Oxygen Evolution Reaction on Nanoporous Gold Modified with Ir and Pt: Synergistic Electrocatalysis between Structure and Composition

Active oxygen evolution reaction electrocatalysts for water splitting have received great attention because of their importance in the utilization of renewable energy sources. Here, the electrochemical oxygen evolution reaction activities of a nanoporous gold (NPG)‐based electrode in acidic media are investigated. The dependence of the oxygen evolution reaction activity on the NPG surface area shows that the large electrochemical surface areas of the NPG are effectively utilized to enhance electrocatalytic activity. The NPG surfaces are modified with Pt using atomic layer electrodeposition methods, and the resulting NPG@Pt exhibited enhanced electrocatalytic activities compared to those of the NPG and flat Pt electrodes. Ir‐modified NPG (NPG@Ir) electrodes are prepared by spontaneous exchange of Ir on NPG surfaces and exhibit enhanced electrocatalytic activity compared to that of flat Ir surfaces. The modification of NPG@Pt with Ir results in NPG@Pt/Ir electrodes, and their electrocatalytic activities exceed those of NPG@Ir. The enhanced oxygen evolution reaction activity on NPG@Pt/Ir over that on NPG@Ir surfaces is examined by X‐ray photoelectron spectroscopy. The oxygen evolution reaction activity on NPG@Pt/Ir surfaces demonstrates synergistic electrocatalysis between the nanoporous surface structure and active electrocatalytic components.     

An Active Hybrid Electrocatalyst with Synergized Pyridinic Nitrogen-Cobalt and Oxygen Vacancies for Bifunctional Oxygen Reduction and Evolution

A hybrid bifunctional oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) NiCo2O4-x/NLG with rich pyridinic-nitrogencobalt coordination and oxygen v...     

FeCo alloy/N,S dual-doped carbon composite as a high-performance bifunctional catalyst in an advanced rechargeable zinc-air battery

The rational design and development of cost-effective,high-performance,and stable bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalysts are essential for rechargeable zinc-air batteries.Herein,a novel FeCo composite composed of alloy nanoparticles embedded in an N,S dual-doped carbon matrix(FeCo/NSC)was prepared via one-step carbonization of amphiphilic dodecanethiol-metal salts wrapped in carbon nitride(C₃N₄).The compact combination of dual metalalloys and dual-doped carbon endowed the composite with the active sites for the ORR and OER,achieving efficient electrical transmission and highly efficient bifunctional catalytic performance.The obtained FeCo-1/NSC catalyst exhibited excellent electrocatalytic activity with a half-wave potential of 0.82 V(vs.RHE)for the ORR and a low overpotential of 0.325 V at 10 mA cm^-2 for the OER.The liquid Zn-air battery with FeCo-1/NSC as an air electrode displayed excellent charge-discharge performance,high power density,and robust charge-discharge stability for 150 h compared to the 20%Pt/C+RuO₂ counterpart.Furthermore,the FeCo-1/NSC-based flexible solid-state Zn-air battery exhibited a higher power density and good charge-discharge stability over 10 h of operation.Thus,a promising strategy for bifunctional electrocatalyst development as part of rechargeable and wearable Zn-air batteries was provided.     

Self-supported hollow Co(OH)2/NiCo sulfide hybrid nanotube arrays as efficient electrocatalysts for overall water splitting

Journal of Solid State Electrochemistry - Developing low-cost and earth-abundant electrocatalysts with high activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER)...     

Earth-abundant coal-derived carbon nanotube/carbon composites as efficient bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

The exploration of active and robust electrocatalysts for both the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is the bottleneck to realize the commercialization of rechargeable metal-air batteries and regenerative fuel cells.Here we report facile synthesis of three-dimensional(3 D)carbon nanotube(CNT)/carbon composites using earth-abundant coal as the carbon source,hydrogen reductant and heteroatom dopant to grow CNTs.The prepared composite featuring 3 D structural merits and multiple active sites can efficiently catalyze both ORR and OER,affording high activity,fast kinetics,and long-term stability.With the additional incorporation of manganese,the developed catalyst afforded a potential difference of 0.80 V between ORR at the half wave potential and OER at a current density of 10 mA cm^-2.The optimized sample has presented excellent OER performance within a constructed solar-powered water splitting system with continuously generating oxygen bubbles at anode.Notably,it can be further used as a durable air-electrode catalyst in constructed Zn-air battery,delivering an initial discharge/charge voltage gap of 0.73 V,a remained voltaic efficiency of 61.2%after 160 cycles and capability to power LED light for at least 80 h.This study provides an efficient approach for converting traditional energy resource i.e.coal to value-added alternative oxygen electrocatalysts in renewable energy conversion systems.     

Current trends in the description of lanthanum strontium manganite oxygen electrode reaction mechanism in a high-temperature solid oxide cell

This review summarizes recent progress in understanding the oxygen reduction and evolution reactions at the lanthanum strontium manganite electrode of a high-temperature solid oxide cell. Information provided here is put into the perspective of the defect chemistry of lanthanum strontium manganite and its impact on the electrode reaction mechanisms itself. After summarizing recent views on the oxygen reduction reaction mechanism, the focus turns to the oxygen evolution reaction, which is significantly less treated in the literature. A combination of the information in the literature on both reactions was the basis for modified reaction mechanism of the oxygen evolution reaction to be proposed under consideration of recent experimental observations and theoretical findings.     

Embedding FeSb alloy nanoparticles in N-doped carbon layers as an efficient bifunctional electrocatalyst for zinc-air battery

Journal of Solid State Electrochemistry - Due to the intrinsic sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), developing highly efficient and inexpensive...     

Hydrogen energy currency: Beyond state-of-the-art transition metal oxides for oxygen electrocatalysis

In this opinion piece, we highlight and discuss beyond state-of-the-art transition metal oxide materials for the oxygen evolution reaction and oxygen reduction reaction, which are essential for the renewable energy conversion and storage of H₂ to electricity. We pinpoint some of the synthetic routes taken and discuss essential measurements required in the highlighted works, which others should undertake to achieve highly active and stable oxygen evolution reaction and oxygen reduction reaction catalysts in both acidic and alkaline media.     

Ag(I)与Co(II)离子对阳极析氧过程的电催化作用

Influence of Ag(Ⅰ), Co(Ⅱ) and Ni(Ⅱ) ions on oxygen anodic evolution at Pt and Ti/Pt/PbO2 electrodes was investigated in surphuric acid solutions. The oxygen evolution reaction at Ti/Pt/PbO2 electrode in surphuric acid solutions is characterized by two linearφ~ lgi relationships. At low c.d. it is close to 2.303RT/(1+β)F, whereas at high c.d. it is close to 2.303RT/βF. In the presence of Ag(Ⅰ) or Ni(Ⅱ) ions in the electrolytic solution the Tafel slope of oxygen evolution tends to be low, 2.303RT/(1+β)F (withβ=0.5). However, the oxygen evolution reaction at Pt electrodes in H2SO4 or CoSO4﹢H2SO4 solutions is characterized by one linearφ~ lgi relationship. The Tafel slope is close to 2.303RT/βF. In the presence of Ag(Ⅰ) or Ni(Ⅱ) ions in the electrolytic solution the Tafel slope of oxygen evolution tends to be low, 2.303RT/(1+β)F. The oxygen anodic evolution reactions are catalyzed by Ag(Ⅰ), Co(Ⅱ) and Ni(Ⅱ) ions in the electrolytic solution. When Ag(Ⅰ) or Ni(Ⅱ) was mixed with Co(Ⅱ), a promising catalyst for oxygen anodic evolution with higher catalyst activity than either of them alone was found. A comparison of the PbO2 electrode and the Pt electrode has also been given.     

Boosting overall water splitting by incorporating sulfur into NiFe(oxy)hydroxide

Developing highly active and cost-effective electrocatalysts for enhancing the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is a significant challenge for overall water splitting.Sulfur-incorporated nickel iron(oxy)hydroxide(S-NiFeOOH)nanosheets were directly grown on commercial nickel foam using a galvanic corrosion method and a hydrothermal method.The incorporation of sulfur into NiFeOOH enhanced the catalytic activity for the HER and OER in 1 M KOH electrolyte.The enhanced catalytic activity is attributed to the change in the local structure and chemical states due to the incorporation of sulfur.High performance for overall water splitting was achieved with an alkaline water electrolyzer.This was realized by employing S-NiFeOOH as a bifunctional electrocatalyst,thereby outperforming a water electrolyzer that requires the usage of precious metal electrocatalysts(i.e.,Pt/C as the HER electrocatalyst and IrO₂ as the OER electrocatalyst).Moreover,when driven by a commercial silicon solar cell,an alkaline water electrolyzer that uses S-NiFeOOH as a bifunctional electrocatalyst generated hydrogen under natural illumination.This study shows that S-NiFeOOH is a promising candidate for a large-scale industrial implementation of hydrogen production for overall water splitting because of its low cost,high activity,and durability.In addition,the solar-driven water electrolyzer using S-NiFeOOH as a bifunctional electrocatalyst affords the opportunity for developing effective and feasible solar power systems in the future.     

Insights into dimethyl sulfoxide decomposition in Li-O2 battery: Understanding carbon dioxide evolution

DMSO has been widely investigated as a potential electrolyte for the Li-air battery systems, however its stability has been a topic of debate in the research community. In this communication we have identified the side reaction products during the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on Au in dimethyl sulfoxide-based electrolyte for Li-air battery by a combination of in-situ analytical tools: EQCM, SNIFTIRS, DEMS and XPS, in particular the evolution of CO₂ from the solvent decomposition.     

Bifunctional Catalysts for Reversible Oxygen Evolution Reaction and Oxygen Reduction Reaction

Metal-air batteries (MABs) and reversible fuel cells (RFCs) rely on the bifunctional oxygen catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Finding efficient bifunctional oxygen catalysts is the ultimate goal and it has attracted a great deal of attention. The dilemma is that a good ORR catalyst is not necessarily efficient for OER, and vice versa. Thus, the development of a new type of bifunctional oxygen catalysts should ensure that the catalysts exhibit high activity for both OER and ORR. Composites with multicomponents for active centers supported on highly conductive matrices could be able to meet the challenges and offering new opportunities. In this Review, the evolution of bifunctional catalysts is summarized and discussed aiming to deliver high-performance bifunctional catalysts with low overpotentials.     

The Common Intermediates of Oxygen Evolution and Dissolution Reactions during Water Electrolysis on Iridium

Understanding the pathways of catalyst degradation during the oxygen evolution reaction is a cornerstone in the development of efficient and stable electrolyzers, since even for the most promising Ir based anodes the harsh reaction conditions are detrimental. The dissolution mechanism is complex and the correlation to the oxygen evolution reaction itself is still poorly understood. Here, by coupling a scanning flow cell with inductively coupled plasma and online electrochemical mass spectrometers, we monitor the oxygen evolution and degradation products of Ir and Ir oxides in situ. It is shown that at high anodic potentials several dissolution routes become possible, including formation of gaseous IrO₃. On the basis of experimental data, possible pathways are proposed for the oxygen‐evolution‐triggered dissolution of Ir and the role of common intermediates for these reactions is discussed.     

Noble-Metal-Free Doped Carbon Nanomaterial Electrocatalysts

Electrocatalytic processes, such as oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO₂RR), play key roles in various sustainable energy storage and production devices and their optimization in an ecological manner is of paramount importance for mankind. In this inclusive Review, we aspire to set the scene on doped carbon-based nanomaterials and their hybrids as precious-metal alternative electrocatalysts for these critical reactions in order for the research community not only to stay up-to-date, but also to get inspired and keep pushing forward towards their practical application in energy conversion.     

Ultrasmall Pt2Sr alloy nanoparticles as efficient bifunctional electrocatalysts for oxygen reduction and hydrogen evolution in acidic media

Electrocatalytic oxygen reduction reaction(ORR)and hydrogen evolution reaction(HER)in acidic media are vital for the applications of renewable energy electrolyzers.However,the low mass activity of noble Pt urgently needs to be improved due to the strong binding energetics of oxygen species(*O)with Pt sites.Here we report fine PtxSr alloy(-2 nm)supported on N-doped carb on(NC)pyrolyzing from ZIF-8 as bifunctional electrocatalysts toward ORR and HER in acidic media.The representative Pt₂Sr/NC exhibits an onset potential of 0.94 V vs.RHE and half-wave potential of 0.84 V toward ORR,and a low over-potential of 27 mV(10 mA cm^-2)toward HER,respectively.Significantly,the mass activities of Pt₂Sr/NC are 6.2 and 2.6 times higher than that of Pt/C toward ORR(at 0.9 V)and HER(at-30 mV),respectively.Simultaneously,Pt₂Sr/NC possesses a retention rate of 90.97%toward acidic ORR after 35000 s of continuous operation.Through density functional theory(DFT)calculations and X-ray photoelectron spectroscopy analysis,the incorporation of Sr into Pt forming Pt₂Sr alloy redistributes the electronic structures of Pt-Pt bonds,changing the rate-determining step for the ORR on Pt sites from the formation of*OH from*O to the generation of*OOH along with decreasing the energy barrier,which is also confirmed by the downshift of d band center.Meanwhile,the downshift of d band center also leads to the optimization of the adsorption energy(H*)with Pt,significantly improving Pt₂Sr/NC toward HER.     

Electrochemical properties of Ebonex®/Pt anodes

The electrochemical behavior of platinized Ebonex® was studied. The electrochemical and semiconductor properties of electrodes can be varied within wide limits by thermal treatment of Ebonex®/Pt, which selectively affects the electrocatalytic activity of anodes in the oxygen evolution reaction. The reduction peak of platinum oxides on the cyclic voltammetry (CV) curves can be used as a correlation parameter when evaluating the electrocatalytic activity of Ebonex®/Pt electrodes in the oxygen evolution reaction.     

二维金属有机框架纳米片的合成及在超电容和电催化领域的应用

二维金属有机框架(2D MOF)纳米片具有丰富且易暴露的表面活性位点、 高度有序的孔结构以及多样且可调的化学成分, 在电化学能量存储与转化中有利于降低反应电位, 提高扩散速率和反应速率. 关于2D MOF应用于电化学存储与转化的研究已有大量报道. 本文综合评述了近几年2D MOF的合成进展及其在超电容(SC)、 析氧反应(OER)、 析氢反应(HER)、 氧还原反应(ORR)和二氧化碳还原反应(CRR)的应用, 并对2D MOF作为电催化材料的研究现状和发展前景进行了总结与展望.     

Carbon‐Based Metal‐Free Catalysts for Electrocatalysis beyond the ORR

Besides their use in fuel cells for energy conversion through the oxygen reduction reaction (ORR), carbon‐based metal‐free catalysts have also been demonstrated to be promising alternatives to noble‐metal/metal oxide catalysts for the oxygen evolution reaction (OER) in metal–air batteries for energy storage and for the splitting of water to produce hydrogen fuels through the hydrogen evolution reaction (HER). This Review focuses on recent progress in the development of carbon‐based metal‐free catalysts for the OER and HER, along with challenges and perspectives in the emerging field of metal‐free electrocatalysis.     

Oxygen evolution on SrFeO3 electrode

Oxygen evolution reactions on SrFeO₃ were investigated in alkaline and acidic solutions. It was found that the catalytic activity for the oxygen evolution reaction in the alkaline solution is high. The following reaction steps (V)+Fe+2H₂O→(O)+FeOH₂+2H⁺+2e^? in acidic solution and FeOH+OH^?→FeO^?+H₂O in alkaline solution are presumed to be rate-controlling in the anodic evolution of oxygen on SrFeO₃ electrode, where (V) denotes oxygen vacancy on the electrode surface. The reaction mechanism and the catalytic property are discussed in connection to the band structure of the oxide.     

Mechanism of oxygen reactions at porous oxide electrodes. Part 2--Oxygen evolution at RuO2, IrO2 and Ir(x)Ru(1-x)O2 electrodes in aqueous acid and alkaline solution

The kinetics and mechanism of the oxygen evolution reaction at a series of RuO(2)/IrO(2) mixed oxides in aqueous acid and alkaline solution has been examined using a variety of electrochemical methods. Factors affecting the electrocatalytic activity have been elucidated and novel oxygen evolution mechanisms in terms of reactive oxyruthenium and oxyiridium surface groups are proposed.