Electronic communication between transition metal nanoparticle and single atom: Endohedral metallofullerenes single-atom catalysts for oxygen reduction reaction catalysis

doi:10.21203/rs.3.rs-2623949/v1

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Electronic communication between transition metal nanoparticle and single atom: Endohedral metallofullerenes single-atom catalysts for oxygen reduction reaction catalysis

https://doi.org/10.21203/rs.3.rs-2623949/v1

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Civil-used proton exchange membrane fuel cell (PEMFC) may be the potential candidate for the construction of the global new energy system including the use of hydrogen energy. Nevertheless, the cathode oxygen reduction reaction (ORR) occurs sluggishly, reining the conversion efficiency of it, which hinders the further commercialization of PEMFC. Currently, the replacement of undesirable Pt catalysts by more stable and economical catalytic materials is the main topic in the field of ORR. Herein, ferromagnetic metal-based endohedral metallofullerenes (EMFs) electrocatalyst with single-atomic shell decoration (M4@MN4C60, M = Fe, Co, Ni) are theoretically constructed and evaluated by the density functional theory method. The encapsulation energy calculation reveals that the synthesis of all EMFs requires additional external energy supply, which can explain why few successfully experimental synesis of EMFs have been reported. Among all studied catalysts, the CoN4C60 stands out with the highest ORR performance comparable to Pt, and the Fe- and Ni- based EMFs shows considerable activity enhancement after the cluster encapsulation. The electronic structure calculation reveals that the encapsulated Fe4 cluster leads to an electron accumulation around the Fe atom in active center, thereby weakening the *OH binding and enhance the ORR performance.

Oxygen reduction reaction

Density functional theory

Fullerene

Single-atom catalyst

Cluster

Energy, a necessity for human progress, highly related to the destiny of a country. In the context of the imminent depletion of fossil energy and the continuous implementation of the energy revolution, hydrogen energy is regarded as an important starting point for the construction of the global new energy system [1,2]. Among many hydrogen conversion and utilization devices, proton exchange membrane fuel cell (PEMFC) is considered to have the most civil potential due of its many advantages, especially low-temperature availability [3−6]. At the cathode of PEMFC, the oxygen reduction reaction (ORR) occurs sluggishly, reining the conversion efficiency of it [7−10]. Currently, platinum (Pt)-group catalysts show the highest ORR activity, which makes it serve as the commercial catalyst in the early promotion process of PEMFC [11,12]. Nevertheless, their disadvantages high cost and easy deactivation indicate that it will eventually be replaced by more stable and economical catalytic materials [13−16].

The discovery of fullerene C₆₀ in 1985 opened a new era in chemistry and material science [17]. Although its intrinsic electrocatalytic activity is low, owing to its unique rigid spherical molecular structure, with all sp²-hybridized carbon atoms and unparalleled electron affinity, its composites have been widely used as electrocatalysts [18−20]. In addition, some modified C₆₀ materials have also explored, for example, heterofullerene derivatives with carbon atoms substituted by another hetero-element were synthesized and reported as potential ORR catalyst [21−23]. A wide variety of exohedral and endohedral C₆₀ complexes with metals were synthesized experimentally and predicted theoretically [24–28]. Nevertheless, metal-substituted fullerenes are still rarely either predicted theoretically or synthesized experimentally [29].

Meanwhile, the single-atom catalysts (SACs) have rapidly become a research frontier in the field of electrocatalysis [30,31]. And the synergetic between metal nanoparticles or clusters has been proved to scale new heights of the electrochemical activity [32–34]. Recently, Su et al. demonstrated that enhanced charge transfer occurred at the interface of Ru NPs and single metal atoms (e.g., Co, Fe and Ni) doped carbon substrate, resulting in synergetic electronic coupling and optimized HER performance [35]. Nevertheless, the complex preparation process and environment may lead to the fact that this kind of electronic communication and synergetic coupling cannot take place uniformly at each active site on two-dimensional or one-dimensional materials like graphene or carbon nanotubes. While for the zero-dimensional spherical core-shell construction, the inner metal cluster could interplay with multiple surrounding single atoms decorated on the shell, resembling the electronic metal-cage interaction of endohedral metallofullerenes (EMFs) [36]. Most recently, Feng et al. have successfully synthesized an Ru nanoparticle encapsulated oxyfullerene-like carbon cage decorated with single-atomic RuN_x species anchored on nitrogen-doped carbon substrate, which display an outstanding electrocatalytic performance for HER both in acid and alkaline [37]. And this synesis method can be expected to extend to other transition metal including commonly studied non-noble VIII group ferromagnetic metal Fe, Co, and Ni.

Herein, ferromagnetic metal-based EMFs electrocatalyst with single-atomic shell decoration are theoretically constructed, namely, M₄@MN₄C₆₀ (M = Fe, Co, Ni), and the density functional theory (DFT) method is employed to investigate the ORR performance of M₄@MN₄C₆₀. Considering that there are two kinds of C pairs in C₆₀ shell, the stability of two type of MN₄C₆₀ are first studied, named as MN₄C₆₀-I and MN₄C₆₀-II. All type I of MN₄C₆₀ show better generation tendency than that of type II. The encapsulation energy calculation suggests that all EMFs require additional external energy supply to synthesis. The CoN₄C₆₀ stands out among all studied catalysts with the highest ORR performance, and the other two MN₄C₆₀ show considerable ORR performance enhancement after the encapsulation of the corresponding M₄ cluster. The charge density deference and frontier molecular orbital calculation further unveil that the encapsulated Fe₄ cluster will play a role of “electron donor” and enrich the electrons on the Fe atom in the active center, which will lead to the weakened *OH binding and performance enhancement. This work will bring a new thought for the future PEMFC cathode electrocatalysts design and move the commercialization of PEMFC forward.

All theoretical calculation were carried out by the DMol³ code of Materials Studio package [38,39]. The electron exchange and correlation effect were performed by the generalized gradient approximation (GGA) of the Perdew−Burke−Ernzerhof (PBE) functional with the double numerical plus polarization (DNP) basis set [40]. A 0.005 Ha smearing was set to push on convergence while retaining the accuracy. The convergence tolerance of energy change, max force, and max displacement was respectively 2×10⁻⁵ Ha, 0.004 Ha/Å, and 0.005 Å.

To evaluate the stability of the two types MN₄C₆₀ (determined by the different substituted C pairs, as shown in Fig. 1), the substitution energy (E_sub) is firstly calculated as follows:

E_sub = E_MN4C60 – E_C60 + N_Cμ_C – N_Mμ_M – N_Nμ_N

(1)

where the E_MN4C60 and E_C60 represent the energy of MN₄C₆₀ materials and C₆₀ substrate. The μ_C, μ_M, and μ_N are the chemical potentials of carbon, metal, and nitrogen atoms, respectively. The more negative the E_sub, the more stable the MN₄C₆₀.

Then, the stability of encapsulated M₄@MN₄C₆₀ structure are evaluated by the encapsulation energy (E_enc), which is calculated as:

E_enc = E_M4@MN4C60 – E_MN4C60 – N_Mμ_M

(2)

where the E_M4@MN4C60 is the energy of M₄@MN₄C₆₀. A more negative E_sub value indicates a more energetical favorable encapsulation process.

Since the four-electron ORR mechanism on such MN₄ structure has been proved in numerous researches experimentally or theoretically [41−43], this work only focuses on the four-electron ORR mechanism, which include following steps:

* + O₂ + H⁺ + e⁻ → *OOH	(3)
OOH + H⁺ + e⁻ → O + H₂O	(4)
O + H⁺ + e⁻ → OH	(5)
OH + H⁺ + e⁻ → + H₂O	(6)

The binding energy (∆E) of ORR intermediates on M₄@MN₄C₆₀ and MN₄C₆₀ is defined as follows:

∆E_OOH = E_OOH – E_cat − (2E_H2O − 3/2E_H2)	(7)
∆E_O = E_O – E_cat − (E_H2O − E_H2)	(8)
∆E_OH = E_OH – E_cat − (E_H2O − 1/2E_H2)	(9)

in which E_*OOH, E_*O, and E_*OH represents the overall energy of catalysts with adsorbed OOH, O, and OH, respectively. E_H2O and E_H2 represents the energy of water molecule and hydrogen molecule, respectively. The smaller the ∆E value, the stronger the binding strength.

The adsorption free energy (ΔG_ads) is calculated based on the computational hydrogen electrode (CHE) model proposed by Nørskov and co-workers [44]: ΔG_ads = ΔE + ΔZPE – TΔS. where ΔZPE, T, and ΔS is the change of zero-point energy, the temperature (298.15 K) and the change of entropy, respectively. According to the summary by Zhang et al., for the ORR species adsorbed on various catalysts, zero-point energy possesses similar value as the entropy [45]. Therefore, the ΔG_ads can be expressed by [46]:

∆G_OOH = ∆E_OOH + 0.40	(10)
∆G_O = ∆E_O + 0.05	(11)
∆G_OH = ∆E_OH + 0.35	(12)

The relationship between ΔG_adsand binding strength of ORR intermediates is similar to that between ΔE and binding strength, that is, a small ΔG_ads value indicates a strong binding strength of intermediates.

The Gibbs free energy change for each step in four-electron pathway can be calculated by the following equations:

∆G₁ = ∆G_*OOH − 4.92	(13)
∆G₂ = ∆G_O − ∆G_OOH	(14)
∆G₃ = ∆G_OH − ∆G_O	(15)
∆G₄ = −∆G_*OH	(16)

The overpotential of ORR (η^ORR) as the key descriptor of the ORR catalytic activity can be obtained by:

η^ORR = 1.23 + max(ΔG₁, ΔG₂, ΔG₃, ΔG₄)/e

(17)

Model and stability

As stated in section 2, the different C pairs make MN₄C₆₀ structure different. Therefore, the calculated E_sub values are plotted in Fig. 2a, and the optimized MN₄C₆₀ structure are shown in Fig. 2b and c (taking CoN₄C₆₀-I and CoN₄C₆₀-II as example). It can be seen that all type I structures are more stable and show more generation tendency than that of type II MN₄C₆₀, suggesting that the energetically more favorable configuration of MN₄C₆₀ is type I. Hence, the MN₄C₆₀-II structures will no longer be considered in following discussion.

To evaluate the difficulty for encapsulating M₄ clusters in C₆₀, the E_enc values are calculated and displayed in Fig. 3a. All E_enc values are as high as ~10 eV, which indicates the thermodynamic instability of M₄@MN₄C₆₀. Meanwhile, this also intrinsically explains why few successfully experimental synesis of EMFs have been reported. The optimized M₄@MN₄C₆₀ structure are shown in Fig. 3b−d. Clearly, the metal cluster is encapsulated in the C₆₀ shell in the form of triangular pyramid, with the shell showing barely extension, indicating that the M₄@MN₄C₆₀ can exist stably.

Thermodynamics of ORR on M₄@MN₄C₆₀

According to Sabatier principle [47], to design a catalyst with promising performance, the appropriate intermediates biding is necessary. Therefore, we explored the binding behaviors of the ORR intermediates on M₄@MN₄C₆₀, as shown in Fig. 4. For FeN₄C₆₀, the negative ΔG_*OH value indicates the extremely *OH binding, which may hinder the last proton-electron transfer step, thus lowering the catalytic activity. After encapsulation, the over-strong *OH binding is significantly improved, making ΔG_*OH as high as 0.90 eV and close to the ideal ΔG_*OH value 1.23 eV. In addition, the ΔG_*O slightly decreased, which may attribute to the slightly collapsed MN₄ sites. Contrarily, the ΔG_ads values on Co₄@CoN₄C₆₀ and Ni₄@NiN₄C₆₀ are decreased to various degrees compared to corresponding MN₄C₆₀, with the bulge MN₄ sites not collapsing obviously. Aiming at ideal ΔG_ads values (ΔG_*OOH = 3.69 eV, ΔG_*O = 2.46 eV, ΔG_*OH = 1.23 eV), the Fe₄@FeN₄C₆₀ possesses the closest ΔG_ads values among all studied catalysts, suggesting the great potential for ORR applying.

Previous work reported that ΔG_*OH and (ΔG_*OH − ΔG_*O) can be recognized as two independent descriptors to descript the ORR activity of catalysts [48−50], the volcano map of η^ORR as the function of these two descriptors are therefore plotted and shown in Fig. 5. It can be seen that the CoN₄C₆₀ data point located at the edge of dark blue region which represents the promising activity with η^ORR below 0.43 V. Meanwhile, the Fe₄@FeN₄C₆₀ also falls on the blue high-activity region, which contrast obviously with FeN₄C₆₀ in undesirable red region. For Ni₄@NiN₄C₆₀, it shows relatively strong *OH binding compared to original NiN₄C₆₀, which makes it left shift from the narrow transition area between blue high-activity region and red poor-activity region to the loose transition area, and it shows higher activity than NiN₄C₆₀.

For deeply investigating the ORR mechanism, the Gibbs free energy diagram are plotted in Fig. 6. It is clearly seen that all studied MN₄C₆₀ and M₄@MN₄C₆₀ can catalyze ORR process spontaneously except for FeN₄C₆₀. Meanwhile, after encapsulated Fe₄ cluster, the Fe₄@FeN₄C₆₀ possesses sharply reduced η^ORR of 0.58 V, which benefiting from the tuned *OH binding and thereby enhanced last patron-electron step of *OH reduction, and the rate-determining step (RDS, step with the highest ΔG) even changed to the third step of *OH generation. For Co-metallofullerenes, the origin CoN₄C₆₀ possesses a low η^ORR of 0.43 V, which is lower than the theoretical model of commercial Pt catalysts (0.45 V) [44]. After encapsulation, the binding of ORR intermediates on Co₄@CoN₄C₆₀ are all became stronger, leading to a hinderance in *OH reduction step. For Ni-metallofullerenes, the over-weak binding of ORR intermediates, especially *OOH, is the main block of the ORR process. Fortunately, it is significantly improved as the encapsulation of Ni₄ cluster. In summary, the binding of ORR intermediates is generally getting tuned after the cluster encapsulation, and the ORR mechanism may also be changed according to the change in RDS.

Activity origin

The electronic structure calculations are performed to unveil the origin of ORR activity for M₄@MN₄C₆₀, and the FeN₄C₆₀ and Fe₄@FeN₄C₆₀ are selected as representative. The charge deformation density of these two catalysts is calculated and displayed respectively in Fig. 7a and b, and the inserts are the profile chart across Fe atom along XY plane. It can be seen that the electron-depletion region obviously reduces after the encapsulation of Fe₄ cluster, while contrarily strengthening for the electron-accumulation region. This indicating that the Fe₄ cluster plays a role of “electron donor”, which can donate electrons to the outer-layer exposed Fe atom, and the enriched electrons of Fe in Fe₄@FeN₄C₆₀ lead to the weakened binding of *OH. This can also be reflected by the lifted highest occupied molecular orbital (HOMO) level and the barely changed lowest unoccupied molecular orbital (LUMO) level (Fig. 7c). The density of states analysis of *OH binding system further confirm the above conclusion, as shown in Fig. 7d. It can be seen that the energy level of σ bonding orbital of O atom in *OH on FeN₄C₆₀ is clearly lower than that on Fe₄@FeN₄C₆₀, and the d-states of Fe in Fe₄ cluster hybrids with the Fe in active center, thereby making upshifted σ bonding orbital of O atom in *OH on Fe₄@FeN₄C₆₀ and weaking the *OH binding.

In summary, this article aims to identify the potential ORR catalysts among ferromagnetic metal-based EMFs with single-atomic shell decoration by DFT calculation. The underlying ORR mechanism and electronic structure varying are unveiled to explore the ORR performance enhancement and the accompanying origin after the encapsulation of M₄ cluster. All type I structures are more stable and show more generation tendency than that of type II MN₄C₆₀, and the synthesis of all M₄@MN₄C₆₀ require additional external energy supply. Among all MN₄C₆₀ and M₄@MN₄C₆₀, CoN₄C₆₀ stands out with the highest ORR activity with the η^ORR as low as 0.43 V. The Fe- and Ni-based EMFs show an enhancement on ORR activity after the encapsulation, and the RDS may therefore change to another elementary reaction step. The electronic structure analysis revealed that the Fe₄ cluster plays a role of “electron donor”, which can donate electrons to the outer-layer exposed Fe atom. The enriched electrons of Fe in Fe₄@FeN₄C₆₀ lead to the weakened binding of *OH and the upshifted σ bonding orbital of O atom in *OH on Fe₄@FeN₄C₆₀, which will benefit for the ORR performance enhancement. This work will give a new train of thought for the future PEMFC-employed cathode electrocatalysts design and drive the commercialization of PEMFC.

Acknowledgments We acknowledge the National Supercomputing Center in Shenzhen for providing the computational resources and Materials Studio.

Funding The authors declare that no funds, grants, or other support were received during the preparation of this manuscript.

Author contribution Conceptualization, Investigation, Writing—original draft preparation, Bo Zhang; Writing—review and editing, Validation, Formal analysis, Hua Ji. All authors have read and agreed to the published version of the manuscript.

Ethics approval This manuscript does not include any experiments on humans or animals.

Competing Interests The authors have no relevant financial or non-financial interests to disclose.

Data Availability The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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Electronic communication between transition metal nanoparticle and single atom: Endohedral metallofullerenes single-atom catalysts for oxygen reduction reaction catalysis

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