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Surface/Interface Modulation in Oxygen Evolution Reaction

Minglong Lu , Xiaoyun Zhang , Fan Yang , Lian Wang , Yuqiao Wang

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (3) : 547 -556.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (3) : 547-556 DOI: 10.7536/PC210322
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Surface/Interface Modulation in Oxygen Evolution Reaction
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Abstract

The increasing clean energy demands have promoted extensive attention on the development of alternative energy conversion technologies with high efficiency. Water splitting is a large-scale and sustainable technology for high-purity hydrogen production. However, the substantial overpotential and unsatisfied stability of oxygen evolution reaction (OER) electrocatalysts are great challenges for the widespread application of water splitting technology. Rational design of the structure of the OER electrocatalyst can significantly optimize its reaction thermodynamics and kinetics, thus improving the energy conversion efficiency of water splitting technology. The surface/interface is regarded as the main place where the electrocatalytic reaction occurs. The electrocatalysts, modified by surface/interface engineering, such as regulating intrinsic properties or designing synergistic interface, can improve their electrocatalytic efficiency and stability effectively. This review summarizes the application of surface/interface modulation strategies in OER, especially focusing on the research progress of layered double hydroxides, perovskite oxides, spinel compounds and alloy based materials. The design principles of high-efficient and stable electrocatalysts for OER are described. Based on the recent progress of surface/interface modulation applied in catalysts for OER,the effects of surface/interface modulation on the microstructure and electronic states of the catalysts are discussed. In addition, the challenges about modifications of above electrocatalysts are discussed. Finally, the opportunities of OER electrocatalysts via surface/interface modulation are prospected.

Contents

1 Introduction

2 Surface/interface modification of electrocatalyst

2.1 Modification based on layered double hydroxides

2.2 Modification based on perovskite oxides

2.3 Modification based on spinel compound

2.4 Modification based on alloy

3 Conclusion and outlook

Graphical abstract

Keywords

surface/interface modulation / electron transport / electrocatalysis / microstructure / oxygen evolution reaction

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Minglong Lu, Xiaoyun Zhang, Fan Yang, Lian Wang, Yuqiao Wang. Surface/Interface Modulation in Oxygen Evolution Reaction. Progress in Chemistry, 2022, 34(3): 547-556 DOI:10.7536/PC210322

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1 Introduction

The problem of excessive energy consumption and environmental pollution is becoming more and more prominent, which has brought severe challenges to the sustainable development of human beings. The development of renewable, clean, safe and efficient new energy has become a research hotspot[1,2]. As hydrogen energy is a kind of renewable clean energy with zero pollution and high efficiency, it has become the main body of the new generation of energy development strategy. The source of hydrogen is wide, the preparation methods are various, and the renewable cycle of water can be realized. At present, hydrogen is mainly produced by natural gas reforming, petroleum cracking, coal gasification and water electrolysis. Among them, the technology of hydrogen production by water electrolysis has the advantages of zero emission, high purity of hydrogen production, utilization of waste heat and other resources, and coupling of renewable energy such as solar energy, wind energy and nuclear energy, which will play a major role in the development of hydrogen energy and have a positive impact on the living environment of mankind[3,4].
Although the technology of hydrogen production from water electrolysis is expected to meet people's demand for clean energy, the actual use of this technology is greatly limited by the current cost. Electrocatalyst is one of the key factors to improve the energy conversion efficiency of water electrolysis. Researchers have made unremitting efforts in the innovation of electrocatalyst to reduce the cost of water electrolysis technology[5]. In the water electrolysis system, oxygen evolution reaction (OER) at the anode involves a complex four-electron charge transfer process compared with hydrogen evolution reaction at the cathode, and its high overpotential restricts the further improvement of the energy conversion efficiency of water electrolysis. Therefore, it is particularly important to develop high-performance oxygen evolution electrocatalysts for hydrogen production from water electrolysis[6,7]. OER electrocatalysts have slow kinetic process, large overpotential and poor stability at high potential, which are the main problems for the practical application of OER catalysts[8].
The electrocatalytic OER process involves the adsorption, transformation, and desorption stages of species. Generally speaking, the surface active sites of OER catalysts have a great influence on the adsorption strength and macroscopic activity of oxygen species. For example, the extremely weak or strong adsorption strength of monometallic materials leads to extremely poor OER performance[9]. In the study of OER reaction, the catalytic mechanism of metal-based materials in alkaline and acidic solutions is as follows[10].
In an alkaline electrolyte:
W + O H - → W - O H + e -
W - O H + O H - → W - O + H 2 O + e -
W - O + W - O → 2 W + O 2
W - O + O H - → W - O O H + e -
W - O O H + O H - → W + O 2 + H 2 O + e -
In acid electrolyte:
W + H 2 O → W - O H + H + + e -
W - O H → W - O + H + + e -
W - O + W - O → 2 W + O 2
W - O + H 2 O → W - O O H + H + + e -
W - O O H → W + O 2 + H + + e -
In these reaction steps, W is a surface active site. In general, the adsorption energy and adsorption/desorption rate of W-O, W-OH and W-OOH are the key factors affecting the macroscopic performance of OER electrocatalysts.
In order to further study the OER process involving solid-liquid-gas three phases and understand the oxygen evolution reaction mechanism, it is essential to understand the changes in the structure of the electrocatalyst during the reaction. In view of this, in situ characterization techniques with real-time and high spatiotemporal resolution are highly expected in the field of electrocatalysts. G Görlin et al. studied the effect of Fe element on the Faradaic efficiency of the catalytic OER reaction in Ni(OH)2 by using in-situ X-ray absorption spectroscopy combined with mass analysis techniques, and found that the content of Fe element determines the relationship between Ni active sites and water oxidation rate[11]. Recently, Mefford et al. Used in situ scanning probe combined with X-ray microscopy to deeply analyze the correlation between the structure of single crystal β-Co(OH)2 and oxygen evolution activity[12]. Co3+(β-CoOOH) was found to be the real active site for catalyzing OER. This indicates that in situ technology plays an important role in characterizing the active sites of electrocatalytic OER.
Based on this background, based on the intrinsic properties of catalysts, researchers have constructed new electrocatalysts combined with advanced characterization techniques to study the performance of OER electrocatalysts. For example, layered double hydroxides, perovskite-type oxides, spinel-type compounds and alloy materials are constructed to improve the electron transport and ion transport behavior, thereby improving the catalytic activity of oxygen evolution reaction[13⇓~15]. However, so far, the design and synthesis of electrocatalysts for oxygen evolution reaction based on structure and mechanism are still in the stage of experimental results-oriented, and the development of new catalysts is still in the screening stage. Therefore, this review will focus on the recent progress in the study of oxygen evolution reaction by surface and interface regulation strategies.

2 Surface and interface regulation of electrocatalyst

Compared with bulk materials, nanomaterials have many new features in the catalytic process, such as large specific surface area and high surface energy. These physical and chemical properties directly affect the thermodynamics and kinetics of the surface and interface reactions of the electrocatalyst[16]. In order to overcome the defects of the materials themselves, further improve the performance of the existing catalysts, and obtain efficient, stable and inexpensive catalysts, it is necessary to further optimize the composition and structure of the materials.
The results show that the surface state of the electrocatalyst in the catalytic OER process is very complex. The surface of the nanocatalyst may be a mixture of local crystalline and amorphous States, and there may be a transition from crystalline state[17]. In the field of catalysis, the exploration of the real active sites of catalysts has always been a major problem. To some extent, the chaotic state of catalyst structure conceals the contribution of active sites to specific chemical reactions, and also causes difficulties in the design of catalysts. Surface and interface regulation refers to the use of weak bonds (such as hydrogen bonds, electrostatic forces, van der Waals forces) or strong bonds (such as covalent bonds) to change the local electronic state of materials, or to enhance the synergistic catalysis between different active sites in various reaction pathways. Interface design, such as electrode wettability, covalent bond, Van der Waals force and electrostatic attraction, can change the local bonding environment and electronic state of the electrode. It can be said that the surface and interface is the main battlefield of electrocatalytic reaction. According to the different ways of regulation, it can be divided into three categories: (1) the construction of highly conductive materials/semiconductor heterostructures; (2) under an electric field, a new effect is obtained by utilizing the protection effect of one component on other components, so that the performance of the catalyst is improved; And (3) designing a new catalyst by utilizing the wettability difference of the electrode and the characteristic that the surface components can be reconstructed under the action of an electric field, such as regulating and controlling the components of an oxidation active layer on the surface of a material and improving the self-reconstruction rate and the like[18][19]. With the continuous development of microscopic technology, the relationship between the structure of OER electrocatalysts and active sites, electron transport and ion transport is expected to be deeply analyzed, which will better guide the design of catalysts.

2.1 Control based on layered double hydroxides

Layered double hydroxides (LDH), also known as hydrotalcite-like materials, are a class of compounds composed of positively charged host laminates and interlayer anions, which have no fixed chemical formula. Because OER occurs under extreme oxidation conditions, the surface of compounds containing metal elements will be oxidized. It is generally believed that LDH is the active component of other bimetallic compounds, such as spinel and perovskite catalysts, so it is particularly suitable for OER catalysis. For example, Song et al. used anodic oxidation to treat CoMn LDH and found that an overpotential of 302 mV could be obtained at a current density of 10 mA·cm-2 with a Co: Mn ratio of 2:1, and the activity could be maintained for 14 H at an overpotential of 300 mV[20]. In view of the fact that the morphology and crystal form of the catalyst have not changed, they preliminarily concluded that the high activity of CoMn LDH comes from the amorphous phase formed on the surface. By preparing porous ZnCo LDH nanosheets (Fig. 1), Qiao et al. found that the porous two-dimensional structure has a larger specific surface area, which can produce more active sites and have faster electron transport properties compared with ZnCo LDH nanoparticles[21].
Chen et al. Found that the OH- would gradually penetrate into the lamellar structure of NiFe LDH in the process of OER catalysis, which made the internal basal plane acidic and caused the dissolution of NiFe LDH, resulting in the decrease of catalytic activity[22]. With the help of dynamic in situ X-ray scattering and absorption spectroscopy, Dionigi et al. Found that at a certain anodic potential, the crystal forms of CoFe LDH and NiFe LDH would transform from the initial α phase to the activated γ phase, and the lattice contraction during the transformation process would lead to the transformation of intercalation ions, thus inferring that the active phase of LDH was not the initial synthesis phase[23].
These studies show that the electrocatalytic performance of a single LDH is not practical, and it is necessary to further regulate the structure of LDH, such as optimizing the edge active sites, improving the conductivity and adding a protective layer, in order to improve the adsorption properties of reactant molecules on the catalyst surface and the electron transport capacity of the catalyst. Jiao et al. Used NaOH to selectively etch the surface of NiFe LDH to synthesize NiFe LDH catalyst with partially amorphous surface, which accurately controlled the distribution of amorphous components, resulting in the decrease of electron cloud density at Fe site and the increase of active area, thus improving the catalytic activity of OER[24]. Xie et al. introduced nanopores with uniform size into NiFe LDH ultrathin nanosheets by etching-ripening process, and found that the nanopores could provide sufficient buffer space for the volume change caused by water decomposition reaction, effectively avoiding structural deformation, thus improving the stability of NiFe LDH[25]. Sun et al. introduced mesoporous structure into CoFeNi LDHs by metal-organic framework-mediated transformation strategy, and found that mesoporous CoFeNi LDHs have atomic edge steps and lattice defects, and metal element centers are more active, thus enhancing OER kinetics[26]. Yu et al. coupled FeNi LDH with Ti3C2MXene and found that the stacking of FeNi LDH could be inhibited by the presence of MXene, and the presence of MXene at the interface could accelerate the redox process of Ni2+/Ni3+/Ni4+ and greatly reduce the OER overpotential[27].
Based on the strong synergistic effect between Fe and Ni, Chen et al. Proposed that the electronic structure of NiFe LDH was changed by introducing Fe in a high oxidation state[28]. By depositing FeOOH nanoparticles on the framework of NiFe LDH (Fig. 2), with the help of X-ray absorption fine structure spectroscopy, it was found that the contraction of Fe — O bonds in FeOOH would improve the electronic structure of the interface between NiFe LDH and FeOOH, thus promoting water decomposition.
In 2020, Gu et al. Considered that the electrocatalyst was supported on the support, and proposed to further improve the OER catalytic activity by using the interaction of the electrocatalyst/support interface[29]. Compared to fluorine-doped conductive glass or glassy carbon substrates, the current density of NiFe LDH is increased by a factor of 10 using Co as the non-noble metal carrier (fig. 3). It was further found that the enhanced activity of NiFe LDH/Co was attributed to the in situ formation of a porous amorphous NiFeCoOxHy layer on the surface of NiFe LDH by the addition of Co, and the conductivity of the catalyst was improved by 2 orders of magnitude.
Therefore, when designing the LDH structure, there is a balance between the surface electronic structure of LDH and the overall conductivity of the catalyst, and these two factors need to be considered comprehensively.
Table 1 summarizes the oxygen evolution properties of the above LDH-based materials. It can be seen that the performance of the catalyst can be effectively improved by controlling the surface morphology of the material and constructing a heterogeneous interface. In general, although the composition of LDH is simple, its surface has a significant impact on the adsorption and activation of water molecules, and the surface/interface with high conductivity in the composite structure determines the electron transport process. In addition, there is an uncontrollable phase transformation in the catalytic process of LDH. The combination of various factors indicates that the design of LDH-based structures needs to be based on more research on the catalytic mechanism of surface and interface, and then guide the design of better structures.

2.2 Control based on perovskite-type oxides

Perovskite-type compounds have the general formula ABO3, where A and B represent cations with different radii. This is because there are many kinds of metal cations A and B in the structure of ABO3, and different catalysts can be prepared by combining different elements. The structures of common perovskite oxides are cubic, tetragonal, orthorhombic, or hexagonal. The electrocatalytic properties of perovskite oxides have attracted more and more attention due to their excellent stability and simple and adjustable composition. Shao-Horn et al. proposed the intrinsic activity change law of ABO3 electrocatalyst in 2011, and proposed that the OER catalytic effect of perovskite oxide is better when the number of electrons filled in the eg orbital is close to 1[30]. On the basis of this design theory, Zhou et al. realized the regulation of the effective electron filling number of Co ion eg orbit from 1.0 to 1.3 by changing the size of LaCoO3 nanoparticles[31]. It was found that when the particle size was about 80 nm, the eg orbital electron number was about 1. 2, and the catalyst achieved more excellent OER catalytic performance (η10=490 mV) in the 0.1 mmol·L-1KOH. In order to further improve the OER catalytic activity of perovskite-type, Li et al. started from the insufficiently exposed active sites of perovskite-type oxides, introduced iron element, and obtained a foam nickel-supported lanthanum cobalt iron perovskite electrocatalyst. It was found that the nanostructure had a stable interface and a well-dispersed surface, and showed excellent OER activity (η10=350 mV) in 0.1 mol·L-1KOH[32]. Wang et al. designed the nanorod LaFexNi1-xO3 perovskite composite oxide, and found that the Fe: Ni element ratio of 1:4 could enhance the valence state of Ni ions on the surface of LaFexNi1-xO3, and then showed an overpotential of 302 mV at a current density of 10 mA·cm-2, with a Tafel slope of only 50 mV·dec-1[33]. By means of surface valence band photoemission spectroscopy, it was found that the synthesized LaFe0.2Ni0.8O3 had the highest valence band center, and the metal ions on the surface of the catalyst had the strongest binding effect with the OH-. They further concluded that this strong binding effect is more conducive to the charge conduction in the OER process of perovskite oxides, thus improving the OER performance. However, the low electrical conductivity and surface defects of perovskite-type oxides are difficult to control, which will limit the OER electrocatalytic performance of perovskite-type oxides.
Therefore, in order to further improve the catalytic efficiency of perovskite-type catalysts, selective introduction of other components and means to control the surface/interface properties of perovskite-type oxides have become the focus of attention, and some progress has been made. Elumeeva et al. First prepared La0.58Sr0.4Fe0.2Co0.8O3 by using the strategy of compounding carbon materials with high conductivity, and then obtained La0.58Sr0.4Fe0.2Co0.8O3/CNT composite by using the characteristic that the existence of Fe/Co ions is beneficial to the deposition and growth of carbon nanotubes (CNTs) on the surface of the material, which significantly improved the OER catalytic performance of La0.58Sr0.4Fe0.2Co0.8O3[34]. Zhu et al. Introduced oxygen vacancies on the surface of PrBa0.5Sr0.5Co1.5Fe0.5O5+δ by hydrogen heat treatment combined with electrochemical reduction, and found that the film with oxygen vacancies had higher Sr content on the surface and was more likely to form Sr-OH bonds, which was conducive to the occurrence of OER[35]. But on the other hand, the introduction of oxygen vacancies brings a larger band gap and lower O 2p centers, which may suppress the OER dynamics. Chen et al. studied the electrocatalytic properties of quaternary metal perovskite oxides, and found that the 10 nm-thick Ba0.5Sr0.5Co0.8Fe0.2O3-δ film had the best intrinsic area catalytic activity, and the electronic structure of transition metals could be optimized by adjusting the film thickness[36]. Kim et al. Obtained triple perovskite electrocatalyst Nd1.5Ba1.5CoFeMnO9-δ by stacking single perovskite, and found that the stacking of A-site elements would cause the structural deformation of the triple perovskite lattice, resulting in additional oxygen vacancies, which is conducive to catalytic OER[37]. Compositing the perovskite-type catalyst with nitrogen-doped graphene was found to further enhance the electrocatalytic activity. Et al. Used graphene-like MoSe2 and perovskite oxide to form a heterojunction structure, and found that there are semiconductor-metal structure phase transition ions in the La0.5Sr0.5CoO3-δ/MoSe2 heterojunction (Figure 4), and the structure will change from semiconductor characteristics to metal characteristics as electrons move from perovskite oxide to MoSe2,MoSe2[38]. This electron movement between transition metal disulfides and perovskite-type oxides can provide new insights into the performance optimization of perovskite-type oxides.
The surface properties of perovskite-type oxides also include the surface oxygen defect concentration. Aiming at the problem that bulk defects are difficult to be utilized in practical electrochemical processes, Li et al. Constructed perovskite-type oxide OER electrocatalysts rich in surface defects[39]. Taking advantage of the fact that p-block metals (referring to the metal elements in the third to seventh main groups in the periodic table) can be lost from the solid phase surface of the catalyst in an alkaline electrolyte solution to form a large number of surface defects, a tin-nickel-iron ternary perovskite oxide was designed with tin as the p-block metal (Figure 5). Under the condition of electrochemical activation, the tin on the perovskite surface is lost and a large number of oxygen vacancies are generated as highly active surface defect sites. The surface-defect-rich tin-nickel-iron ternary perovskite oxide exhibits a low overpotential of 350 mV at a current density of 10 mA·cm-2. Based on this, they constructed an "oxygen pool" model to describe the electrocatalytic process of defect-rich surface perovskite-type oxides, specifically, reactants are integrated into the surface oxygen pool and accelerate the electrocatalytic reaction to precipitate products from the oxygen pool.
Table 2 summarizes the oxygen evolution properties of the above perovskite-type materials. It can be seen that the introduction of metal elements to regulate the surface electronic structure and oxygen defect concentration of the material effectively improves the performance of the catalyst. In general, the application of perovskite-type oxides in the field of electrocatalytic oxygen evolution can be combined with a variety of control means to precisely adjust the concentration of oxygen defects on the surface of the catalyst, and to optimize the catalytic activity and stability of perovskite-type oxides for OER by using the protection or buffering effect of other components on the interface.

2.3 Control based on spinel-type compound

The general formula of spinel is AB2X4, divalent cation occupy 1/8 of that tetrahedral interstices, trivalent cation B occupy 1/2 of the octahedral interstices, and divalent anions X (O, S or Se) are arranged in cubic close PAC. The results show that the oxidation States of the cations in spinel compounds can be flexibly changed between tetrahedral sites and octahedral sites, thus affecting their catalytic properties[40,41]. Among various types of spinel compounds, Co3O4 is a monometallic spinel oxide electrocatalyst suitable for use in alkaline solutions, and its physical and chemical properties have attracted wide attention[42,43]. Based on the understanding that the control of surface morphology affects the electron transport of the catalyst, Xu et al. designed Co3O4 particles with spherical, layered and massive morphologies of sea urchin, and found that the Co3O4 with spherical morphology of sea urchin showed better OER performance[44]. To further illustrate the effect of morphology on the catalyst, Liu et al. Synthesized nanotubes with exposed (100) crystal face, nanosheets with exposed (110) crystal face, and nanoplate-like Co3O4 particles with exposed (111) crystal face.Considering that the (100) and (111) crystal planes of the Co3O4 with octahedral coordination environment mainly contain Co2+,(110), and the crystal planes mainly contain Co2+ and Co, they proposed that the existence of Co3+ on the surface of the Co3O4 is the reason for its high OER activity[45]3+[46].
Because the spinel structure has two coordination environments of octahedron with high symmetry and tetrahedron with low symmetry of metal cations, before the in-situ observation technology is widely used and recognized,According to the electrochemical test results at that time, the researchers believed that the isolated tetrahedral metal centers in spinel would prohibit the OER mediated by bimetallic sites, while the adjacent octahedral centers would cooperate to promote the OER kinetics. Based on this understanding, Grewe et al. studied the effect of pore structure on the OER catalytic performance of Co3O4 in alkaline solution. The introduction of a small amount of Fe into Co3O4 increased its pore volume (Fig. 6), reduced the symmetry of the mesoscopic structure, and thus enhanced the OER activity of the material[47]. This indicates that the coordination environment of spinel compounds can be adjusted by controlling the Co3O4 with pore structure.
Liu et al. Further explained the role of Co ions with different coordination environments in OER in Co3O4 by means of in situ X-ray absorption spectroscopy[48]. Which adopts an ion substitution method to prepare a Co3O4, a ZnCo2O4 and a CoAl2O4 with the same appearance and crystal form, and discovers that the Co — O bond containing the Co tetrahedral coordination Co3O4 and the CoAl2O4 can be shortened along with the increase of electrode potential,However, this change did not occur in the ZnCo2O4 of octahedral Co ligands, and the ZnCo2O4 had poor OER catalytic activity. Based on the electrochemical properties of the samples, it was finally confirmed that in the Co3O4, the octahedrally coordinated Co3+ played a major role in the electric double layer in the catalytic process, thus promoting the driving force of the whole reaction process, while the tetrahedrally coordinated Co2+ was directly related to the oxidation of water, promoting the formation of intermediate CoOOH in the OER process, as a practical OER catalyst. This result promotes the research progress of OER catalytic mechanism. The study of the dominant role of catalysis of octahedrally coordinated Co3+ and tetrahedrally coordinated Co2+ in the spinel structure is of great significance for the design of such compounds. Based on the synergistic catalytic effect between transition metal elements, Du et al studied the OER electrocatalytic activity of MnO2 nanotubes /Co3O4 nanoparticles by the method of composite MnO2.The results showed that the synergetic effect and interfacial effect of MnO2 and Co3O4 promoted the reaction kinetics of Co3O4[49].
Controlling the surface defects of spinel compounds will also have a greater impact on the electrocatalytic activity. Wang et al. Used NaBH4 solution to reduce the Co3O4, and introduced a large number of mesopores and oxygen vacancies on the surface while retaining the nanowire structure of the Co3O4.It was found that the large number of mesopores exposed more active sites, and the existence of oxygen vacancies made the electrons of Co — O bond tend to delocalize, which increased the conductivity of the material, so that the reduced Co3O4 showed higher current density and lower overpotential[50].
Xiao et al. Selected Co3S4 with high conductivity as the research object, and prepared atomic-scale thin-layer Co3S4 nanosheets by solution exfoliation, which had superior OER activity in neutral electrolyte[51]. For the highly active source of atomic-scale thin-layer Co3S4 nanosheet structure, they assumed that tetrahedral Co site ions were inert to OER, and explored the 3D orbital electron arrangement of Co3+ in Co3S4 by means of electron paramagnetic resonance technology.It is deduced that the 3D orbital of the Co3+ at the octahedral site in the bulk Co3S4Co3S4It is revealed that the good catalytic activity of atomic-scale thin layer Co3S4 comes from the exposed octahedron and the adaptive transition of Co3+ spin state from low spin to high spin in octahedron. With The development of in-situ observation technology, Yan et Al. Substituted Co ions in Co3O4 with different contents of Al ions, and combined the experimental and theoretical results.It was found that when Al3+ occupied the tetrahedral site of Co2+ in alkaline solution, a large number of electrophilic O 2 2 - /O- species with high oxidation state were generated on the electrode surface, which made the adsorption, activation and desorption of OER intermediates tend to be balanced, thus making the Co1.75Al1.25O4 show superior OER activity[52].

2.4 Control based on alloy material

Metal alloy nanomaterials are a class of electrocatalysts that have been developed rapidly in recent years. In the alloy, the packing mode of metal atoms in different crystal structures directly determines its electronic structure, and then affects the electrocatalytic activity. At present, the activity of noble metal-based electrocatalysts is still the most efficient. In order to reduce the cost of electrocatalysts, alloying noble metals with transition metals is one of the current focuses. Based on the limited active sites exposed by the bulk alloy, Luo et al. designed ultrathin platinum-molybdenum alloy nanosheets with sub-nanometer thickness, which made the alloy have outstanding electrochemical active surface area and high atom utilization, thus showing excellent OER reactivity in alkaline electrolytes[53]. Yao et al. Designed atomically dispersed Ru on PtCu alloy by compressive strain from the point of view of improving the utilization rate of atoms, and found that it could greatly promote the occurrence of OER[54]. Specifically, only an overpotential of 90 mV is required for Ru1-Pt3Cu to reach the current density of 10 mA·cm-2. Further studies show that the compressive strain of the Pt3Cu shell changes the electronic structure of Ru1 and optimizes the oxygen binding. In order to reduce the amount of Pt used, Sun et al. Designed PtPd nanorings, which can expose a large number of unsaturated step atoms on the surface, thereby enhancing the transport of reactants on the catalyst surface[55]. At the same time, they used transition metal elements to replace some noble metal elements, and found that PtPdCo nanorings could show excellent OER catalytic performance in alkaline electrolyte.
In addition, because the d electrons of transition metal elements can form a strong synergistic catalytic effect, which is not limited to the limited properties of a single element, it is expected to enhance the intrinsic catalytic activity of materials, making the study of the electrocatalytic properties of low-cost transition metal alloys another focus. Fu et al. design NiCo alloy particles disper on nitrogen-doped carbon nanofibers based on that dispersibility of the alloy catalyst, and found that the overpotential at 10 mA·cm-2 current density was 490 mV. At the same time, it was found that adjusting the ratio of Ni to Co could indirectly affect the OER catalytic activity[56].
Considering that alloys with different crystal phases have different crystal structures and electronic properties, Wang et al. designed a nitrogen-doped carbon-coated hexagonal close-packed NiFe alloy catalyst (hcp-NiFe @ NC) in order to protect the activity of the alloy catalyst in the electrocatalytic process[57]. The results show that the hcp-NiFe @ NC has an overpotential of 226 mV when the current density reaches 10 mA·cm-2 in 1.0 mol·L-1KOH electrolyte, and the coating of nitrogen-doped carbon effectively avoids the electrochemical oxidation of the alloy. Dai et al. accelerated the surface oxidation process of the alloy through an electrochemical mode by directly utilizing the surface oxidation characteristic of the alloy catalyst, which is different from designing a carbon material coating type structure to avoid the oxidation process of the alloy,A composite oxide nanosheet is directly grown on the surface of the MnFeCoNi high-entropy alloy particle through regulation and control to form a core-shell structure of the high-entropy alloy wrapped by the oxide[58]. The results show that the in situ generated core-shell structure helps to expose more active sites, and the high conductivity of the high-entropy alloy strengthens the electron transport of OER. Therefore, the core-shell structure exhibits much better OER electrocatalytic activity than the alloy itself.
Although the strategy of surface coating and electrochemical pre-oxidation is expected to obtain electrocatalysts with higher activity, the lack of electrochemical stability of catalysts is still a major problem. Based on this, the study of amorphous alloy electrocatalysts with the characteristics of disordered surface atom arrangement and unsaturated surface atom coordination has attracted the interest of researchers. Considering that increasing the specific surface area of amorphous alloy materials, changing the composition ratio of amorphous alloy raw materials, optimizing the corrosion parameters of amorphous alloys and changing the structure of amorphous alloy materials can change the electrocatalytic properties of amorphous alloys, it is necessary to accurately control the composition of amorphous alloys. In order to control the stoichiometric ratio of amorphous alloy elements, Glasscott et al. confined metal salt precursors in water nanodroplets suspended in dichloroethane, and prepared amorphous alloy catalysts by electrodeposition[59]. The method is characterize in that metal salt precursor atoms are deposite on a substrate at a liquid drop/electrode contact interface, and when nano liquid drops collide with a conductor, a specific number of precursor metal salt molecules are independently transmit to a local nucleation area and a local growth area, so that that stoichiometric control of the amorphous alloy is realized. The experimental results show that the CoFeLaNiPt amorphous alloy nanocatalyst has good electrocatalytic effect, and only an overpotential of about 377 mV is required to reach the current density of 10 mA·cm-2 in 0.1 mol·L-1KOH electrolyte.
Table 3 summarizes the oxygen evolution properties of the above alloy materials. It can be seen that the OER performance can be effectively improved by constructing alloy/carbon composites and regulating the surface properties of the alloy. The synergistic effect and structural stability of alloy make it a potential electrocatalyst, but the complex phase change process in the preparation of alloy catalyst and the stress change between metals in the electrocatalytic process will affect the morphology and electronic structure of alloy catalyst, so how to effectively design this kind of catalyst is an urgent problem to be solved.

3 Conclusions and outlook

In this paper, the research progress of surface/interface control strategy in oxygen evolution reaction is summarized, including layered double hydroxides, perovskite-type oxides, spinel compounds and alloy materials. Researchers have done a lot of work to promote the application of surface/interface regulation in the field of oxygen evolution reaction electrocatalysis. Controlling the intrinsic structure of materials, the concentration of surface defects and the construction of heterogeneous surface/interface can effectively enhance the electrocatalytic activity, but there are still challenges for the current electrocatalysts to meet the next generation of energy needs:
(1) It is difficult to characterize the active sites on the surface/interface of the catalyst. It is generally believed that metal atoms are catalytic sites, but non-metal species also have an important impact on the catalytic activity.Direct observation of the catalytic sites for oxygen evolution reaction is limited, and more in-depth studies are needed to further clarify the location and role of the active sites with the help of relevant characterization methods.
(2) The "synergistic effect" between different components is not enough to explain the reason for the improvement of activity, which needs more detailed elaboration. When controlling different components of nanomaterials, not a single factor affects the performance of catalysts in the reaction, such as nitrogen-doped carbon-coated alloy particle composite catalysts, the role of nitrogen-doped carbon in the catalytic process is not yet clear. The synergistic effect of defects in different structures can effectively improve the OER activity of materials, and how to accurately design different defect States to effectively regulate the OER process is a major problem[60]. Continuous efforts are needed to explore the synergistic effect between various components from theoretical and experimental studies.
(3) The oxygen evolution reaction electrocatalyst is actually unstable in the electrochemical reaction process, the surface composition and electronic structure may change dynamically, and there is a difference between the surface of the prepared target catalyst and the surface and interface structure in the actual reaction. Therefore, attention should be paid to exploring the real catalytic active structure of the prepared nanocatalysts and establishing the relationship between the active sites at the surface/interface and the apparent electrochemical properties.
(4) Great progress has been made in electrode materials after years of research. However, complex preparation strategies, low yields and weak mechanical stability between the electrode and the catalyst make these materials still a long way from practical application. The potential electrocatalysts in the laboratory will be transferred to the industrial large-scale actual production, and the systematic optimization of the large-scale production process of electrocatalysts will attract attention in the next research stage.

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Funding

National Natural Science Foundation of China(61774033)

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