Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

Luo, Guanyu; Song, Min; Zhang, Qian; An, Lulu; Shen, Tao; Wang, Shuang; Hu, Hanyu; Huang, **ao; Wang, Deli

doi:10.1007/s40820-024-01463-9

Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

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Published: 09 July 2024

Volume 16, article number 241, (2024)
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Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

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Guanyu Luo¹,
Min Song¹,
Qian Zhang¹,
Lulu An¹,
Tao Shen¹,
Shuang Wang¹,
Hanyu Hu¹,
**ao Huang¹ &
…
Deli Wang¹

Highlights

Fundamental principles for designing synergistic composite catalysts are reviewed.
The synergistic effect between various active sites, promoting electrocatalytic performance in different reactions are highlighted.
The challenges and perspectives for multiple active sites catalysts are discussed.

Abstract

Combining single atoms with clusters or nanoparticles is an emerging tactic to design efficient electrocatalysts. Both synergy effect and high atomic utilization of active sites in the composite catalysts result in enhanced electrocatalytic performance, simultaneously provide a radical analysis of the interrelationship between structure and activity. In this review, the recent advances of single-atomic site catalysts coupled with clusters or nanoparticles are emphasized. Firstly, the synthetic strategies, characterization, dynamics and types of single atoms coupled with clusters/nanoparticles are introduced, and then the key factors controlling the structure of the composite catalysts are discussed. Next, several clean energy catalytic reactions performed over the synergistic composite catalysts are illustrated. Eventually, the encountering challenges and recommendations for the future advancement of synergistic structure in energy-transformation electrocatalysis are outlined.

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1 Introduction

The development and utilization of sustainable fuels present a highly promising approach to tackle energy and environmental challenges. Electrocatalysis has gained substantial attention and research focus within the realm of energy conversion processes [1]. Over the past few decades, considerable research effort has been directed toward investigating the electrocatalytic reaction mechanism on metallic nano-catalysts, including mono-metals, alloys and transition metal compounds, etc. [2]. Compared with mono-metallic catalysts, alloy nanoparticles have exhibited significantly enhanced electrocatalytic capabilities due to the interaction of diverse elements, which optimizes electronic structures [34]. Copyright 2021, Wiley–VCH GmbH

a–c High-resolution HAADF-STEM images for presenting metal single atoms within M–N-C aerogels and Pt-based particles locating on it, inset images presenting the ordered intermetallic structure of PtFe, PtCo, PtNi. Reproduced with permission [45].

Full size image

Coupled with microscopy technique, local electron energy loss spectroscopy (EELS) is indispensable to analyze existence and distribution of specific element, especially as the loading amounts of atoms is at a minute quantity. For instance, Shao et al. [3g, most of cobalt singe atomic site dispersed uniformly on nitrogen doped carbon substrate at 200 °C, despite a bit of them diffused into Platinum nanoparticles. However, more and more Co sites anchored on support proliferated into Pt nanoparticles to form PtCo alloy nanoparticles as elevating temperatures from 200 to 1000 °C. The size of alloy increased during the process, without the observation of Co nanoparticles. As evidenced by EDX map** results, the measured atomic ratio of Co/Pt in PtCo (Fig. 3h) showed a gradual increase to approximately 0.3 during annealing up to 1000 °C, which was in line with the expected Pt₃Co intermetallic stoichiometry.

Except for physical characterization, fundamental electrochemical measurement can be applied to explore the interaction between single atoms and cluster/nanoparticles. Poisoning experiments are carried out, using ethylenediaminetetraacetic acid disodium (EDTA-2Na) and potassium thiocyanide (KSCN). EDTA-2Na has been proved that it possesses selectivity in coordinating with individual metal atoms, while KSCN possesses the capability to impede the activities of both metal/alloy nanoparticles and single-atom metals [49].

Through the illustration of above samples, the significance of coordinating diverse methods has been elucidated for getting comprehensive analysis of definitive structure, as each characterization technique has its own advantages and limitations.

2.3 Synergistic Mechanism of Single Atomic Site-Clusters/NPs

The essence of investigating synergistic mechanism is to clarify the interaction between single atoms and cluster/nanoparticles. In addition to characterization, density functional theory calculation (DFT) is significant to develop in parallel with experiments [50,51,52,53,54]. It is capable of acquiring the charge distribution, adsorption energies, and elucidating reaction mechanism. In particular, for the synergistic composite catalysts constructing single atom sites with clusters and nanoparticles, DFT can be applied to investigate the synergistic effect. Specially, Jiao et al. [55] utilized DFT to comprehend the synergistic mechanism between Pt–O_x and Co–O_y. Based on the results of characterization, (Pt–O_x)-(Co–O_y) structure was built, which was perfectly nonbonding at atomic scale (Fig. 4a, b). As a comparative model, the defective carbon substrates were employed to simulate a distinct Pt–O_x structure, exclusively loaded with it (Fig. 4c, d). A noticeable shift in charge density revealed a decrease in Pt charge within the Pt–O_x site, while the presence of numerous non-localized charges was observed in close proximity to oxygen atoms. Therefore, the variation of charge density is the primary and fundamental manifestation after constructing them in a unified system.

Secondly, the spin-state transition of atoms can be altered via an integration strategy. Zhu et al. [39] achieved that Pd clusters was dispersed well on Fe–N–C. The spin-state transition of Fe–N₄ sites was change from low-spin (LS) to intermediate-spin (MS) through the introduction of Pd_NC. In comparison to Fe–N–C, the presence of a higher spin state at the Fe site in Fe–N–C/Pd_NC resulted in an expanded spin-related pathway, thereby facilitating charge transport. Considering the perpendicular orientation of d ²_z in relation to the Fe–N–C plane, the transition from an unoccupied d ²_z orbital in low-spin Fe(II) configuration to a partially occupied one in intermediate-spin configuration, effectively modulated the extent of orbital overlap with oxygen intermediates (Fig. 4e, f). Moreover, the incorporation with Pd_NC facilitated the transfer of electrons from Fe single atoms to Pd_NC, thereby inducing significant reorganization of electron distribution in Fe 3d-orbital. This phenomenon could be primarily attributed to the pronounced enhancement of Fe d_z² orbital spin state, as evidenced by meticulous orbital analysis (Fig. 4g).

Besides, Hu et al. [56] conducted DFT calculations to investigate the influence of CO adsorption on the structure constructed according to different effect, as it played a crucial role in determining the electrocatalysts’ ability to withstand CO-tolerance. The study involved the construction of four distinct models, including Pt/C, Pt/Fe–N–C, PtNiMo/C and PtNiMo/Fe–N–C. The second sample was built following strong metal-support interaction (SMSI) effect. Third one was constructed corresponding to alloying effect. The sample containing Fe single atom and alloy combined alloying with SMSI effect (Fig. 4h). By effectively harnessing the synergistic advantages of alloying and SMSI effect, PtNiMo/Fe–N–C demonstrated a remarkably diminished CO adsorption energy of − 1.44 eV, indicating a synergistic attenuation of CO adsorption and assisting CO poisoning in mitigating on Pt sites during hydrogen oxidation reaction (HOR). Subsequently, the Pt d-band centers were calculated. Through comparison, it was observed that the integration of PtNiMo alloy with substrate full of Fe single atoms yielded a significantly reduced value of the d-band center (− 2.190 eV), emphasizing the potential utilization of synergistic function caused by both alloying and SMSI effect to modulate Pt d-band centers effectively (Fig. 4i). As exemplified by Fig. 4j, the location of the d-band center exhibited a significant correlation with the CO adsorption energies. Moreover, from the perspective of mechanism, the PtNiMo/Fe–N–C catalyst, with its d-band center positioned at the lowest level, effectively mitigated electron back donation from Pt 5d to CO 2π* (Fig. 4k). This theoretical finding suggests that it demonstrates superior resistance against CO in HOR.

Although the impact of the interaction between synergistic sites on their own is manifested through alterations in electronic structure, there are different functions when synergistic sites work for various reaction. It can be classified into four types. The first type is that the main catalytic reaction is promoted on one active species by nearby shielding, which suppresses a competitive reaction on another active species. This kind of catalysts are usually employed in oxidation of micro-molecule. The second type involves only one active species serving as the reaction site, while the adjacent modifier regulates its electronic structure. The third type involves that the active species independently catalyze one or multiple electron-transferring steps in catalytic reactions involving multiple electrons, synergizing the overall catalytic process within a specific reaction route, typically in CO₂RR. The catalysts of the fourth type can be referred to as bifunctional catalysts, ascribed that two active species catalyze two contrast catalytic reactions at anode and cathode in devices, respectively, synergizing in the overall catalytic process. The enhancement of this type is often observed at the device level, such as proton exchange membrane water electrolysis.

Ultimately, optimizing integration introduces new active sites and leads to the modulation of electronic structure, which can promote the reaction kinetics in various way. DFT calculation is an effective method to demonstrate electronic configuration definitely and the dynamics of synergy through the simulation in reaction processes.

3 Synergistic Components of Single Atomic Site Catalysts

3.1 Single Atomic Site-Mono-Metal Nanoparticle

SACs often exhibit inadequate reaction activity. Thus, integrating other metal nanoparticles with SACs is regarded as a novel strategy to enhance the reaction performance through modulating the electronic structure [57,58,72,73,74,75,76,77]. As pioneers, Liu et al. [28] reported a synergistic composite catalyst combining nitrogen doped carbon derived from Zn-ZIF with Fe atoms and in situ generated core–shell PtFe nanoparticles containing ordered structure (named as Pt_A@Fe_SA–N–C). According to the AC–TEM, the PtFe intermetallic was encompassed by heavily distributed Fe and residual Zn after vaporization anchored on carrier. Theoretical calculations indicated that the rate-determining step for single atom sites and synergistic sites involved the detachment of the OH* intermediate. The onset potential of synergistic model was highest (1.01 V) either, indicating improved catalytic activity due to the synergistic function of Pt and Fe–N₄. This phenomenon was attributed to the higher electro-negativity of the Pt atom compared with the Fe atom, causing an electron transfer.

In another example, **-adsorption phosphatization. The typical sample showed that many nanoparticles (Fe₂P NPs) were surrounded by highly dispersed single atoms, with the optimal catalytic performance. This finding elucidated that introduction of phosphide was functional to improve single atomic catalysis either. The synergistic effect between them was able to weaken the adsorption of oxygen containing intermediates and supply new reaction pathway.

5 Summary and Outlooks

Single atoms, atomic clusters, as well as nanoparticles have been explored extensively regarding their individual activation and optimization as distinct active species. Their intrinsic catalytic activity is primarily governed by the rich partial micro-region of active centers. The surrounding and electronic state of active sites can be regulated by coupling synergistic components. The integration strategy proves to be a successful approach in enhancing the quantity of operational centers and improving the interaction between catalytic sites and support materials. Besides, the synergistic effect between these elements tunes the electron distribution, valence states, thereby optimizing the electro-catalytic performance.

In this review, latest advances of the synergistic composite catalysts employed for electrocatalysis are overviewed comprehensively, encompassing preparation methods and characterization aimed at determining active center. Moreover, promoting dynamic nature of coupling structure is discussed, combining with their exceptional performance in energy conversion reaction, such as HER, OER, ORR, and CO₂RR. A more comprehensive understanding is gained into the reaction mechanism via synergistic effect. Alternatively, the evolution of synergistic electrocatalysts involving various components still faces significant challenges, hindering sufficient progress. The forthcoming phase of research requires addressing numerous obstacles for advance (Fig. 14).

1.
The synergistic effect of multiple active sites should be taken into consideration, especially for mutual correlation among electron configuration which will be regulated after integration. Before that, it is crucial adjective to forecast the catalytic site structure through advanced calculation, or data from machine learning. A utilization of an integration strategy enables the determination of feasible combinations of metal atoms and the identification of optimal atomic arrangements within the coupling system.
2.
As we know, revealing unhindered routes for electron transfer and significantly reducing interacting distances are prerequisite for strong interaction between components. Thus, obtaining high density and uniformity can transfer from specific properties to Holistic nature. However, it is a great challenge to guarantee the uniformity while increasing the density of active sites.
3.
Various active sites optimize the reaction pathway. The new descriptors could be introduced to simply the description of reaction path way. It is widely recognized that establishing a clear correlation between the chemical structure and inherent activity represents an effective approach, providing valuable insights for enlightenment of electrocatalyst design and accurate performance prediction.
4.
The synergistic effect usually induces the promotion of activity, but the promotion of stability is limited. Thus, taking account into the balance of activity and stability is indispensable. Meanwhile, this composite synergistic catalyst needs to be utilized in devices in different actual application environments to study its practical application value.

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (22279036), the Innovation Talent Recruitment Base of New Energy Chemistry Device (B21003) and the Fundamental Research Funds for the Central Universities (no. 2019kfyRCPY100).

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Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology) Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, People’s Republic of China
Guanyu Luo, Min Song, Qian Zhang, Lulu An, Tao Shen, Shuang Wang, Hanyu Hu, **ao Huang & Deli Wang

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Guanyu Luo
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Min Song
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Qian Zhang
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Lulu An
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Tao Shen
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Shuang Wang
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Hanyu Hu
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**ao Huang
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Deli Wang
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Correspondence to Deli Wang.

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Luo, G., Song, M., Zhang, Q. et al. Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters. Nano-Micro Lett. 16, 241 (2024). https://doi.org/10.1007/s40820-024-01463-9

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Received: 19 April 2024
Accepted: 16 June 2024
Published: 09 July 2024
DOI: https://doi.org/10.1007/s40820-024-01463-9

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Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

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Abstract

1 Introduction

2.3 Synergistic Mechanism of Single Atomic Site-Clusters/NPs

3 Synergistic Components of Single Atomic Site Catalysts

3.1 Single Atomic Site-Mono-Metal Nanoparticle

5 Summary and Outlooks

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