Novel electrocatalysts for generating oxygen from alkaline water electrolysis

We have obtained spinel-type Co₃O₄ and La-doped Co₃O₄ in the form of thin film on Ni, using microwave-assisted synthesis, which dramatically exhibit very low overpotentials for the oxygen evolution reaction (OER). Investigations have shown that at the apparent current density of 100 mA cm⁻² in 1 mol dm⁻³ KOH at 25 °C, the new electrodes, Co₃O₄ (oxide loading = 3.4 ± 0.3 mg cm⁻²) and La-doped Co₃O₄ (oxide loading = 2.8 ± 0.4 mg cm⁻²), produce overpotentials, 235 ± 7 and 224 ± 8 mV, respectively. Such low overpotentials for the OER, to our knowledge, have not been found on any mixed oxide electrode material reported in literature till today. Small La addition improved the BET surface area and porosity of the oxide catalyst powder and reduced the charge transfer resistance for the OER on the electrode made of oxide powder.     

Tuning the electronic structure of the earth-abundant electrocatalysts for oxygen evolution reaction(OER)to achieve efficient alkaline water splitting-A review

Tuning the electronic structure of the electrocatalysts for oxygen evolution reaction(OER)is a promising way to achieve efficient alkaline water splitting for clean energy production(H2).At first,this paper introduces the significance of the tuning of electronic structure,where modifying the electronic structure of the electrocatalysts could generate active sites having optimal adsorption energy with OER intermediates,and that could diminish the energy barrier for OER,and that could improve the activity for OER.Later,this paper reviews the tuning of electronic structure along with catalytic performances,synthetic methodologies,chemical properties,and DFT calculations on various nanostructured earth-abundant electrocatalysts for OER in alkaline environment.Further,this review discusses the tuning of the electronic structure of the several nanostructured earth-abundant electrocatalysts including oxide,(oxy)hydroxide,layered double hydroxide,alloy,metal phosphide/phosphate,nitride,sulfide,selenide,carbon containing materials,MOF,core-shell/hetero/hollow structured materials,and materials with vacancies/defects for OER in alkaline environment(including activity:overpotential(η)of ≤200 mV at10 m A cm^-2;stability:≥100 h;durability:≥5000 cycles).Then,this review discusses the robust stability of the electrocatalysts for OER towards practical application.Moreover,this review discusses the in situ formation of thin layer on the catalyst surface during OER.In addition,this review discusses the influence of the adsorption energy of the OER intermediates on OER performance of the catalysts.Finally,this review summarizes the various promising strategies for tuning the electronic structure of the electrocatalysts to achieve enhanced performance for OER in alkaline environment.     

Recent advances in metal-organic frameworks for oxygen evolution reaction electrocatalysts

The anodic oxygen evolution reaction(OER) can be combined with various cathodic reactions to enable the electrochemical synthesis of diverse chemicals and fuels, particularly in water electrolysis for hydrogen production. It is however exhibiting a high overpotential due to the sluggish four-electron transfer process, which is considered the decisive reaction in energy conversion systems. In recent years, metal-organic frameworks(MOFs) have emerged as the ideal catalysts for accelerating OER. Th...     

Recent advances in spinel-type electrocatalysts for bifunctional oxygen reduction and oxygen evolution reactions

The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electrolysers, fuel cells, and metal–air batteries emerge in response to the need for developing sustainable energy carriers, in which the oxygen evolution reaction and the oxygen reduction reaction play key roles. However, both reactions suffer from sluggish kinetics that restricts the reactivity. Therefore, it is vital to probe into the structure of the catalysts to exploit high-performance bifunctional oxygen electrocatalysts. Spinel-type catalysts are a class of materials with advantages of versatility, low toxicity, low expense, high abundance, flexible ion arrangement, and multivalence structure. In this review, we afford a basic overview of spinel-type materials and then introduce the relevant theoretical principles for electrocatalytic activity, following that we shed light on the structure–property relationship strategies for spinel-type catalysts including electronic structure, microstructure, phase and composition regulation,and coupling with electrically conductive supports. We elaborate the relationship between structure and property, in order to provide some insights into the design of spinel-type bifunctional oxygen electrocatalysts.     

Disorder engineering in transition metal dichalcogenides toward efficient high current density reduction electrocatalysts

In this perspective, we highlight the importance of nanoscale disorder and mesoscale morphology to enhance the activity and tune the selectivity of group VI transition metal dichalcogenide electrocatalysts toward two paramount reductions reactions as H₂ evolution reaction and CO₂ reduction. The strategy we propose takes advantage of the metastable nanoscale atomic arrangement of highly disordered and amorphous materials, to overcome the limits of the typical transition metal dichalcogenide crystalline catalysts. For the H₂ evolution reaction, going beyond the creation of point defects in crystalline structures in favor of fully amorphous organizations not only increases the per-site activity and active surface area but also improves the conductivity and the reaction kinetics. In addition, the incorporation of nanoscale disorder promotes the formation of complex products in CO₂ reduction through reaction pathways inaccessible on other sites. On the other hand, the mesoscale architecture of the catalyst controls mass transport in both the liquid and gas phase, as well as determines the real-world performance of catalysts. We suggest that by exploiting disordered nanoscale organization and controlled mesoscale features, the performances can be drastically improved to reach the state-of-art metallic electrocatalysts.     

Bimetallic cobalt-nickel coordination polymer electrocatalysts for enhancing oxygen evolution reaction

Coordination polymers（CPs） have great potential to be used in electrocatalysis owing to their designable compositions and structures. It is highly challenging to apply CPs as electrocatalysts for oxygen evolution reaction（OER） on account of insufficient catalytic efficiency and relatively poor stability of current electrocatalysts. Herein, through a mixed-metal strategy, one-dimensional Co_xNi_1-x-HIPA with dual active sites was synthesized and studied for OER electrocatalyst...     

过渡金属电催化剂在硅基光阳极分解水产氧中的作用

光电化学分解水可将太阳能转换为绿色的氢能,为目前的能源危机和环境问题提供了一种理想的解决方案.在分解水反应中,涉及四空穴过程的产氧半反应是制约性能的关键步骤,往往需要在半导体表面沉积电催化剂以加速产氧反应动力学.因此,全面理解电催化剂在光电化学分解水体系中的作用至关重要.在目前的产氧电催化剂中,过渡金属羟基氧化物电催化剂(MOOH,M=Fe,Co,Ni)因其环保、廉价、高效以及稳定的特性,已被广泛用于半导体光阳极分解水器件中.而且,MOOH可用简单的电沉积方法沉积在光电极表面,易于大面积制备.然而,电沉积法制备的MOOH具有复杂的结构,对其作用机制的全面理解更加困难.因此,本文以电沉积MOOH修饰的硅基光阳极(n⁺p-Si/SiO_x/Fe/FeOx/MOOH)作为模型,研究了不同电催化剂对硅光阳极光电化学产氧性能的影响.实验发现电催化剂的界面优化在电催化剂修饰的光电极中发挥着重要作用,这是因为优化的界面可以提升界面电荷传输,提供更多的催化反应活性位点以及更高的本征催化活性,从而更有利于光解水性能的提升.该项研究揭示了电催化剂在光解水器件中的作用,并为今后高效光解水器件的设计提供了一定指导.首先在多晶n⁺p-Si基底上热蒸镀了一层30 nm的金属Fe膜,并通过电化学活化将Fe膜表面转换为FeOx得到Fe/FeOx(记作aFe)界面层,然后利用电沉积方法制备MOOH表面修饰层,最终得到n⁺p-Si/SiO_x/aFe:MOOH光阳极.X射线光电子能谱、拉曼光谱以及扫描电子显微镜表面元素成像的表征结果均证实电极表面由于界面层金属Fe元素的掺杂而形成了Fe1-xNixOOH.在模拟太阳光下用于光解水产氧时,n⁺p-Si/SiO_x/aFe:NiOOH电极的起始电位为~1.01 VRHE(相对于可逆氢电极的电势),在1.23 VRHE下的光电流为38.82 mA cm^-2,显著优于n⁺p-Si/SiO_x/aFe、n⁺p-Si/SiO_x/aFe:FeOOH以及n⁺p-Si/SiO_x/aFe:CoOOH三个对比样品,且其稳定性达到75 h.另外,我们发现n⁺p-Si/SiO_x/aFe:MOOH电极的光电化学产氧性能均显著高于n⁺p-Si/SiO_x/aFe电极,且p++-Si/SiO_x/aFe:MOOH的电催化产氧性能也高于p++-Si/SiO_x/MOOH,不仅证明了aFe界面层对Si与MOOH层之间的界面接触作用的有效调控,而且表明双电催化剂体系(aFe:MOOH)的电催化产氧活性高于单电催化剂(MOOH).热力学分析表明,n⁺p-Si/SiO_x/aFe:MOOH光阳极的光电压大小与其光解水产氧性能并不一致,从而排除了热力学因素对性能的关键影响.进一步从塔菲尔斜率、电化学活性表面积和电化学阻抗谱对各电极的动力学进行了分析,证明了动力学因素在上述光阳极产氧性能中的主导作用.同时发现,由于aFe:NiOOH双电催化剂具有更高的本征电催化产氧性能,提供了更多的表面活性位点以及更有效地促进了光生载流子的传输,对动力学的提升效果更显著,从而使n⁺p-Si/SiO_x/aFe:NiOOH光阳极表现出最高的光解水产氧性能.     

电催化析氧反应过渡金属磷化物和硫化物催化剂研究进展（英文）

对化石能源的依赖所造成的环境污染和能源危机在全球引起了广泛的关注.氢能由于其高能量密度、低分子质量以及清洁无污染的优点,被认为是人类根本性解决能源与环境等全球性问题的理想替代能源.电解水是生产高纯度氢的重要方法,是现代清洁能源技术的重要组成部分.水电解由阴极析氢(HER)和阳极析氧(OER)两个半反应构成.对于HER反应,其反应是基于二电子转移过程,反应过程相对容易进行.相比于HER反应,OER反应涉及四电子转移及氧-氧键形成,其反应动力学缓慢,是影响水电解效率的主要原因.因此,为了提高电解水制氢的能量转化效率,发展OER电催化剂成为水电解制氢技术的关键.在过去的十余年间,硫化物、硒化物、磷化物、硼化物等非贵金属基OER电催化剂被大量地研究及报道并取得了长足发展.在这些催化剂中,金属磷化物和硫化物不仅具有成本优势,而且在析氧过电位、耐久性方面正趋接近甚至超越RuO_2和IrO_2等贵金属催化剂,颇具应用潜力.本文总结磷化物和硫化物作为OER电催化剂的研究进展,重点介绍了磷化物和硫化物性能提升策略及其在OER过程中催化反应活性位的变化.本文首先介绍了电解水析氧反应在不同电解质中的反应机理,讨论了析氧反应在动力学和热力学过程的主要障碍.通过对大量文献的归纳,本文分别综述了磷化物和硫化物的化学性质、合成方法和催化性能,介绍了近年来磷化物和硫化物的重要研究进展.通过分析催化剂导电性、质子传输、活性面积、界面化学等因素对催化析氧反应的影响,总结了磷化物和硫化物电催化OER性能提升的策略.由于磷化物和硫化物在OER强氧化条件下,电催化剂表面的成分、物相及结构均会发生显著变化,进而催化反应活性位也会发生相应改变.本文综述了磷化物和硫化物在OER反应过程前后表面组分的变化,探讨了磷化物和硫化物作为OER电催化剂的活性组分,为进一步提高磷化物和硫化物的电催化析氧反应性能提供了崭新的思路.     

Ultrathin NiFeS nanosheets as highly active electrocatalysts for oxygen evolution reaction

The development of efficient and cost-effective oxygen evolution reaction (OER) electrocatalysts is crucial for clean energy conversion and storage devices, such as water-splitting, CO₂ reduction, and metal-air batteries. Herein, we report an efficient 2-dimensional OER catalyst of ultrathin nickel-iron sulfide nanosheets (NiFeS-NS). Dodecanethiol is employed in the synthesis, which prohibits the growth along the Z-axis, thus a nanosheet is obtained. The NiFeS-NS shows high OER catalytic activity, which only requires a small overpotential of 273 mV to achieve the OER current density of 10 mA/cm² in alkaline electrolyte, and almost no decay after 150 h of chronopotentiometry test. The high performance is attributed to the 2-dimensional structure, the synergistic effect from the Ni and Fe components which promotes the formation of the high valence Ni species, and the tuning effect from the in-situ generated sulfate doping. This work demonstrates the advantages of the 2-dimensional sulfides in electrocatalysis.     

Cu-alanine complex-derived CuO electrocatalysts with hierarchical nanostructures for efficient oxygen evolution

Nowadays,Cu-based materials have attracted extensive attention as electrocatalysts,while the inherent reason of the filling of high anti-bonding state of Cu d band(3 d~(10)4 s~1) makes it difficult to hybridize with O2 p band of oxygen intermediates during the adsorption process of oxygen evolution reaction(OER).To increase the efficiency of Cu-based electrocatalysts,efforts have been made to optimize the electronic structures and to create surface defects and hierarchical nanostructures with more exposed accessible active sites.Herein,we report a facile method for preparing CuO electrocatalysts with hierarchical nanostructures using the Cu-alanine complex as a precursor through room-temperature chemical precipitation and subsequent calcination in air.Investigations of products obtained at different calcination temperatures reveal the relationship between OER activities and the material characteristics such as specific surface areas,crystal growth orientations,and element components.The product obtained at 500℃ exhibits the smallest overpotential of 290 mV in 1.0 mol/L KOH for electrocatalyzing OER.Combining with various characterizations of CuO electrocatalysts after OER activities,the possible catalytic mechanism and the influence factors of their OER performance are also discussed.     

Nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for oxygen reduction and oxygen evolution reactions

The oxygen reduction/evolution reactions (ORR/OER) are a key electrode process in the development of electrochemical energy conversion and storage devices,such ...     

Ag nanobelts: synthesis, morphological evolution, and their use as electrocatalysts for oxygen reduction

The recent development of 1D nanomaterials of controllable size, composition, and structure has opened up enormous possibilities for engineering catalysts with enhanced activity and selectivity. Herein, we report a one-step strategy for the fabrication of versatile silver nanomaterials. Tailored structures, such as nanobelts, nanowires, and nanocables, were conveniently synthesized by adjusting the reaction conditions. The novelty of this synthesis is in a one-pot procedure that combines the sequential formation of precursor nucleation, in situ polymerization, and crystal shaping under mild conditions. The as-synthesized cables consisted of a metallic core (Ag) and an organic outer shell (poly(o-anisidine), POA). Control experiments demonstrated that the introduced organic monomer (OA) not only acted as the nanoreactor and capping agent, but also a modest reducer for controlled crystal growth at the hydrophilic interface. Electrocatalytic tests showed enhanced stability and activity towards the reduction of oxygen, which was believed to be closely associated with the core-shell structural characteristics of the nanomaterials. Their electrocatalytic performance and tunable structure makes such silver nanobelts promising candidates for applications in catalysis and as sensors in nanoelectrochemical devices.     

NiFe-oxide electrocatalysts for the oxygen evolution reaction on Ti doped hematite photoelectrodes

Nickel iron binary oxide electrocatalysts prepared from different precursors were evaluated to facilitate the oxygen evolution reaction (OER) on semiconducting metal-oxide photoelectrodes. The electrocatalysts deposited from Ni(II) and Ni(II)Fe(II) precursors had the highest activity for OER, however, their presence on the surface of the Ti doped hematite photoelectrode decreased the incident photon-to-current efficiency (IPCE) of the photoelectrode for water splitting in an alkaline electrolyte. In contrast, the NiFe-oxide deposited from the Ni(II)–Fe(III) precursor which had a lower OER activity was found to increase the IPCE of the photoelectrode by as much as a factor of 5.     

Biomass-derived bifunctional electrocatalysts for oxygen reduction and evolution reaction: A review

Oxygen electrode catalysts are important as inter-conversion of O₂ and H₂O is crucial for energy technologies.However,the sluggish kinetics of oxygen reduction and evolution reactions(ORR and OER)are a hindrance to their scalable production,whereas scarce and costly Pt and Ir/Ru-based catalysts with the highest electrocatalytic activity are commercially unviable.Since good ORR catalysts are not always efficient for OER and vice versa,so bifunctional catalysts on which OER and ORR occurs on the same electrode are very desirable.Alternative catalysts based on heteroatom-doped carbon nanomaterials,though showed good electrocatalytic activity yet their high cost and complex synthesis is not viable for scalable production.To overcome these drawbacks,biomass-derived heteroatom-doped porous carbons have recently emerged as low-cost,earth-abundant,renewable and sustainable environment-friendly materials for bifunctional oxygen catalysts.The tunable morphology,mesoporous structure and high concentration of catalytic active sites of these materials due to heteroatom(N)-doping could further enhance their ORR and OER activity,along with tolerance to methanol crossover and good durability.Thus,biomassderived heteroatom-doped porous carbons with large surface area,rich edge defects,numerous micropores and thin 2 D nanoarchitecture could be suitable as efficient bifunctional oxygen catalysts.In the present article,synthesis,N-doping,ORR/OER mechanism and electrocatalytic performance of biomassderived bifunctional catalysts has been discussed.The selected biomass(chitin,eggs,euonymus japonicas,tobacco,lysine and plant residue)except wood,act as both C and N precursor,resulting in N selfdoping of porous carbons that avoids the use of toxic chemicals,thus making the synthesis a facile and environment-friendly green process.The synthetic strategy could be further optimized to develop future biomass-based N self-doped porous carbons as metal-free high performance bifunctional oxygen catalysts for commercial energy applications.Recent advances and the importance of biomass-based bifunctional oxygen catalysts in metal-air batteries and fuel cells has been highlighted.The material design,perspectives and future directions in this field are also provided.     

Nickel (II) tetrapyridyl complexes as electrocatalysts and precatalysts for water oxidation

Two nickel complexes, [Ni(tpen)](ClO₄)₂.0.5CH₃COCH₃ ( 1 ) and [Ni(tpbn)](ClO₄)₂ ( 2 ), of tetrapyridyl ligands N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,2-ethanediamine (tpen) and N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn) were prepared and their catalysis for water oxidation reaction (WOR) studied. In 0.1 M phosphate buffer solution (PBS) of pH 8.0, complex 1 is a homogeneous molecular catalyst with an overpotential of ~440 mV and a Faradaic efficiency of 89%. At pH ≥ 9.0, complex 1 degraded gradually during the catalytic process and formed NiO_x composite (nickel oxide with general formula Ni_xO_yH_z) active for WOR. In contrast, complex 2 deteriorated under measured conditions (pH 8.0–12.0) and formed NiO_x composite active for WOR. The NiO_x composite derived from 1 in 0.1 M PBS at pH 11.0 showed an activity with an overpotential of ~500 mV, a Tafel slope of ~90 mV/decade and a Faradaic efficiency of 97%. Mechanisms were proposed for water oxidation catalyzed by 1 and 2 . This work revealed that the catalytic activity of the nickel complexes was related to the flexibility of the tetrapyridyl ligands and the adaptability of the coordination sphere of the nickel(II) center.     

Carbon-based bifunctional electrocatalysts for oxygen reduction and oxygen evolution reactions:Optimization strategies and mechanistic analysis

Electrocatalysts are one of the essential components for the devices of high-efficiency green energy storage and conversion, such as metal-air cells, fuel cells, and water electrolysis systems. While catalysts made from noble metals possess high catalytic performance in both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER), their scarcity and expensiveness significantly limit large-scale applications. In this regard, metal-free/non-noble metal carbon-based catalysts have become c...