Adsorption Strength Of Intermediates Research Articles

Frustrated Lewis Pair Mediated f‐p‐d Orbital Coupling: Achieving Selective Seawater Oxidation and Breaking *OH and *OOH Scaling Relationship

The development of materials for hydrogen production via seawater electrolysis at high current densities plays a crucial role in producing renewable hydrogen energy. However, during the seawater electrolysis process, the anode inevitably undergoes chloride oxidation reaction (ClOR) due to Cl‐ adsorption, making the seawater electrolysis process difficult to sustain. Inspired by the selective permeability of cell membranes, we propose a biomimetic design of frustrated Lewis pairs (FLPs) layers. Combining experimental results and molecular dynamics simulations, it has been demonstrated that cerium dioxide layers with FLPs sites can decompose water molecules, capture hydroxyl anions, and repel chloride ions simultaneously. DFT theoretical analysis indicates that the FLP sites regulate the Ce 4f‐O 2p‐Ni 3d gradient orbital coupling, providing additional oxygen non‐bonding (ONB) to stabilize the Ni‐O bond and optimize the adsorption strength of intermediates, thereby breaking the *OH and *OOH scaling relationship. Assembled anion exchange membrane electrolyzers exhibit an efficiency of 95.7% at a current density of 0.1 A cm‐2 and can stably operate for 250 hours at a current density of 0.2 A cm‐2.

Frustrated Lewis Pair Mediated f-p-d Orbital Coupling: Achieving Selective Seawater Oxidation and Breaking *OH and *OOH Scaling Relationship.

The development of materials for hydrogen production via seawater electrolysis at high current densities plays a crucial role in producing renewable hydrogen energy. However, during the seawater electrolysis process, the anode inevitably undergoes chloride oxidation reaction (ClOR) due to Cl- adsorption, making the seawater electrolysis process difficult to sustain. Inspired by the selective permeability of cell membranes, we propose a biomimetic design of frustrated Lewis pairs (FLPs) layers. Combining experimental results and molecular dynamics simulations, it has been demonstrated that cerium dioxide layers with FLPs sites can decompose water molecules, capture hydroxyl anions, and repel chloride ions simultaneously. DFT theoretical analysis indicates that the FLP sites regulate the Ce 4f-O 2p-Ni 3d gradient orbital coupling, providing additional oxygen non-bonding (ONB) to stabilize the Ni-O bond and optimize the adsorption strength of intermediates, thereby breaking the *OH and *OOH scaling relationship. Assembled anion exchange membrane electrolyzers exhibit an efficiency of 95.7% at a current density of 0.1 A cm-2 and can stably operate for 250 hours at a current density of 0.2 A cm-2.

Modulating the Electronic Structure of Metal Halide Perovskites for Efficient Selective CO2 Photoreduction to CO

Metal halide perovskites (MHPs) have recently held great promise for solar-to-fuel conversion via artificial photosynthesis technology. However, the conversion efficiency of most MHP photocatalysts is still far below that necessary for their practical implementation. Modulating the electronic structure is a promising strategy to solve this issue. Here, taking Cs2AgBiBr6 as a prototype, we investigate the interplay between the local electronic structure of Cs2AgBiBr6 and its photocatalytic performance via introducing heteroatoms. Theoretical calculations reveal that Au heteroatom-mediated orbital rehybridization induces high electron densities and tailors the d-band center of Cs2AgBiBr6, endowing more upshifted d-band center and enhanced adsorption strength of intermediates, thereby resulting in decreased energy barriers for selective CO2 photoreduction to CO product. Experimentally, we report the Cu-incorporated Cs2AgBiBr6 catalyst for selective photoreduction of CO2 to CO in a solid-gas system without sacrificial agents, yielding an on average CO generation rate of 47.3 μmol g−1 with approximately 100% selectively, outperforming the pure Cs2AgBiBr6 and comparable to the reported MHP-based photocatalysts. This work showcases modulating the electronic structure of MHP photocatalysts offering a powerful route for effective solar fuel generation.

Activity trends of Pd clusters supported on C2N for oxygen evolution and reduction reactions

Developing highly efficient electrocatalysts for the oxygen evolution reaction (OER) and reduction reaction (ORR) is crucial for future renewable energy technology. Here, we use first-principles calculations combined with genetic algorithm to determine the structures of various Pd clusters supported on experimentally available C2N monolayer and evaluate the OER and ORR performance. Our findings show that the activity of the supported Pd clusters is closely linked to the local geometrical and electronic structure of the active site. Furthermore, we establish the activity trends of the clusters based on the adsorption free energies of intermediates. In particular, C2N supported Pd7 and Pd8 clusters exhibit outstanding OER activity with low overpotentials. We identify a volcano relation for the OER on the clusters, suggesting that the high activity of the cluster is related to the moderate adsorption strength of intermediates. Mechanistic analysis indicates that the second water formation is the potential-determining step for ORR on the clusters due to the strong adsorption of *OH. Additionally, we identify a linear scaling relationship between the ORR overpotentials and adsorption free energies of *OH, demonstrating that reducing the adsorption strength of reaction intermediates on Pd clusters can improve the activity. This work unravels the activity trends of cluster catalysts and provides strategies for the rational design of highly efficient single-cluster catalysts for OER and ORR.

In situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction

Single-atom catalysts, especially those with metal−N4 moieties, hold great promise for facilitating the oxygen reduction reaction. However, the symmetrical distribution of electrons within the metal−N4 moiety results in unsatisfactory adsorption strength of intermediates, thereby limiting their performance improvements. Herein, we present atomically coordination-regulated Co single-atom catalysts that comprise a symmetry-broken Cl−Co−N4 moiety, which serves to break the symmetrical electron distribution. In situ characterizations reveal the dynamic evolution of the symmetry-broken Cl−Co−N4 moiety into a coordination-reduced Cl−Co−N2 structure, effectively optimizing the 3d electron filling of Co sites toward a reduced d-band electron occupancy (d5.8 → d5.28) under reaction conditions for a fast four-electron oxygen reduction reaction process. As a result, the coordination-regulated Co single-atom catalysts deliver a large half-potential of 0.93 V and a mass activity of 5480 A gmetal−1. Importantly, a Zn-air battery using the coordination-regulated Co single-atom catalysts as the cathode also exhibits a large power density and excellent stability.

Coordination Environment Engineering to Regulate the Adsorption Strength of Intermediates in Single Atom Catalysts for High-performance CO2 Reaction Reduction.

The modulation of the coordination environment of single atom catalysts (SACs) plays a vital role in promoting CO2 reduction reaction (CO2RR). Herein, N or B doped Fe-embedded graphyne (Fe-GY), Fe-nXGYm (n = 1, 2, 3; X = N, B; m = 1, 2, 3), are employed as probes to reveal the effect of the coordination environment engineering on CO2RR performance via heteroatom doping in SACs. The results show that the doping position and number of N or B in Fe-GY significantly affects catalyst activity and CO2RR product selectivity. In comparison, Fe-1NGY exhibits high-performance CO2RR to CH4 with a low limiting potential of -0.17V, and Fe-2NGY3 is demonstrated as an excellent CO2RR electrocatalyst for producing HCOOH with a low limiting potential of -0.16V. With applied potential, Fe-GY, Fe-1NGY, and Fe-2NGY3 exhibit significant advantages in CO2RR to CH4 while hydrogen evolution reaction is inhibited. The intrinsic essence analysis illustrates that heteroatom doping modulates the electronic structure of active sites and regulates the adsorption strength of the intermediates, thereby rendering a favorable coordination environment for CO2RR. This work highlights Fe-nXGYm as outstanding SACs for CO2RR, and provides an in-depth insight into the intrinsic essence of the promotion effect from heteroatom doping.

Dual-Atom Co/Ni Electrocatalyst Anchored at the Surface-Modified Ti3C2Tx MXene Enables Efficient Hydrogen and Oxygen Evolution Reactions.

Dual-atom catalytic sites on conductive substrates offer a promising opportunity for accelerating the kinetics of multistep hydrogen and oxygen evolution reactions (HER and OER, respectively). Using MXenes as substrates is a promising strategy for depositing those dual-atom electrocatalysts, if the efficient surface anchoring strategy ensuring metal-substrate interactions and sufficient mass loading is established. We introduce a surface-modification strategy of MXene substrates by preadsorbing L-tryptophan molecules, which enabled attachment of dual-atom Co/Ni electrocatalyst at the surface of Ti3C2Tx by forming N-Co/Ni-O bonds, with mass loading reaching as high as 5.6 wt %. The electron delocalization resulting from terminated O atoms on MXene substrates, N atoms in L-tryptophan anchoring moieties, and catalytic metal atoms Co and Ni provides an optimal adsorption strength of intermediates and boosts the HER and OER kinetics, thereby notably promoting the intrinsic activity of the electrocatalyst. CoNi-Ti3C2Tx electrocatalyst displayed HER and OER overpotentials of 31 and 241 mV at 10 mA cm-2, respectively. Importantly, the CoNi-Ti3C2Tx electrocatalyst also exhibited high operational stability for both OER and HER over 100 h at an industrially relevant current density of 500 mA cm-2. Our study provided guidance for constructing dual-atom active metal sites on MXene substrates to synergistically enhance the electrochemical efficiency and stability of the energy conversion and storage systems.

Site-specific metal-support interaction to switch the activity of Ir single atoms for oxygen evolution reaction

The metal-support interactions (MSI) could greatly determine the electronic properties of single-atom catalysts, thus affecting the catalytic performance. However, the typical approach to regulating MSI usually suffers from interference of the variation of supports or sacrificing the stability of catalysts. Here, we effectively regulate the site-specific MSI of Ir single atoms anchored on Ni layered double hydroxide through an electrochemical deposition strategy. Cathodic deposition drives Ir atoms to locate at three-fold facial center cubic hollow sites with strong MSI, while anodic deposition drives Ir atoms to deposit onto oxygen vacancy sites with weak MSI. The mass activity and intrinsic activity of Ir single-atom catalysts with strong MSI towards oxygen evolution reaction are 19.5 and 5.2 times that with weak MSI, respectively. Mechanism study reveals that the strong MSI between Ir atoms and the support stimulates the activity of Ir sites by inducing the switch of active sites from Ni sites to Ir sites and optimizes the adsorption strength of intermediates, thereby enhancing the activity.

Rare-earth Element-based Electrocatalysts Designed for CO2 Electro-reduction.

Electrochemical CO2 reduction presents a promising approach for synthesizing fuels and chemical feedstocks using renewable energy sources. Although significant advancements have been made in the design of catalysts for CO2 reduction reaction (CO2RR) in recent years, the linear scaling relationship of key intermediates, selectivity, stability, and economical efficiency are still required to be improved. Rare earth (RE) elements, recognized as pivotal components in various industrial applications, have been widely used in catalysis due to their unique properties such as redox characteristics, orbital structure, oxygen affinity, large ion radius, and electronic configuration. Furthermore, RE elements could effectively modulate the adsorption strength of intermediates and provide abundant metal active sites for CO2RR. Despite their potential, there is still a shortage of comprehensive and systematic analysis of RE elements employed in the design of electrocatalysts of CO2RR. Therefore, the current approaches for the design of RE element-based electrocatalysts and their applications in CO2RR are thoroughly summarized in this review. The review starts by outlining the characteristics of CO2RR and RE elements, followed by a summary of design strategies and synthetic methods for RE element-based electrocatalysts. Finally, an overview of current limitations in research and an outline of the prospects for future investigations are proposed.

Breaking Scaling Relations for Highly Efficient Electroreduction of CO2 to CO on Atomically Dispersed Heteronuclear Dual-Atom Catalyst.

Conversion of CO2 into value-added products by electrocatalysis provides a promising way to mitigate energy and environmental problems. However, it is greatly limited by the scaling relationship between the adsorption strength of intermediates. Herein, Mn and Ni single-atom catalysts, homonuclear dual-atom catalysts (DACs), and heteronuclear DACs are synthesized. Aberration-corrected annular dark-field scanning transmission electron microscopy (ADF-STEM) and X-ray absorption spectroscopy characterization uncovered the existence of the Mn─Ni pair in Mn─Ni DAC. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy reveal that Mn donated electrons to Ni atoms in Mn─Ni DAC. Consequently, Mn─Ni DAC displays the highest CO Faradaic efficiency of 98.7% at -0.7V versus reversible hydrogen electrode (vs RHE) with CO partial current density of 16.8mAcm-2. Density functional theory calculations disclose that the scaling relationship between the binding strength of intermediates is broken, resulting in superior performance for ECR to CO over Mn─Ni─NC catalyst.

Stay hydrated! Impact of solvation phenomena on the CO2 reduction reaction on Pb (100) and Ag(100) surfaces.

This article presents a comprehensive computational study of the impact of solvation on the reduction reaction of CO2to formic acid (HCOOH) and carbon monoxide (CO) at Pb(100) and Ag(100) surfaces. Results further the understanding of how solvation phenomena influence the adsorption energies of reaction intermediates. We applied an explicit solvation scheme harnessing a combined density functional theory (DFT)/microkinetic modeling approach for the CO2reduction reaction. This approach reveals high selectivities for CO formation at Ag and HCOOH formation at Pb, successfully reconciling the disparity between ab initio calculations and experimental observations. Furthermore, the detailed analysis of adsorption energies of relevant reaction intermediates shows that the total number of hydrogen bonds formed by HCOO plays a primary role for the adsorption strength of intermediates and the electrocatalytic activity. Results emphasize the importance of explicit solvation for adsorption and electrochemical reaction phenomena on metal surfaces.

Boosting Reaction Kinetics and Mass Transfer of Bifunctional Co‐Based Oxygen Electrocatalyst Prepared from CoAl‐LDH

AbstractThe simultaneous optimization of sluggish reaction kinetics and mass transfer in bifunctional oxygen electrocatalysts for air cathodes remains a great challenge. This study utilizes CoAl‐layered double hydroxide as a metal precursor to fabricate a bifunctional oxygen electrocatalyst, denoted as CoAlOXD‐Thin. This electrocatalyst features a specific core–shell structure of Co species, which grows on an aerophilic and conductive substrate composed of Al2O3 and carbon. It is successfully demonstrated that the thickness of Co@Co3O4 core–shell structure can be easily controlled by selecting different precursors and the combination of Co core and Co3O4 shell optimizes the adsorption strength of intermediates, leading to enhanced catalytic performance. Additionally, the Al species plays a dual role. It not only facilitates the mass transfer of oxygen species but also hinders the 2e− pathway of oxygen reduction reaction, leading to improved selectivity. Notably, the Zn–air batteries utilizing CoAlOXD‐Thin demonstrate an impressive peak power density of 216.2 mW cm−2, a high specific capacity of 800.8 mAh gZn−1, and excellent cycling stability and reversibility, surpassing those of the Pt/C + RuO2 catalyst. This study presents a novel approach to enhance air cathode performance by optimizing reaction kinetics and mass transfer through precursor design.

Reinforce the Co-O Covalency via Ce(4f)-O(2p)-Co(3d) Gradient Orbital Coupling for High-efficiency Oxygen Evolution.

Rare-earth (RE)-based transition metal oxides (TMO) are emerging as a frontier towards oxygen evolution reaction (OER), yet the knowledge regarding their electrocatalytic mechanism and active sites is very limited. Herein, we successfully design and synthesize atomically dispersed Ce on CoO by an effective plasma (P)-assisted strategy as a model (P-Ce SAs@CoO) to investigate the origin of OER performance in RE-TMO systems. The P-Ce SAs@CoO exhibits favorable performance with an overpotential of only 261mV at 10mA cm-2 and robust electrochemical stability, superior to individual CoO. X-ray absorption spectroscopy and in-situ electrochemical Raman spectroscopy uncover that the Ce-induced electron redistribution inhibits Co-O bond breakage in the Co-O-Ce unit site. Theoretical analyses demonstrate that the gradient orbital coupling reinforces the Co-O covalency of Ce(4f)-O(2p)-Co(3d) unit active site with an optimized Co-3d-eg occupancy, which can balance the adsorption strength of intermediates and in turn reach the apex of the theoretical OER maximum, in excellent agreement with experimental observations. We believe the establishment of this Ce-CoO model can set a basis for the mechanistic understanding and structural design of high-performance RE-TMO catalysts. This article is protected by copyright. All rights reserved.

Understanding the Activity and Design Principle of Dual-Atom Catalysts Supported on C2N for Oxygen Reduction and Evolution Reactions: From Homonuclear to Heteronuclear

Using large-scale ab initio calculations and taking the two-dimensional C2N monolayer as a substrate, we sampled a large combinatorial space of C2N-supported homonuclear and heteronuclear dual-atom catalysts and built a detailed view of catalytic activity and stability toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The results indicate that regulating combinations of metal pairs could widely tune the catalytic performance. Pd2-, Pt2-, and PdPt-C2N could effectively balance the adsorption strength of intermediates and achieve optimal bifunctional activity. The favorable catalytic performance could also be realized on GaPd-C2N for the ORR and PdRh-C2N for the OER, surpassing corresponding homonuclear counterparts. The thermodynamic and electrochemical stability simulations reveal that these metal pairs can be stably anchored onto the C2N matrix. Multiple-level descriptors, including Gibbs free energy, d-band center, and bonding/antibonding orbital population, are established to track the activity trend and reveal the origin of activity, indicating that catalytic activity is intrinsically governed by the d-band center of metal pairs.

Screening of single-atom catalysts of transition metal supported on MoSe2 for high-efficiency nitrogen reduction reaction

Two-dimensional single-atom catalysts (2D SACs) have attracted much more attention in the field of ammonia synthesis via electrochemical nitrogen reduction reaction (NRR). In this work, we comprehensively study the NRR performance of 28 transition metals SACs loaded on 2D MoSe2 using density functional theory calculations. In view of thermodynamics and electrochemical stability, adsorption of N2, selectivity and activity of NRR, Mn, Os, V@MoSe2 exhibit outstanding performances with the most favorable potentials of -0.39 V, -0.36 V and -0.36 V, respectively. The excellent NRR performances are comprehensively related to the electronic states, kinetics, and NN bond length. Furthermore, aiming at three vital processes of NRR (adsorption and activation of N2, adsorption strength of intermediates, and the limiting potential), three independent descriptors (φ, ICOHP, ΔG*N) are adopted to make the activity trend clear. The results are of guiding significance to the design of high-efficiency NRR using SAC.

CoP@Ni core-shell heterostructure nanowire array: A highly efficient electrocatalyst for hydrogen evolution

The inferior performance of non-precious metals on electrocatalytic hydrogen evolution can be mainly attributed to the inappropriate adsorption strength of intermediates. A core–shell heterostructure of CoP@Ni is developed by hydrothermal reaction, thermal phosphorization and subsequent electrodeposition, with metallic Ni supported by CoP nanowire array. The as-prepared CoP@Ni core–shell heterostructure nanowire array has a superior activity on hydrogen evolution in alkaline electrolyte, with an overpotential of 71 mV to drive 10 mA cm−2 and a Tafel slope of 66 mV dec-1. The electronic structure of CoP@Ni is tuned for modulating the adsorption strength of intermediates. The theoretical calculations reveal that CoP@Ni has metallic characteristics with a zero-bandgap, which leads to the promoted charge transfer. More importantly, the intrinsic activity of CoP@Ni is greatly increased, with a lower energy barrier in the reaction pathway. This work points out the importance of constructing the heterostructure for improving the intrinsic activity, which can pave the way to the exploration of high-performance and cost-effective electrocatalysts for hydrogen production.

Oxo transition metal anchored on C3N4 with constructing a high-activity bifunctional electrocatalyst for rechargeable metal-air batteries.

It is urgent to find efficient bifunctional electrocatalysts of oxygen reduction and evolution reactions to catalyze the oxygen electrode reaction of metal-air batteries. Herein, oxo transition metal anchored on C3N4 as bifunctional oxygen electrocatalyst is investigated using density functional theory calculations. Various stability analysis results show that all catalysts in this study have excellent stability. In particular, for the two sites of the catalyst, the calculated results show that the effect of the β site on the reaction species is generally stronger than that of the α site, while the catalytic activity of the α site is slightly better than that of β site. In particular, the α site on Ni2@C3N4 has the lowest overpotential (ηORR = 0.44 V, ηOER = 0.51 V) and bifunctional index value (BI = 0.95 V). Finally, the linear relationships between eight activity descriptors and the adsorption strength of reaction intermediates are used to analyze the influencing factors of the effective activity of the catalyst. The results reflect that the activity descriptors can well describe the change in adsorption strength of intermediates on the catalyst. Thus, this work provides a good idea for designing excellent bifunctional catalysts for rechargeable metal-air batteries.

Selective and high-rate CO2 electroreduction by metal-doped covalent triazine frameworks: a computational and experimental hybrid approach.

The electrochemical CO2 reduction reaction (CO2RR) has attracted intensive attention as a technology to achieve a carbon-neutral society. The use of gas diffusion electrodes (GDEs) enables the realization of high-rate CO2RRs, which is one of the critical requirements for social implementation. Although both a high reaction rate and good selectivity are simultaneously required for electrocatalysts on GDEs, no systematic study of the relationship among active metal centers in electrocatalysts, reaction rate, and selectivity under high-rate CO2RR conditions has been reported. In the present study, we employed various metal-doped covalent triazine frameworks (M-CTFs) as platforms for CO2 reduction reaction (CO2RR) electrocatalysts on GDEs and systematically investigated them to deduce sophisticated design principles using a combined computational and experimental approach. The Ni-CTF showed both high selectivity (faradaic efficiency (FE) > 98% at -0.5 to -0.9 V vs. reversible hydrogen electrode) and a high reaction rate (current density < -200 mA cm-2) for CO production. By contrast, the Sn-CTF exhibited selective formic acid production, and the FE and partial current density reached 85% and 150 mA cm-2, respectively. These results for the CO2RR activity and selectivity at high current density with respect to metal centers correspond well with predictions based on first-principles calculations. This work is the first demonstration of a clear relationship between the computational adsorption energy of intermediates depending on metal species and the experimental high-rate gaseous CO2RR.

Tuning the d-Band States of Ni-Based Serpentine Materials via Fe3+ Doping for Efficient Oxygen Evolution Reaction.

The serpentine germanate materials are promising oxygen evolution reaction (OER) electrocatalysts due to their unique layered crystal structure and electronic structure. However, the catalytic activities still need to be improved to satisfy the practical applications. Adjusting the d-band center of metal active site to balance the adsorption and desorption of intermediates is considered an effective approach to improve the OER activity. In this work, an element dopant strategy was proposed to optimize the d-band state of Ni3Ge2O5(OH)4 serpentine to improve the OER activity. The density functional theory calculations revealed that Fe3+ doping increased the d-band center of the Ni3Ge2O5(OH)4 serpentine, which optimized the adsorption strength of intermediates on surface Ni and Fe atoms so that the Fe3+ doped Ni3Ge2O5(OH)4 (Ni2.25Fe0.75Ge2O5(OH)4) exhibited much reduced Gibbs free energy changes in the rate-determining step compared with pristine serpentine. Inspired by the theoretical calculations, the NixFe3-xGe2O5(OH)4 nanosheets with different amounts of doped Fe3+ were designed and synthesized. The structural characterizations indicated that Fe3+ was successfully doped into Ni3Ge2O5(OH)4 and replaced the Ni2+. The Fe3+ doped NixFe3-xGe2O5(OH)4 nanosheets showed greatly improved OER activity than Ni3Ge2O5(OH)4 and Fe3Ge2O5(OH)4. Further electrochemical analysis illustrated that Fe3+ doping reduced the adsorptive/formative resistance of intermediates and the charge transfer resistance and facilitated the kinetic process of OER. The in situ Raman spectra indicated that the Fe3+ doped Ni3Ge2O5(OH)4 possesses a more active Ni-O bond than pristine Ni3Ge2O5(OH)4. This work provides an effective strategy to tune the d-band center of serpentines for efficient electrocatalytic OER.

Tailoring of Active Sites from Single to Dual Atom Sites for Highly Efficient Electrocatalysis

Single atom catalysts (SACs) have been attracting extensive attention in electrocatalysis because of their unusual structure and extreme atom utilization, but the low metal loading and unified single site induced scaling relations may limit their activity and practical application. Tailoring of active sites at the atomic level is a sensible approach to break the existing limits in SACs. In this review, SACs were first discussed regarding carbon or non-carbon supports. Then, five tailoring strategies were elaborated toward improving the electrocatalytic activity of SACs, namely strain engineering, spin-state tuning engineering, axial functionalization engineering, ligand engineering, and porosity engineering, so as to optimize the electronic state of active sites, tune d orbitals of transition metals, adjust adsorption strength of intermediates, enhance electron transfer, and elevate mass transport efficiency. Afterward, from the angle of inducing electron redistribution and optimizing the adsorption nature of active centers, the synergistic effect from adjacent atoms and recent advances in tailoring strategies on active sites with binuclear configuration which include simple, homonuclear, and heteronuclear dual atom catalysts (DACs) were summarized. Finally, a summary and some perspectives for achieving efficient and sustainable electrocatalysis were presented based on tailoring strategies, design of active sites, and in situ characterization.