The simultaneous presence of two active metal centres in diatomic catalysts (DACs) leads to the occurrence of specific interactions between active sites. Such interactions, referred to as long‐range ...interactions (LRIs), play an important role in determining the rate and selectivity of a reaction. The optimal combination of metal centres must be determined to achieve the targeted efficiency. To date, various types of DACs have been synthesised and applied in electrochemistry. However, LRIs have not been systematically summarised. Herein, the regulation, mechanism, and electrocatalytic applications of LRIs are comprehensively summarised and discussed. In addition to the basic information above, the challenges, opportunities, and future development of LRIs in DACs are proposed in order to present an overall view and reference for future research.
Diatomic catalysts have attracted much attention, especially in electrochemistry. However, there have been no comprehensive reviews on long‐range interactions (LRIs) between metallic centres. This Minireview introduces the key aspects of LRIs and highlights opportunities for regulating electrocatalytic mechanisms, thus presenting guidelines for the targeted usage of LRIs.
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It is still of great difficulty to develop the non‐platinum catalyst with high catalytic efficiency towards hydrogen evolution reaction via the strategies till now. Therefore, it is necessary to ...develop the new methods of catalyst designing. Here, we put forward the catalyst designed by the electronic metal–support interaction (EMSI), which is demonstrated to be a reliable strategy to find out the high‐efficiency catalyst. We carried out the density functional theory calculation first to design the proper EMSI of the catalyst. We applied the model of M1‐M2‐X (X=C, N, O) during the calculation. Among the catalysts we chose, the EMSI of Rh1TiC, with the active sites of Rh1‐Ti2C2, is found to be the most proper one for HER. The electrochemical experiment further demonstrated the feasibility of the EMSI strategy. The single atomic site catalyst of Rh1‐TiC exhibits higher catalytic efficiency than that of state‐of‐art Pt/C. It achieves a small overpotential of 22 mV and 86 mV at the at the current density of 10 mA cm−2 and 100 mA cm−2 in acid media, with a Tafel slope of 25 mV dec−1 and a mass activity of 54403.9 mA cm−2 mgRh−1 (vs. 192.2 mA cm−2 mgPt−1 of Pt/C). Besides, it also shows appealing advantage in energy saving compared with Pt/C (≈20 % electricity consuming decrease at 2 kA m−2) Therefore, we believe that the strategy of regulating EMSI can act as a possible way for achieving the high catalytic efficiency on the next step of SACs.
The electronic metal–support interaction (EMSI) is closely related to the electronic structure of active sites, which determines the catalytic activity. We put forward a method of designing the EMSI of single‐atomic site catalysts (SACs) to achieve high efficiency. The SACs achieve a lower overpotential and higher mass activity than any other SACs towards hydrogen evolution reaction, demonstrating the benefits of this method.
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The exploitation of highly efficient carbon dioxide reduction (CO2RR) electrocatalyst for methane (CH4) electrosynthesis has attracted great attention for the intermittent renewable electricity ...storage but remains challenging. Here, N‐heterocyclic carbene (NHC)‐ligated copper single atom site (Cu SAS) embedded in metal–organic framework is reported (2Bn‐Cu@UiO‐67), which can achieve an outstanding Faradaic efficiency (FE) of 81 % for the CO2 reduction to CH4 at −1.5 V vs. RHE with a current density of 420 mA cm−2. The CH4 FE of our catalyst remains above 70 % within a wide potential range and achieves an unprecedented turnover frequency (TOF) of 16.3 s−1. The σ donation of NHC enriches the surface electron density of Cu SAS and promotes the preferential adsorption of CHO* intermediates. The porosity of the catalyst facilitates the diffusion of CO2 to 2Bn‐Cu, significantly increasing the availability of each catalytic center.
A catalyst with N‐heterocyclic carbene‐ligated Cu SAS as the active site, accompanied by many micro‐nano reactors, synergistically promotes the electrochemical synthesis of methane.
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Chlorine evolution reaction has been applied in the production since a century ago. After times of evolution, it has been widely realized by the electrocatalytic process on anode nowadays. However, ...the anode applied in production contains a large amount of precious metal, increasing the cost. It is thus an opportunity to apply sub‐nano catalysts in this field. By regulating the tip effect (TE) of the catalyst, it was discovered that the oxidized sub‐nano iridium clusters supported by titanium carbide exhibit much higher efficiency than the single‐atom one, which demonstrates the significance of modifying the electronic interaction. Moreover, it exhibits a ≈20 % decrease of the electricity, ≈98 % selectivity towards chlorine evolution reaction, and high durability of over 350 h. Therefore, this cluster catalyst performs great potential in applying in the practical production and the comprehension of the tip effect on different types of catalysts is also pushed to a higher level.
The tip effect (TE) has not been mentioned enough in catalysts designing, having a large space to explore. Based on the model of oxidized sub‐nano clusters, the TE was regulated and found to be efficient in designing catalysts, making TiC perform a high activity during the chlor‐alkali industry. This cluster system exhibits great potential in applying in the practical production and the comprehension of the TE is also pushed to a higher level.
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Consuming one of the largest amount of electricity, the chlor‐alkali industry supplies basic chemicals for society, which mainly consists of two reactions, hydrogen evolution (HER) and chlorine ...evolution reaction (CER). Till now, the state‐of‐the‐art catalyst applied in this field is still the dimensional stable anode (DSA), which consumes a large amount of noble metal of Ru and Ir. It is thus necessary to develop new types of catalysts. In this study, an organocatalyst anchored on the single‐atom support (SAS) is put forward. It exhibits high catalytic efficiency towards both HER and CER with an overpotential of 21 mV and 20 mV at 10 mA cm−2. With this catalyst on both electrodes, the energy consumption is cut down by 1.2 % compared with the commercial system under industrial conditions. Based on this novel catalyst and the high activity, the mechanism of modifying non‐covalent interaction is demonstrated to be reliable for the catalyst's design. This work not only provides efficient catalysts for the chlor‐alkali industry but also points out that the SACs can also act as support, providing new twists for the development of SACs and organic molecules in the next step.
Constructing a bridge between single‐atom catalysts and organocatalysts, organic molecules anchored on single‐atom supports exhibit high efficiency, durability, and bifunctional properties on both electrodes used in the chlor‐alkali industry. This work not only provides an alternative choice for the chlor‐alkali industry but also provides a new platform to study the catalyst consisting of inorganic and organic species together, which performs well in both reduction and oxidation process.
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Conventional ion batteries utilizing metallic ions as the single charge carriers are limited by the insufficient abundance of metal resources. Although supercapacitors apply both cations and anions ...to store energy through absorption and/or Faradic reactions occurring at the interfaces of the electrode/electrolyte, the inherent low energy density hinders its application. The graphite‐cathode‐based dual‐ion battery possesses a higher energy density due to its high working potential of nearly 5 V. However, such a battery configuration suffers from severe electrolyte decomposition and exfoliation of the graphite cathode, rendering an inferior cycle life. Herein, a new surface‐modification strategy is developed to protect the graphite cathode from the anion salvation effect and the deposition derived from electrolyte decomposition by generating an artificial solid electrolyte interphase (SEI). Such SEI‐modified graphite exhibits superior cycling stability with 96% capacity retention after 500 cycles under 200 mA g−1 at the upper cutoff voltage of 5.0 V, which is much improved compared with the pristine graphite electrode. Through several ex situ studies, it is revealed that the artificial SEI greatly stabilizes the interfaces of the electrode/electrolyte after reconstruction and gradual establishment of the optimal anion‐transport path. The findings shed light on a new avenue toward promoting the performance of the dual‐ion battery (DIB) and hence to make it practical finally.
An artificial layer of a solid electrolyte interphase is fabricated on a graphite cathode for a dual‐ion battery (DIB). Such surface modification can alleviate the electrolyte decomposition at the high working voltage of the anion de‐/intercalation processes and the solvation effect of anions, much improving the cycling stability of the Li//graphite DIB.
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Although ether‐based electrolytes have been extensively applied in anode evaluation of batteries, anodic instability arising from solvent oxidability is always a tremendous obstacle to matching with ...high‐voltage cathodes. Herein, by rational design for solvation configuration, the fully coordinated ether‐based electrolyte with strong resistance against oxidation is reported, which remains anodically stable with high‐voltage Na3V2(PO4)2O2F (NVPF) cathode under 4.5 V (versus Na+/Na) protected by an effective interphase. The assembled graphite//NVPF full cells display superior rate performance and unprecedented cycling stability. Beyond that, the constructed full cells coupling the high‐voltage NVPF cathode with hard carbon anode exhibit outstanding electrochemical performances in terms of high average output voltage up to 3.72 V, long‐term cycle life (such as 95 % capacity retention after 700 cycles) and high energy density (247 Wh kg−1). In short, the optimized ether‐based electrolyte enriches systematic options, the ability to maintain oxidative stability and compatibility with various anodes, exhibiting attractive prospects for application.
By rational design of the solvation configuration, a cation–solvent fully coordinated ether‐based electrolyte with strong oxidation resistance up to 4.5 V (versus Na+/Na) was developed and applied in graphite//NVPF and LHC//NVPF full cells which showed superior rate performance and unprecedented cycling stability.
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Hard carbon is regarded as a promising anode material for sodium‐ion batteries (SIBs). However, it usually suffers from the issues of low initial Coulombic efficiency (ICE) and poor rate performance, ...severely hindering its practical application. Herein, a flexible, self‐supporting, and scalable hard carbon paper (HCP) derived from scalable and renewable tissue is rationally designed and prepared as practical additive‐free anode for room/low‐temperature SIBs with high ICE. In ether electrolyte, such HCP achieves an ICE of up to 91.2% with superior high‐rate capability, ultralong cycle life (e.g., 93% capacity retention over 1000 cycles at 200 mA g−1) and outstanding low‐temperature performance. Working mechanism analyses reveal that the plateau region is the rate‐determining step for HCP with a lower electrochemical reaction kinetics, which can be significantly improved in ether electrolyte.
A self‐supporting, flexible, additive‐free and scalable hard carbon paper (HCP) derived from tissue is rationally developed, and it achieves outstanding Na‐storage properties in terms of high initial Coulombic efficiency (91.2%), superior high‐rate capability, ultralong cyclic stability, as well as outstanding low‐T performance in ether electrolyte. More significantly, the Na‐storage and capacity attenuation mechanism of the HCP anode is revealed.
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Covalent organic frameworks (COF) possess a robust and porous crystalline structure, making them an appealing candidate for energy storage. Herein, we report an exfoliated polyimide COF composite ...(P‐COF@SWCNT) prepared by an in situ condensation of anhydride and amine on the single‐walled carbon nanotubes as advanced anode for potassium‐ion batteries (PIBs). Numerous active sites exposed on the exfoliated frameworks and the various open pathways promote the highly efficient ion diffusion in the P‐COF@SWCNT while preventing irreversible dissolution in the electrolyte. During the charging/discharging process, K+ is engaged in the carbonyls of imide group and naphthalene rings through the enolization and π‐K+ effect, which is demonstrated by the DFT calculation and XPS, ex‐situ FTIR, Raman. As a result, the prepared P‐COF@SWCNT anode enables an incredibly high reversible specific capacity of 438 mA h g−1 at 0.05 A g−1 and extended stability. The structural advantage of P‐COF@SWCNT enables more insights into the design and versatility of COF as an electrode.
We prepare a polyimide covalent organic framework composite anode by effective in‐situ condensation of anhydride and amine on the surface of single‐walled carbon nanotubes. The construction of the conductive network accelerates the transport of electron. Dual electroactive sites in the framework, carbonyls and aromatic naphthalene rings, could store more potassium ions by the enolization and π‐K+ effect.
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Impossible voltage plateau regulation for the cathode materials with fixed active elemental center is a pressing issue hindering the development of Na‐superionic‐conductor (NASICON)‐type ...Na3V2(PO4)2F3 (NVPF) cathodes in sodium‐ion batteries (SIBs). Herein, a high‐entropy substitution strategy, to alter the detailed crystal structure of NVPF without changing the central active V atom, is pioneeringly utilized, achieving simultaneous electronic conductivity enhancement and diffusion barrier reduction for Na+, according to theoretical calculations. The as‐prepared carbon‐free high‐entropy Na3V1.9(Ca,Mg,Al,Cr,Mn)0.1(PO4)2F3 (HE‐NVPF) cathode can deliver higher mean voltage of 3.81 V and more advantageous energy density up to 445.5 Wh kg−1, which is attributed by the diverse transition‐metal elemental substitution in high‐entropy crystalline. More importantly, high‐entropy introduction can help realize disordered rearrangement of Na+ at Na(2) active sites, thereby to refrain from unfavorable discharging behaviors at low‐voltage region, further lifting up the mean working voltage to realize a full Na‐ion storage at the high voltage plateau. Coupling with a hard carbon (HC) anode, HE‐NVPF//HC SIB full cells can deliver high specific energy density of 326.8 Wh kg−1 at 5 C with the power density of 2178.9 W kg−1. This route means the unlikely potential regulation in NASICON‐type crystal with unchangeable active center becomes possible, inspiring new ideas on elevating the mean working voltage for SIB cathodes.
A high‐entropy effect is delicately introduced into fluorophosphate cathode for sodium‐ion batteries by in situ partial substitution of active V central atom, preparing a high‐entropy carbon‐free Na3V1.9(Ca,Mg,Al,Cr,Mn)0.1(PO4)2F3 cathode, suppressing the occurrence of detrimental phase transition process in the low‐voltage region, and further lifting up the mean working voltage of pristine Na3V2(PO4)2F3, enhancing sodium storage behavior, rate capability, and cycle performance.
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