Exploring the Influence of Halogen Coordination Effect of Stable Bimetallic MOFs on Oxygen Evolution Reaction

The energy crisis and environmental pollution have forced scientists to explore alternative energy conversion and storage devices. The anodic reactions of these devices are all oxygen evolution reactions (OER), so the development of efficient OER electrocatalysts is of great significance. At the same time, understanding the reaction mechanism of OER is conducive to the rational design of efficient OER electrocatalysts. In general, catalytic active centers play a direct role in OER performance. In this paper, a series of stable bimetallic metal–organic frameworks (MOFs, named as Fe₃-Co_n-X₂, n=2, 3 and X=F, Cl, Br) with similar structure were synthesized by changing the halogen coordinated with the cobalt metal active center, aiming to investigate the influence of halogen substitution effect on OER performance. It was found that the OER activity of Fe₃-Co₃-F₂ is much better than Fe₃-Co₂-Cl₂ and Fe₃-Co₂-Br₂, indicating that the regulation of the electronegativity change of the coordination halogen atom can regulate the coordination electron structure of the metal active center, thereby achieving effective regulation of OER performance.     

Stable Hierarchical Bimetal–Organic Nanostructures as HighPerformance Electrocatalysts for the Oxygen Evolution Reaction

The integration of heterometallic units and nanostructures into metal–organic frameworks (MOFs) used for the oxygen evolution reaction (OER) can enhance the electrocatalytic performance and help elucidate underlying mechanisms. We have synthesized a series of stable MOFs (CTGU‐10a1–d1) based on trinuclear metal carboxylate clusters and a hexadentate carboxylate ligand with a (6,6)‐connected nia net. We also present a strategy to synthesize hierarchical bimetallic MOF nanostructures (CTGU‐10a2–d2). Among these, CTGU‐10c2 is the best material for the OER, with an overpotential of 240 mV at a current density of 10 mA cm^?2 and a Tafel slope of 58 mV dec^?1. This is superior to RuO₂ and confirms CTGU‐10c2 as one of the few known high‐performing pure‐phase MOF‐OER electrocatalysts. Notably, bimetallic CTGU‐10b2 and c2 show an improved OER activity over monometallic CTGU‐10a2 and d2. Both DFT and experiments show that the remarkable OER performance of CTGU‐10c2 is due to the presence of unsaturated metal sites, a hierarchical nanobelt architecture, and the Ni–Co coupling effect.     

NiSe2-CoSe2 with a Hybrid Nanorods and Nanoparticles Structure for Efficient Oxygen Evolution Reaction

Hetero-structure induced high performance catalyst for oxygen evolution reaction(OER)in the water splitting reaction has received increased attention.Herein,we demonstrated a novel catalyst system of NiSe₂-CoSe₂ consisting of nanorods and nanoparticles for the efficient OER in the alkaline electrolyte.This catalyst system can be easily fabricated via a low-temperature selenization of the solvothermal synthesized NiCo(OH)x precursor and the unique morphology of hybrid nanorods and nanoparticles was found by the electron microscopy analysis.The high valence state of the metal species was indicated by X-ray photoelectron spectroscopy study and a strong electronic effect was found in the NiSe₂-CoSe₂ catalyst system compared to their counterparts.As a result,NiSe₂-CoSe₂ exhibited high catalytic performance with a low overpotential of 250 mV to reach 10 mA·cm^-2 for OER in the alkaline solution.Furthermore,high catalytic stability and catalytic kinetics were also observed.The superior performance can be attributed to the high valence states of Ni and Co and their strong synergetic coupling effect between the nanorods and nanoparticles,which could accelerate the charge transfer and offer abundant electrocatalytic active sites.The current work offers an efficient hetero-structure catalyst system for OER,and the results are helpful for the catalysis understanding.     

非贵金属电催化析氧催化剂的最新进展

氢气具有环境友好、含量丰富、高能量密度等特点,是一种可以替代化石能源的绿色环保可再生能源. 电解水是制备氢气最有效途径之一. 但在电解水过程中,动力学过程非常缓慢,过电位较大的阳极析氧半反应严重限制了阴极析氢反应效率. 因此,研究高效、稳定和低成本的催化剂来降低析氧反应的过电位,从而提高析氢反应效率受到了广泛关注. 基于非贵金属催化剂本身特性及其在高浓度OH-条件下具有较高OER催化活性等原因,本文首先简要介绍碱性条件下析氧反应机理及其性能的评价方法,然后重点讨论非贵金属电催化析氧催化剂的最新研究进展. 最后对如何深入研究催化机理、设计高效、双功能及新型非贵金属电催化析氧催化剂进行了展望.     

Phase‐Selective Syntheses of Cobalt Telluride Nanofleeces for Efficient Oxygen Evolution Catalysts

Cobalt‐based nanomaterials have been intensively explored as promising noble‐metal‐free oxygen evolution reaction (OER) electrocatalysts. Herein, we report phase‐selective syntheses of novel hierarchical CoTe₂ and CoTe nanofleeces for efficient OER catalysts. The CoTe₂ nanofleeces exhibited excellent electrocatalytic activity and stablity for OER in alkaline media. The CoTe₂ catalyst exhibited superior OER activity compared to the CoTe catalyst, which is comparable to the state‐of‐the‐art RuO₂ catalyst. Density functional theory calculations showed that the binding strength and lateral interaction of the reaction intermediates on CoTe₂ and CoTe are essential for determining the overpotential required under different conditions. This study provides valuable insights for the rational design of noble‐metal‐free OER catalysts with high performance and low cost by use of Co‐based chalcogenides.     

Exploring the Performance Improvement of the Oxygen Evolution Reaction in a Stable Bimetal–Organic Framework System

Despite wide applications of bimetallic electrocatalysis in oxygen evolution reaction (OER) owing to their superior performance, the origin of the improved performance remains elusive. The underlying mechanism was explored by designing and synthesizing a series of stable metal–organic frameworks (MOFs: NNU‐21–24 ) based on trinuclear metal carboxylate clusters and tridentate carboxylate ligands. Among the examined stable MOFs, NNU‐23 exhibits the best OER performance; particularly, compared with monometallic MOFs, all the bimetallic MOFs display improved OER activity. DFT calculations and experimental results demonstrate that introduction of the second metal atom can improve the activity of the original atom. The proposed model of bimetallic electrocatalysts affecting their OER performance can facilitate design of efficient bimetallic catalysts for energy storage and conversion, and investigation of the related catalytic mechanisms.     

硫掺杂镍铁层状双氢氧化物的氧析出电催化性能

氧析出反应(OER)是裂解水、二氧化碳还原、以及可充电的锌空电池等许多技术中重要的半反应,但受限于其迟缓的反应动力学,开发高效的氧析出催化剂迫在眉睫.在OER出反应中,性能较好的非贵金属催化剂主要是第四周期过渡金属的一些化合物,如氧化物、氢氧化物、硫化物、硒化物、磷化物等等.在这些材料中,镍铁双金属化合物被认为是最优的氧析出材料,尤其是镍铁层状双氢氧化物(Ni Fe-LDHs)它拥有较大的电化学活性面积以暴露较多活性位点,同时镍铁两种过渡金属元素存在协同效应,使得其具有良好的催化性能.然而,这一类材料的OER性能仍然有优化的空间.研究表明,将硫化物氧化得到的氢氧化物会有少量的硫元素残留,这种硫残留的氢氧化物拥有十分优异的OER性能.为了进一步认识硫的引入对Ni Fe-LDHs的OER行为的影响,本文通过水热法合成了硫掺杂的Ni Fe-LDHs,考察了硫的掺杂量对催化剂性能的影响,验证了微量硫的存在对Ni Fe-LDHs的OER性能的贡献.扫描电镜图片显示,水热合成的催化剂是厚度为几十纳米的薄片,拥有较高的比表面积, X射线荧光光谱分析证明合成的硫掺杂Ni Fe-LDHs中镍铁的元素比例为4:1,而且硫的掺杂量并不影响催化剂的形貌和其中镍铁元素比.X射线光电子能谱分析表明,硫原子的引入使得铁原子结合能降低,即硫与铁的相互作用部分降低了铁的价态,这种硫和铁的相互作用能够优化OER反应中间体OH*与O*在铁活性位点上的吸附自由能,降低氧析出反应的过电势.电化学测试表明,拥有0.43%的硫掺杂Ni Fe-LDHs拥有最好的氧析出性能, 10 m A cm^-1下超电势仅有257 m V, Tafel斜率61.5 m V dec^-1.此后,随着硫掺杂量的提升,其性能先保持稳定,随后有所下降.在稳定测试中,硫掺杂的镍铁层状双氢氧化物在10 m Acm-1电流密度下循环30 h后过电位仅衰减14 m V.在对稳定性测试后的催化剂进行表征表明,催化剂发生了轻微了变形,但这对性能的影响不大.综上,本文提供了一种简便的通过非金属元素掺杂调控过渡金属氧化物的结构和电子态的方法,有望为设计高活性OER电催化剂提供新思路.     

具有高效析氧催化性能的铁基双元金属有机框架纳米棒研究

析氧反应(OER)是电解水制氢的关键步骤,开发高效、稳定、廉价的OER电催化剂是目前该领域的研究热点.碱性电解液中的OER电催化剂成分以Mn、Fe、Co、Ni等为主,其中单一组分的Fe基化合物催化活性不高,但碱性电解液中的痕量铁杂质极易掺入Ni、Co等非Fe基材料的结构中,极大影响其OER催化性能,即现有大部分非Fe基...     

Autologous Cobalt Phosphates with Modulated Coordination Sites for Electrocatalytic Water Oxidation

The correlation between metal coordination and electrocatalytic water oxidation performance is elusive in many cobalt‐based materials. Herein, we designed an ideal Co phosphate‐based platform to explore the effect of coordination environment on oxygen evolution reaction (OER) activity. The cobalt geometry was modulated from octahedral to tetrahedral by simple removal of water ligands in Co₃(PO₄)₂?8 H₂O. Other features except the coordination structure in the two autologous materials remain similar. The two analogues display the same OER kinetics, but the anhydrous Co₃(PO₄)₂ exhibits a greatly enhanced OER activity. On the basis of Raman and operando XAS results, the higher intrinsic activity of the Co tetrahedral sites is because they facilitate the formation of active high valent cobalt (hydr)oxide intermediates during OER. This work not only brings insights of OER on Co‐based electrocatalysts but also provides a reference system to study the effect of metal geometry on electrocatalysis.     

From pseudocapacitive redox to intermediary adsorption in oxygen evolution reaction

The mechanism of oxygen evolution reaction (OER) is somehow related to that of the pseudocapacitance of metal oxide electrocatalysts in potentials lower than the OER standard potential. Although pseudocapacitance of metal oxide electrocatalysts is usually studied in the investigations of OER, this dependence is not profoundly inspected. During the pseudocapacitive behavior, some high valence cations are formed over a broad range of potential in an underpotential region before the formal redox potential. This is due to the exceptional activities of some sites, which are capable of further oxidation at the OER potential to form active sites for the OER electrocatalysis. Therefore, a well-defined pseudocapacitance is somehow a requirement for the OER performance. Almost all OER electrocatalysts reported in the literature display considerable pseudocapacitive behavior at the lower potentials. The corresponding pseudocapacitance explains the difference between the OER activities of IrO₂ and RuO₂. Here, the focus is on noble metals as the well-defined OER electrocatalysts, but the reasoning can be extended to other metal oxides. The electrochemical behaviors including the pseudocapacitance of almost all inexpensive OER electrocatalysts such as cobalt oxide, nickel oxide, etc. are similar to that of IrO₂ as described here. Moreover, despite the high cost, noble metals still have the practical potentials for OER, subject to further enhancement in the OER efficiency or as additives in inexpensive electrocatalysts.     

CD spectra of polynuclear complexes of diimine ligands: theoretical and experimental evidence for the importance of internuclear exciton coupling

We have recently reported on dinuclear complexes Lambda,Lambda-[Co(2)L(2)Cl(2)]CoCl(4) of two novel chiral ligands (1a and 1b) which contain pyridyl-imine chelate groups (Telfer, S. G.; Sato, T.; Kuroda, R. Chem. Commun. 2003, 1064-1065). The absolute configuration of the cobalt(II) centers was unambiguously assigned by X-ray crystallography. However, the sign of the exciton couplets in their CD spectra was opposite to that expected on the basis of the stereochemistry of the metal centers. We present a rationalization of these anomalous spectra in terms of an "internuclear" exciton coupling model which takes into account the coupling of chromophores located on different metal centers. We have performed a series of semiempirical (ZINDO) calculations which provide quantitative support to this model. These findings show that the absolute configuration of the metal centers in a polynuclear complex may be incorrectly assigned on the basis of CD data if internuclear coupling effects are not taken into consideration. We summarize the CD spectral data of number of other chiral polynuclear complexes from the literature, including dinuclear complexes bridged by the 2,2'-bipyrimidine ligand, complexes of the HAT ligand, and dinuclear triple-stranded helicates. The amplitude of the CD spectra of many of these complexes is not additive with the number of chromophores. These anomalous spectra can be accounted for by taking internuclear coupling effects into consideration.     

Bimetallic Metal‐Organic Framework‐Derived Nanosheet‐Assembled Nanoflower Electrocatalysts for Efficient Oxygen Evolution Reaction

Non‐noble metal‐based metal–organic framework (MOF)‐derived electrocatalysts have recently attracted great interest in the oxygen evolution reaction (OER). Here we report a facile synthesis of nickel‐based bimetallic electrocatalysts derived from 2D nanosheet‐assembled nanoflower‐like MOFs. The optimized morphologies and large Brunauer–Emmett–Teller (BET) surface area endow FeNi@CNF with efficient OER performance, where the aligned nanosheets can expose abundant active sites and benefit electron transfer. The complex nanoflower morphologies together with the synergistic effects between two metals attributed to the OER activity of the Ni‐based bimetallic catalysts. The optimized FeNi@CNF afforded an overpotential of 356 mV at a current density of 10 mA cm^?2 with a Tafel slope of 62.6 mV dec^?1, and also exhibited superior durability with only slightly degradation after 24 hours of continuous operation. The results may inspire the use of complex nanosheet‐assembled nanostructures to explore highly active catalysts for various applications.     

A bifunctional perovskite oxide catalyst:The triggered oxygen reduction/evolution electrocatalysis by moderated Mn-Ni co-doping

ABO₃-type perovskite oxides(e.g.,LaCoO₃)with flexible and adjustable A-and B-sites are ideal model catalysts to unravel the relationship between the electronic structure and electrocatalytic activity(e.g.,oxygen reduction/evolution reactions,ORR/OER).It has been well understood in our recent work that the secondary metal dopant at B-site(e.g.,Mn in LaMn_xCo_1-xO₃)can regulate the electronic structure and improve the ORR/OER activity.In this work,the Mn-Ni pairs are employed as the dual dopant in LaMn_xNi_yCo_zO₃(x+y+z=1)catalysts toward bifunctional ORR and OER.The structure-property relationships between the triple metal B-site(Mn,Ni and Co)and the electrochemical performance are particularly investigated.Compared to the individual Mn doping(e.g.,LaMnCoO3(Mn:Co=1:3)catalyst),the dual Mn-Ni doping significantly improves the ORR mass activity@0.8 V by 1.54 times;meanwhile,the OER overpotential@10 mA cm^-2 is reduced from 420 to 370 mV,and the OER current density at 1.55 V is increased by 2.43 times.Reasonably,the potential gap between EDRR@-1 mA cm^-2 and EDER@10 mA cm^-2 is achieved as only 0.76 V by using the optimal LaMn_xNi_yCo_zO₃(x:y:z=1:2:3)catalyst.It is revealed that the dual Mn-Ni dopant efficiently optimizes electron structures of the LaMnNiCoO₃(1:2:3)catalyst,which not only decreases the e_g orbital electron number,but also modulates the O 2 p-band closer to the Femi level,accounting for the enhanced bifunctional activity.     

Theoretical study of the relationship between the nearest-neighbor exchange coupling interactions and the number of peripheral complexes in the cyano-bridged CrMn6(CN)6 and CrMn2(CN)2 clusters

A theoretical density functional study of the relationship between the nearest-neighbor constants and the number of peripheral complexes in the cyano-bridged [Cr[CNMn(salen)(H2O)]6]3+ and [(5-Brsalen)2(H2O)2Mn2Cr(CN)6] clusters is presented. Two approaches show that the antiferromagnetic coupling interactions between nearest neighbors decrease with the increase of the number of peripheral complexes, although the second approach provides better results using several exchange-correlation functionals. The first approach consisted of evaluating the exchange coupling constant J(ij) between two paramagnetic metal centers i and j in the hexanuclear molecule by calculating the energy differences between the highest and broken-symmetry spin states of a model molecule in which metal atoms except for i and j are substituted by diamagnetic Zn(II) cations, while the second consisted of calculating the different spin-state energies of hexanuclear complexes and using the Heisenberg Hamiltonian to obtain the exchange coupling constants between different metal centers. Moreover, Kahn's qualitative theory succeeded in being applied to interpret the trend.     

Coupling Magnetic Single‐Crystal Co2Mo3O8 with Ultrathin Nitrogen‐Rich Carbon Layer for Oxygen Evolution Reaction

Transition‐metal oxides as electrocatalysts for the oxygen evolution reaction (OER) provide a promising route to face the energy and environmental crisis issues. Although palmeirite oxide A₂Mo₃O₈ as OER catalyst has been explored, the correlation between its active sites (tetrahedral or octahedral) and OER performance has been elusive. Now, magnetic Co₂Mo₃O₈@NC‐800 composed of highly crystallized Co₂Mo₃O₈ nanosheets and ultrathin N‐rich carbon layer is shown to be an efficient OER catalyst. The catalyst exhibits favorable performance with an overpotential of 331 mV@10 mA cm^?2 and 422 mV@40 mA cm^?2, and a full water‐splitting electrolyzer with it as anode catalyst shows a cell voltage of 1.67 V@10 mA cm^?2 in alkaline. Combined HAADFSTEM, magnetic, and computational results show that factors influencing the OER performance can be attributed to the tetrahedral Co sites (high spin, t₂³e⁴), which improve the OER kinetics of rate‐determining step to form *OOH.     

Metal Doping and Ligand Engineering as Tools for Tailoring the Electronic Structure of Coordination Polymers and their Oxygen Evolution Electrocatalytic Activity

Electrocatalytic production of fuels [green hydrogen from water, C1-high energy molecules from CO₂, NAD(P)H from NAD(P)⁺], utilizing renewable energy sources, has in the oxygen evolution reaction (OER) its Achilles’ heel. Among the catalysts developed for facilitating OER, those based on coordination polymers (CPs) are attracting considerable interest due to their simplicity of preparation and modularity. In this review, after having recalled the key-parameters that have to be considered when evaluating and benchmarking electrocatalysts, it is shown how the performance of CP-based OER catalysts can be rationally improved by a) the suitable selection of the metal ion combination and b) engineering CPs with appropriate organic linkers. It is inferred that the catalytic effect of adding a different metal ion, than that of the CP structure (metal doping), occurs through an indirect alteration of the electronic features of the active metal center, which might be described by considering the energy of the d-band with respect to that of the Fermi level (E_d), the e_g occupancy or the metal ionic electronegativity (MIE). In rare cases, it is assumed that the added metal center can directly and synergistically participate at the catalytic process. The much less explored strategy b) to improve the performance of OER electrocatalysts, by properly engineering organic linkers, is related not only to an alteration of the electron density (acidity) of the metal center but also to a modification of the electron localization and conductivity of CPs.     

CoOx@Co-NC Catalyst with Dual Active Centers for Enhanced Oxygen Evolution: Breaking Trade-Off of Particle Size and Metal Loading

Increasing the metal loading and downsizing the metal particle size are two effective ways to boost the electrochemical performance of catalysts. However, it is difficult to simultaneously increase the metal loading and reduce the particle size since isolated individual atoms are easy to aggregate into nanoparticles when increasing the metal loading. To tackle this contradiction, we report a bottom-up ligand-mediated strategy to facilely prepare ultrafine CoO_x nanoclusters anchored on a Co-N-containing carbon matrix (CoO_x@Co-NC). The co-exist of N and O atoms prevent Co atoms agglomerating into large particles and allowing the formation of ultrafine dispersed Co species with large Co loading (up to 20 wt.%). Since the relationship between ultrasmall size and large metal loading is well balanced, the CoO_x nanoclusters have no inhibitory effect, but facilitate the catalytic performance of Co-N₄ sites during OER process. Consequently, due to the synergistic effect of ultrafine CoO_x nanoclusters and Co-N₄ macrocycles, the as-synthesized CoO_x@Co-NC exhibit promising OER activity (η₁₀=370 mV, Tafel plot=40 mV/dec), bettering than that of benchmark RuO₂ (η₁₀=411 mV, Tafel plot=72 mV/dec). This ligand-mediated strategy to synthesize carbonaceous materials containing dual active centers with large metal loading is promising for developing active and stable catalysts for electrocatalytic applications.     

Electrocatalysts Based on Transition Metal Borides and Borates for the Oxygen Evolution Reaction

Electrochemical water splitting is a clean and sustainable process for hydrogen production on a large scale as the electrical power required can be obtained from various renewable energy resources. The key challenge in electrochemical water splitting process is to develop low-cost electrocatalysts with high catalytic activity for the hydrogen evolution reaction (HER) on the cathode and the oxygen evolution reaction (OER) on the anode. OER is the most important half-reaction involved in water splitting, which has been extensively studied since the last century and a large amount of electrocatalysts including noble and non-noble metal-based materials have been developed. Among them, transition metal borides and borates (TMBs)-based compounds with various structures have attracted increasing attention owing to their excellent OER performance. In recent years, many efforts have been devoted to exploring the OER mechanism of TMBs and to improving the OER activity and stability of TMBs. In this review, recent research progress made in TMBs as efficient electrocatalysts for OER is summarized. The chemical properties, synthetic methodologies, catalytic performance evaluation, and improvement strategy of TMBs as OER electrocatalysts are discussed. The electrochemistry fundamentals of OER are first introduced in brief, followed by a summary of the preparation and performance of TMBs-based OER electrocatalysts. Finally, current challenges and future directions for TMBs-based OER electrocatalysts are discussed.     

An Interfacial View of Cation Effects on Electrocatalysis Systems

The identity of alkali metal cations in the electrolyte of electrocatalysis systems has been recently introduced as a crucial factor to tailor the kinetics and Faradaic efficiency of many electrocatalytic reactions. In this Minireview, we have summarized the recent advances in the molecular-level understanding of cation effects on relevant electrocatalytic processes such as hydrogen evolution (HER), oxygen evolution (OER), and CO₂ electroreduction (CO₂RR) reactions. The discussion covers the effects of electrolyte cations on interfacial electric fields, structural organization of interfacial water molecules, blocking the catalytic active sites, stabilization or destabilization of intermediates, and interfacial pHs. These cation-induced interfacial phenomena have been reported to impact the performance (activity, selectivity, and stability) of electrochemical reactions collaboratively or independently. We describe that although there is almost a general agreement on the relationship between the size of alkali cations and the activities of HER, OER, and CO₂RR, however, the mechanism by which the performance of these electrocatalytic reactions is influenced by alkali metal cations is still in debate.