metalfree bifunctional electrocatalyst for oxygen. Iro2 is the only known oer catalyst with both high catalytic activity and stability in. Results revealed nanocristalline powder materials with ni 0. Heteroatomdoped carbon nanom aterials have been reported to be efficient metalfree electrocatalysts for orr in fuel cells for energy conversio n, as well as orr and oer in metalair batteries for energy. Covalencyreinforced oxygen evolution reaction catalyst. Using advanced quantum mechanics qm methods, we find that the ni,feooh systems feature synergy between fe and ni, in which the two. Compared with individual element doping, doping carbon materials with multiple heteroelements has more advantages for enhancing the oer performance. Pressurepromoted irregular comop2 nanoparticles activated.
Pdf optimizing the oxygen evolution reaction for electrochemical. Journal of the electrochemical society, 163 11 f3105f3112 2016 f3105 jes focus issue on electrolysis for increased renewable energy penetration activity and durability of iridium nanoparticles in the oxygen evolution reaction shaun m. Sunlightdriven water splitting or carbon dioxide co 2 reduction to make solar fuels is a promising solution to solar energy storage 1. Grafting cobalt diselenide on defective graphene for. Oxygen evolution from water is effected by oxygenic photosynthesis, electrolysis of water, and thermal decomposition of various oxides. Traditional metal refinery techniques such as electrodeposition see entry electrodeposition of electronic. Developing metal free catalysts with high catalytic activity for oxygen evolution reaction oer is essentially important for energy and environmentrelated techniques.
Here we report an iridium oxidestrontium iridium oxide iro x sriro3 catalyst formed during electrochemical testing by strontium leaching from surface layers. The high conductivity of graphene, coupled with the catalytic performance of nitrogen sites makes ndoped graphenic materials excellent candidates for metalfree oerorr. Oxygen evolution is a fourelectron process requiring two water molecules that. The reaction mechanism with free energy barriers at. Nife layered double hydroxides ldhs are promising for catalyzing the oxygen evolution reaction oer in alkaline media. Three seemingly simple reactions, the oxygen reduction reaction orr, oxygen evolution reaction oer and hydrogen evolution reaction her, are critical for clean and renewable energy technologies, such as fuel cells, batteries and watersplitting processes. Pdf oxygen evolution electrocatalysis on cobalt oxide.
Oxygen reduction reaction orr and oxygen evolution re action oer are critical to renewable energy conversion and storage technologies. A major challenge to the implementation of artificial photosynthesis ap, in which fuels are produced from abundant materials water and carbon dioxide in an electrochemical cell through the action of sunlight, is the discovery of active, inexpensive, safe, and stable catalysts for the oxygen evolution reaction oer. Perovskites have recently received substantial interest as they could be more costeffective than, while possess comparable catalytic activities with, the stateof. Owing to the increased surface area and ndoping, the selfsupporting electrocatalyst could effectively catalyze the oxygen evolution reaction, and was also utilized as the anode for an alkaline. Accomplishing these electrocatalytic reactions stresses the development of catalysts that are capable of mediating reactions that are in net multielectron, multiproton transformations. Orientation sensitivity of oxygen evolution reaction on hematite. It proved difficult to obtain reproducible polarisation data for bright anodes, and so an electrochemical pretreatment routine was devised. Highly efficient metalfree, carbonbased, bifunctional electrocatalysts for the oxygen evolution reaction oer and oxygen reduction reaction orr have attracted increased attention for use in electrochemical energy conversion systems, owing to their low cost and high activity. Herein, we develop an alcohol intercalation method to prepare ultrathin nife ldh with a unitcell.
Obviously, the slope of s 1 larger than s 2 and s 3 in fig. Goddard iii,b luca sementaa and giovanni barcaroa electrochemical waterbased energy cycles provide a most promising alternative to fossilfuel sources of energy. It utilizes the energy of light to split a water molecule into its protons and electrons for photosynthesis. Mar 19, 2018 highly efficient metal free, carbonbased, bifunctional electrocatalysts for the oxygen evolution reaction oer and oxygen reduction reaction orr have attracted increased attention for use in electrochemical energy conversion systems, owing to their low cost and high activity. Carbothermal reduction of semiconducting tio 2 into highly conductive titanium oxycarbide tio x c y was investigated. The oxygen evolution reaction oer is an enabler of several technological applications. Electrochemical reduction of co2 to useful chemicals or fuels is critical to closing the carbon cycle and preventing further deterioration of the environmentclimate. However, the kinetics of the oer are sluggish, even when facilitated by. The oxygen evolution reaction oer is a key component to applications of electrochemistry in energy and environment, but the reaction mechanism for oer on a bestperforming catalyst, the fedoped niooh ni,feooh, is under debate. Although noble metalbased catalysts such as iro 2 and ruo 2 exhibit good oer activity, their scarcity and high cost pose great constrains for largescale. Targeted efficiency of water electrolysis is still serious challenge predominantly due to the limitations in the performance of anode. Using advanced quantum mechanics qm methods, we find that the ni,feooh systems feature synergy between fe and ni, in which the two components assume the two. Pdf models and mechanisms of oxygen evolution reaction on. Oxygen evolution reaction on ni substituted co3o4 nanowire array electrodes.
Developing novel platinum group metalfree catalysts for. Pdf the oxygen evolution reaction on passive oxide. Herein, we reported the mndoped cop nanosheet arrays on flexible activated carbon cloth mncopcc for the effective oxygen evolution reaction oer at low overpotential and high current density. How to efficiently oxidize h2o to o2 oxygen evolution reaction, oer in photoelectrochemical cells pec is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. This work addresses the lowenergyefficiency problem of co2 reduction limited by sluggish oxygen evolution reaction oer on the anode side.
Nevertheless, cat alysts are needed to promote the her for hydrogen fuel. Identification of catalytic sites for oxygen reduction and. Stabilization of reactive co4o4 cubane oxygenevolution. Conventional noblemetalbased oer electrocatalysts like iro 2 and ruo 2 suffer from the limitations of high cost and scarce availability. The reaction mechanism with free energy barriers at constant. The gibbs free energies obtained from dft calculations for. Developing highly ordered and conductive phosphorousbased materials and identifying their active sites are critical to improve the catalytic performance for oxygen evolution reactions oers. In this thesis, the simple preparation of a cobaltbased catalyst for the oxygen evolution reaction oer is described and details of its structure, valency, mechanism of action, and. The oxygen reduction reaction orr and the oxygen evolution reaction oer are at the heart of metalair batteries. The electrocatalytic evolution of oxygen and hydrogen by. So far no oer mechanism has been fully explained atomistically with both thermodynamic and kinetics. Water splitting involves hydrogen evolution reaction her and oxygen evolution reaction oer, in which oer is the limiting factor and has attracted extensive research interest in the past few years. Aug 09, 2016 essential to the water splitting and co 2 reduction reactions is the oxygen evolution reaction oer.
Beyond the ratedetermining step in the oxygen evolution. By comparing the three morphologies of co3o4, the electrocatalytic properties show that the urchinlike spheres of co3o4 electrode has relative low overpotential and good electrocatalysis stability, indicating that the structure of urchinlike co3o4 spheres exhibit an easy. Herein, we report a templatefree and rapid highpressure synthesis protocol to fabricate irregular comop2 nanoparti. Us4497698a lanthanum nickelate perovskitetype oxide for. Both cubic, metallic perovskites have similar coiv intermediate spin states and onset potentials, but a substantially smaller lattice parameter and shorter. Here, we apply the free energy diagram approach to resolve the reaction mechanism of the oer over an iro2110 model anode in both acidic and alkaline. Beyond the volcano limitations in electrocatalysis oxygen.
The oxygen evolving reaction oer and the oxygen reduction reaction orr are key processes occurring in solar water splitting devices, fuel cells and metalair batteries. Optimizing the oxygen evolution reaction for electrochemical. In this work, ndoped carbon nanocages nccs with a porous selfsupported architecture and high specific surface. Oxygen evolution is the process of generating molecular oxygen o 2 by a chemical reaction, usually from water. Us4497698a us06521,973 us52197383a us4497698a us 4497698 a us4497698 a us 4497698a us 52197383 a us52197383 a us 52197383a us 4497698 a us4497698 a us 4497698a authority us united states prior art keywords anode lanthanum nickelate electrode cathode oxygen evolution prior art date 19830811 legal status the legal status is an assumption and is not a legal conclusion. Trends in electrocatalytic activity of the oxygen evolution reaction oer are investigated on the basis of a large database of ho and hoo adsorption energies on oxide surfaces. A highly active and stable iroxsriro3 catalyst for. Herein, a threedimensional monolithic and metalfree ndoped porous carbon cloth electrocatalyst was fabricated.
Department of chemistry and chemical biology, northeastern university. The mechanism of photosynthetic oxygen evolution has been studied for a. Conventional noblemetalbased oer electrocatalysts like iro2 and ruo2 suffer from the limitations of high cost and scarce availability. Herein, we report a hybrid catalyst consisting of cose 2 nanosheets grafted on defective graphene dg. Pdf the oxygen evolution reaction on passive oxide covered. Pdf beyond the volcano limitations in electrocatalysis. Pdf a profound change has taken place in understanding surface electrochemistry during watersplitting. Electrochemical behavior of nimo electrocatalyst for.
A monolithic metalfree electrocatalyst for oxygen evolution. The high conductivity of graphene, coupled with the catalytic performance of nitrogen sites makes ndoped graphenic materials excellent candidates for metal free oerorr. Developing novel platinum group metal free catalysts for alkaline hydrogen and oxygen evolution reactions deee0008082 pi. Uncovering nearfree platinum singleatom dynamics during. Highperformance oxygen evolution reaction oer electrocatalysts are needed to produce hydrogen for energy generation through a carbonfree route. Effect of morphology of co3o4 for oxygen evolution reaction. The thermally produced uniform carbon layer on tio 2 degussa p25 protects the tio 2 nanoparticles from sintering and, at the same time, supplies the carbon source for doping tio 2 with carbon. Goddard iii,b luca sementaa and giovanni barcaroa electrochemical waterbased energy cycles provide a most promising alternative to. Threedimensional structures of mn doped cop on flexible. Orientation sensitivity of oxygen evolution reaction on. I am investigating the electrochemical oxygen evolution reaction in alkaline solution.
The more vertical the slope of the straight line in the low frequency, the better performance in oxygen evolution reaction. Organic small molecule activates transition metal foam for efficient. Highly active oxygen evolution integrated with efficient. The free energies of four proton coupled electron transfer pcet steps and the oer overpotential were calculated and. Effect of morphology of co3o4 for oxygen evolution. Requiring four proton and electron transfers per oxygen molecule, the oer is the more complex of the two half reactions and is consequently responsible for the majority of inefficiency in electrolyzer. The development of electrocatalysts with high activity and low cost has attracted growing attentions in recent years. Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction oer limit the performance and commercialization of such devices. Herein, we reported the mndoped cop nanosheet arrays on flexible activated carbon cloth mncopcc for the effective oxygen evolution.
Apr 22, 2020 i am investigating the electrochemical oxygen evolution reaction in alkaline solution. Jun 05, 2018 the oxygen evolution reaction oer is a key component to applications of electrochemistry in energy and environment, but the reaction mechanism for oer on a bestperforming catalyst, the fedoped niooh ni,feooh, is under debate. Sujit kumar ghosh, hasimur rahaman, in noble metalmetal oxide hybrid nanoparticles, 2019. Oxygen evolution reaction oer is a limiting reaction in the process of generating molecular oxygen through chemical reaction, such as the oxidation of water during oxygenic photosynthesis, electrolysis of water into oxygen and hydrogen, and electrocatalytic oxygen. Exceptional oxygen evolution reactivities on cacoo3 and. This reaction is kinetically sluggish and demands an efficient electrocatalyst 2. Pdf electrochemical waterbased energy cycles provide a most promising alternative to. The development of efficient and durable noble metal.
Essential to the water splitting and co 2 reduction reactions is the oxygenevolution reaction oer. Fully oxidized nife layered double hydroxide with 100%. Oxygen evolution reaction oer plays a vital role in many renewable energy conversion and storage processes. Oer oer is the name of a german noble family from oererkenschwick, westphalia. Herein, a threedimensional monolithic and metal free ndoped porous carbon cloth electrocatalyst was fabricated. So far, dopedfree and noncovalent cnts with co3o4hybrid bifunctional catalyst for orr. However, the catalytic performance of uptonow reported cose 2based oer catalysts is still far below commercial expectation. The reaction is part of the lightdependent reactions of photosynthesis in cyanobacteria and the chloroplasts of green algae and plants. Sep 25, 2014 the oxygen evolution reaction oer is an enabler of several technological applications. Identification of catalytic sites for oxygen reduction and oxygen evolution in ndoped graphene materials.
Cobalt diselenide cose 2 has been demonstrated to be an efficient and economic electrocatalyst for oxygen evolution reaction oer both experimentally and theoretically. Optimal geometrical configuration of cobalt cations in spinel. In this paper, three different morphological co3o4 electrodes for oxygen evolution reaction oer have been synthesized. Optimal geometrical configuration of cobalt cations in. Targeted efficiency of water electrolysis is still serious challenge predominantly due to the limitations in the performance of anode reaction oxygen evolution reaction. Reaction mechanism of the oxygen evolution reaction on conventional rutile ruthenia and ni and co modified ruthenia on the 110 surface. Oxygen evolution mediated by cobased thin film electrocatalysts. Although noble metalbased catalysts such as iro 2 and ruo 2 exhibit good. The only active oer catalysts for coupling co2 reduction in neutral conditions are. Catalysts free fulltext oxygen evolution reaction of comno. Perovskites have recently received substantial interest as they could be more costeffective than, while possess comparable catalytic activities with, the stateoftheart iro 2 and ruo 2 electrocatalysts for the oer. Universality in oxygen evolution electrocatalysis on oxide. Oxygen evolution reaction water electrolysis as a key technology for the storing of renewable electricity is one of the principal research areas in our group. Introduction one major roadblock on the way to a sustainable energy infrastructure based on renewable energies is an appropriate gridscale chemical energy storage solution.
Herein, we shed light on the behavior of li2o2 oxidation by exploiting various in situ imaging, gas analysis, and electrochemical methods. Optimizing the oxygen evolution reaction for electrochemical water oxidation by tuning solvent properties alessandro fortunelli,a,b william a. Mar 16, 2011 trends in electrocatalytic activity of the oxygen evolution reaction oer are investigated on the basis of a large database of ho and hoo adsorption energies on oxide surfaces. The theoretical overpotential was calculated by applying standard density functional theory in combination with the computational standard hydrogen electrode she model. Sanjeev mukerjee department of chemistry and chemical biology, northeastern university 360 huntington ave, boston, ma 02115 april 30th, 2019 project id. A nickel iron diselenidederived efficient oxygenevolution. Activity and durability of iridium nanoparticles in the. Electrophoretic deposition of znco2o4 spinel and its electrocatalytic properties for oxygen evolution reaction.
1195 1397 577 1091 301 656 250 272 54 1033 1328 1282 690 570 1605 1360 666 345 1351 656 438 383 1369 1470 1214 1573 826 689 424 279 726 612 1579 697 745 484 931 554 270 1065 519 363 959 240 1254