Electrocatalytic nitrogen reduction directed through the p-band center of boron on B_SAC@Mo₂C

Abstract

Greener modes of ammonia synthesis via the electrocatalytic route have been investigated on pristine and defective Mo₂C based monolayers anchored with metal-free boron atom catalysts. Boron single atom catalysts (SACs) on the defective Mo₂C monolayer has been found to activate N₂ strongly with an adsorption energy of −1.92 eV and reduce it to NH₃ efficiently with a significantly low overpotential of 0.41 eV. The exothermic adsorption of N₂ and low overpotential for the nitrogen reduction reduction (NRR) appertain to the p-band center of the boron atom catalyst and charge transfer between the adsorbed N₂ and the catalyst, respectively. This work brings forth the correlation between electron occupancy on the boron center and NRR catalytic efficiency on a metal-free SACs@Mo₂C monolayer couple, thereby serving as a lead in designing metal free electrocatalysts for the NRR.

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1 Introduction

With the rise in global temperature and greenhouse gas emissions, most industrial processes aim to achieve carbon neutrality. However, one process with an extremely high carbon footprint accounting for 6% of global CO₂ emissions and the consumption of approximately 1–2% of global energy¹ is the Haber–Bosch² ammonia synthesis process. With ammonia being an irreplaceable precursor in agriculture, various industries and energy applications,^3,4 there is an urgent need to develop greener techniques for NH₃ synthesis through photocatalytic, electrocatalytic or photo-electrocatalytic routes to meet the current demands.^5,6 The optimal goal towards achieving ammonia economy is to develop a catalyst that reduces N₂ to NH₃ under ambient conditions like the nitrogenase enzyme. The electrocatalytic route of nitrogen fixation is an attractive alternative owing to its efficiency and environment-friendly nature.^7,8 However, with N₂ being a highly stable molecule with a N–N triple bond energy of 940 kJ mol⁻¹, the kinetics associated with the electrocatalytic nitrogen reduction reaction (NRR) are sluggish and the faradaic efficiency is low.⁷ As a result, the competing hydrogen evolution reaction (HER) is usually preferred over the sluggish NRR. Therefore, it is essential to design new and smart materials with high electrical conductivity that have the capability to subjugate the HER and enhance the NRR. Several scarce metals such as Ru,^9,10 Au^11,12 and Pd^13,14 have been reported as highly efficient electrocatalysts for the NRR with faradaic efficiencies of up to 36.6%,¹³ their cost and availability are issues that cannot be overcome. Hence, identifying cost effective electrocatalysts based on earth abundant metals such as Mo, Fe, and Co, etc. as potential alternatives for the NRR is the need of the hour.¹⁵

Notably, Mo metal is present as an active centre in nitrogenase enzymes, and possesses the requisite electronic structure to capture N₂ molecules and has been extensively studied for the NRR.¹⁶ Several other Mo-based two-dimensional (2D) materials, nanoparticles and nanoclusters, single atom catalysts (SACs) and organometallic complexes have been reported as efficient catalysts for the NRR.^17–26 While Mo-containing organic and inorganic complexes efficiently adsorb and form stable dinitrogen complexes, their application as electrocatalysts or electrodes are not warranted.¹⁸ Mo clusters and SACs, on the other hand, require a conducting/semi-conducting support for further usage as electrocatalysts.^19,20,22,27 In this regard, Mo-based 2D materials such as MoS₂,^24,28–31 MXenes (Mo₂C)^32–34 and MBenes (Mo₂B₂)^35,36 are appealing electrocatalysts owing to their high electrical conductivity and the presence of active Mo metal centres. These 2D materials not only show high hydrophilicity, stability and conductivity but are interesting from the catalytic aspect of nitrogen reduction as the Mo metal is accessible to the nitrogen molecule. Compared to MBenes, MXenes have been extensively investigated experimentally for the electrocatalytic NRR.^32,37–39

While computational studies on the electrochemical applications of Mo₂C based 2D materials have been extensively carried out, they have rarely been explored for the electrocatalytic NRR. One notable study on the electrocatalytic application of Mo₂C for the NRR was made recently by Zhang et al. wherein Mo₂C monolayers were investigated for the NRR through density functional theory (DFT) calculations.³⁴ It would be imperative to recollect that effective strategies to fine tune and improve the N₂ binding efficacy on a 2D monolayer are structural modifications and incorporating active atomic centers on it.⁴⁰ Thereby, pristine and defective Mo₂C monolayers coupled with a metal free single atom catalyst, in particular boron, are expected to enhance the N₂ adsorption and inherently improve the NRR process. Several experimental and computational studies have reported boron based metal free catalysts on 2D materials to remarkably augment the electrocatalytic NRR by promoting N₂ adsorption and inhibiting the HER.^41–43 The boron center behaves as a Lewis acid with empty p-orbitals, thereby resulting in a strong π–π* interaction with N₂ and less energy demanding subsequent protonation steps for the NRR.^44,45

The correlation between charge transfer from the catalytic center and nitrogen reduction efficacy is one aspect of paramount importance that has not been explored to date. Thus, in the present work, we conducted a comprehensive investigation to provide a complete picture concerning the fundamental understanding of nitrogen activation and reduction on active boron atoms anchored on a pristine Mo₂C monolayer. Specifically, the coupling effect of boron single atom catalysts with defects on the Mo₂C monolayer and its influence on nitrogen activation and reduction was thoroughly investigated. The p-band center and electronic structure of 2D Mo₂C monolayers upon the anchoring of non-metallic boron atoms directly influences their NRR catalytic efficiency. Based on our results, we found that a single boron atom catalyst anchored on a defective Mo₂C monolayer can effectively produce NH₃ with a record low overpotential of 0.41 eV.

2 Computational details

All DFT calculations were carried out with the Vienna ab initio Simulation Package (VASP).⁴⁶ The generalized gradient approximation (GGA) and the Perdew–Burke–Ernzerhof (PBE)⁴⁷ functional has been employed with an energy cutoff of 532 eV to describe all electron core–interactions. A DFT-D3 correction method has been incorporated to account for the long-range van der Waals (vdW) interactions.⁴⁸ All the catalyst systems sampled with a (5 × 5 × 1) Monkhorst–Pack k-point grid and a vacuum space of 20 Å along the Z-direction are relaxed until the atomic energy and forces converge to 10⁻⁵ eV per atom and 0.005 eV Å⁻¹, respectively. For the density of states and electronic structure calculations, a higher (11 × 11 × 1) Monkhorst–Pack k-point grid has been employed.

The stability of atomic boron catalysts on Mo₂C and its analogues is evaluated in terms of binding energy, E_b which is calculated by using the equation,

E_b = (E_Bcat@Mo2C) − (E_Mo2C) − (E_Bcat) (1)

where, E_Bcat@Mo2C and E_Mo2C are the total electronic energies of the 2D Mo₂C monolayer with and without atomic boron catalysts and E_Bcat is the electronic energy of atomic boron. The adsorption of N₂ on the 2D Mo₂C monolayer has been computed for the parallel and perpendicular modes and the efficiency of these materials to chemisorp N₂ molecule has been calculated in terms of the N₂ adsorption energy, (E_ads) as given below,

E_ads = (E_{Bcat@Mo2C–N2}) − (E_Bcat@Mo2C) − (E_N2) (2)

where, E_BcatMo₂C–N₂, E_Bcat@Mo2C and E_N2 are the total electronic energies of N₂ adsorbed systems, B_cat@Mo₂C and free N₂ molecules, respectively.

The Gibbs free energy change, ΔG in every protonation step of the NRR has been calculated by employing the computational SHE (standard hydrogen electrode) model proposed by Nørskov et al.⁴⁹ using the equation,

ΔG = ΔE + ΔZPE − TΔS (3)

where, ΔE is the change in electronic energy, ΔZPE is the change in zero-point energy, T is the room temperature (298.15 K) and ΔS is the change in entropy. The zero-point energies and entropy contributions are calculated by considering the vibrational frequencies of the adsorbed gas phase species. Furthermore, the overpotential for the electrocatalytic NRR on the Mo₂C monolayer and its analogues has been calculated as η = U_SHE − U_PDS, where U_SHE = −0.16 eV, is the standard reduction potential of N₂ to NH₃ and U_PDS = ΔG_max/e for the NRR pathway.

3 Results and discussion

3.1 N₂ adsorption on B_catMo₂C

The stability of atomic boron catalysts on Mo₂C is one of the fundamental prerequisites for their implementation as electrocatalysts for the NRR. Boron has been anchored on conventional pristine 1T-Mo₂C as a single atom catalyst (SAC) or a diatom catalyst (DAC), respectively referred to as B_SAC@Mo₂C and B_DAC@Mo₂C from now onwards. The geometric structures of the B_SAC@Mo₂C and B_DAC@Mo₂C catalysts are presented in Fig. S2 (see the ESI†). Anchoring B_DAC on Mo₂C was found to be more feasible with a binding energy of −7.07 eV as compared to B_SAC (−6.90 eV). The 2D Mo₂C monolayer was then subjected to two major surface modifications: a Mo-vacancy and defective Mo₂C with non-metal dopants as shown in Fig. 1. Mo₂C with a vacant Mo-site is referred to as Mo₂C–Mo_vac and defective Mo₂C obtained by replacing one Mo atom from the surface with metal-free dopants is designated as Mo₂C–X_def, where X = B, C, N, P and S. On these Mo-vacant and defective analogues of Mo₂C, we next adsorbed B single atoms to create a metal-free catalyst couple for nitrogen activation and reduction. The binding energy of B_SAC ranges from −5.35 eV on the Mo₂C–Mo_vac catalyst to −6.25 eV, −5.37 eV, −7.92 eV, −5.81 eV and −4.77 eV respectively, on the Mo₂C–B_def, Mo₂C–C_def, Mo₂C–N_def, Mo₂C–P_def and Mo₂C–S_def catalysts. The exothermic binding energies of the boron atom catalysts on all Mo₂C analogues illustrates the stability of the boron SAC integrated on the defective Mo₂C monolayers.

Fig. 1 The model 2D 1T-Mo₂C monolayer with surface modifications considered in this study.

We next investigated the N₂ adsorption efficacy and electronic properties of the B_cat@Mo₂C catalysts through the d-band centre of Mo, the p-band centre of B and the projected density of states (PDOS) with reference to pristine 1T-Mo₂C. Fig. 2 highlights the N₂ adsorption energies of the B_cat@Mo₂C catalysts with reference to 1T-Mo₂C and the correlation between N₂ adsorption with the d-band center of Mo and the p-band center of B. B_SAC@Mo₂C and B_DAC@Mo₂C exhibit a lower exothermic end-on mode of dinitrogen adsorption with E_ads values of −0.64 eV and −0.55 eV, respectively with respect to −1.10 eV on 1T-Mo₂C. It can also be noted that there are no significant changes in the Mo d-band center when B_SAC and B_DAC are anchored on Mo₂C, however the B p-center on B_SAC@Mo₂C is more positive than that of B_DAC@Mo₂C. A more positive B p-band center infers that the B p-orbitals are closer to the Fermi level (E_F = 0 eV), which in turn leads to the feasible adsorption of N₂. Generating a Mo-vacancy on the Mo₂C monolayer leads to a less positive Mo d-band center, but in contrast, the B p-band becomes more positive, which in turns leads to higher chemisorption (−1.92 eV) of N₂ on B_SAC@Mo₂C–Mo_vac. Moreover, on analysing the Bader charges on the B_cat centers, all the B_cat centers are found to be negatively charged, thereby implying that there is a charge transfer from the Mo₂C monolayer to B. The only exception being the B_SAC@Mo₂C–N_def and B_SAC@Mo₂C–S_def systems with positively charged or nearly neutral B_cat centers, respectively. Interestingly, these two systems possess a more negative B p-band center as compared to the rest of the systems, and thereby show lower exothermic N₂ adsorption. It is also important to note that a higher exothermic N₂ adsorption is not only influenced by the B p-band center but also by a more pronounced overlap between the π orbitals of the B and N atoms. The parallel/side-on mode of N₂ adsorption involves two B–N bonds, and results in two peaks in the PDOS plot (inset) with a greater electron density overlap (see Fig. 3(a)) compared to a single B–N bond for the perpendicular/end-on mode of N₂ adsorption (Fig. 3(b)) on B_SAC@Mo₂C–Mo_vac. The B_SAC@Mo₂C–X_def catalysts follow a similar pattern of N₂ adsorption. For instance, B_SAC@Mo₂C–C_def with a more positive B p-band center exhibits better chemisorption of N₂ when compared to B_SAC@Mo₂C–N_def with a highly negative p-band center of B. It can be established that the adsorption and activation of N₂ is influenced by the p-band center of B_cat on the B-anchored Mo₂C catalysts. Interestingly, it was noticed that the N₂ chemisorption efficacy of B_SAC with a Mo-vacancy is on a par with that of B_SAC with C-defective Mo₂C, while the rest of the non-metals, i.e. B, P, S and N show moderate to minimal adsorption of N₂. Apart from the B p-band center, the N₂ adsorption trends could also be rationalized in terms of electronic properties such as charge difference density (CDD) and the PDOS plots provided in Fig. S3 of the ESI.† The PDOS plots also show the very interesting phenomenon of a synergistic effect between the C from the Mo₂C and B_cat centers. The systems that show a higher exothermic N₂ adsorption, in turn show a more pronounced overlap between the C p-orbitals and B p-orbitals, thus the synergistic effect of C and B enhances the N₂ adsorption efficiency in the B_cat@Mo₂C catalysts.

Fig. 2 N₂ adsorption energies in different modes, and the Mo d-band center and B p-band center on different B_cat@Mo₂C catalysts.

Fig. 3 PDOS of N₂ adsorbed on B_SAC@Mo₂C–Mo_vac with the insets showing hybridisation of the N p-orbitals and B p-orbitals and the CDD plot generated isosurface density set to 0.003 e Å⁻³. (a) PDOS and CDD plots of N₂ adsorbed on B_SAC@Mo₂C–Mo_vacvia the parallel/side-on mode. (b) PDOS and CDD plots of N₂ adsorbed on B_SAC@Mo₂C–Mo_vacvia the perpendicular/end-on mode.

3.2 N₂ reduction on B_cat@Mo₂C catalysts

Finally we explored the thermodynamics for the reduction of N₂ to NH₃ on the B_cat@Mo₂C catalysts that showed strong exothermic N₂ chemisorption. Also the NRR pathways on B_SAC@Mo₂C and B_DAC@Mo₂C were analysed to deduce whether the role of a second B atom enhances or inhibits the reduction process. Among the defective monolayers with surface modification, B_SAC@Mo₂C–Mo_vac and B_SAC@Mo₂C–C_def were considered as both showed highly exothermic chemisorption of dinitrogen in both the parallel as well as the perpendicular mode. Previous studies have revealed that the reduction of N₂ can proceed via three pathways, viz. distal or alternating and enzymatic, respectively, for N₂ adsorbed in the perpendicular and parallel modes. On the B_SAC@Mo₂C and B_DAC@Mo₂C catalysts with N₂ adsorbed preferentially in an end-on mode, the NRR pathway was explored through the distal and alternating routes as shown in Fig. S4 and S5 of the ESI.† The last protonation step, i.e. *NH₂ → *NH₃ has been found to be the potential determining step (PDS) for nitrogen reduction on B_SAC@Mo₂C and B_DAC@Mo₂C for both the distal and alternating route with a ΔG_max of 1.10 eV and 0.90 eV, respectively. The corresponding overpotentials, η for reducing nitrogen to ammonia on the two catalysts are therefore, 0.94 eV and 0.74 eV, respectively. It would be interesting to note that B_SAC@Mo₂C, which is more exergonic towards N₂ (−0.15 eV) as compared to B_SAC@Mo₂C (−0.05 eV) follows a more uphill first protonation step (0.21 eV) and a complementary more uphill PDS. For the B_SAC@Mo₂C–Mo_vac monolayer with one Mo-atom vacancy that shows exothermic N₂ adsorption in the side-on as well as end-on modes, the NRR mechanisms for all three possible routes were computed and are are presented in Fig. 4. Although, the parallel mode of N₂ adsorption is more exergonic than the the perpendicular mode, and we expect the enzymatic route to be favoured over the distal or alternating route, the limiting potential for the NRR on the B_SAC@Mo₂C–Mo_vac catalyst was found to be 0.57 eV (*NH₂ → *NH₃) for the distal, 1.05 eV (*N–NH → *NH–NH) for the alternating and 1.83 eV (*NH₂–*NH₂ → *NH₂) for the enzymatic route. The distal route, which involves the protonation of only one nitrogen atom to form the first ammonia molecule, can be seen to show downhill reaction steps until the fourth protonation step. The preference for the distal mode could be accounted for by less steric hindrance caused by subsequent protonation on the nitrogen atoms. It is interesting to note that the B_SAC@Mo₂C–Mo_vac catalyst shows a high affinity for capturing the *NH₂ moiety as it can be found from the enzymatic route. The *NH₂–*NH₂ intermediate shows a highly exergonic adsorption with dissociation of the N–N bond and the adsorption of one *NH₂ on the Mo atom of the monolayer. Dissociating the N–N bond would be the ultimate goal of the NRR, however, if the catalyst holds onto the ammonia molecule strongly, the effectiveness and applicability of the catalyst is restricted. As a result, the enzymatic route would be a highly unlikely and unfavoured route for reducing N₂ molecules. A similar case of the high exergonic adsorption of the *NH₂–*NH₂ intermediate can be seen for the B_SAC@Mo₂C–C_def catalyst (Fig. S6, ESI†), wherein the limiting potentials for nitrogen reduction were found to be 1.42 eV for the distal and alternating routes (*NH₂ → *NH₃) and 2.26 eV for the enzymatic route (*NH₂–*NH₂ → *NH₂). The limiting potentials and the corresponding potential determining steps on the above mentioned B_cat@Mo₂C catalysts are summarised in Table 1.

Fig. 4 Free energy profile of the nitrogen reduction reaction via the distal, alternating and enzymatic routes on the B_SAC@Mo₂C–Mo_vac catalyst.

Table 1 Gibbs free energies, ΔG (eV) of N₂ adsorption, first protonation and rate determining step (ΔG_max) and overpotential, η for all routes of the NRR on the B_cat@Mo₂C catalysts

Bcat@Mo2C catalysts	NRR route	ΔG*N2 (eV)	ΔG*N2 → ΔG*N2H (eV)	Rate determining step	ΔGmax (eV)	η (eV)
BSAC@Mo2C	Distal	−0.15	0.21	*NH2 → *NH3	1.10	0.94
	Alternating	−0.15	0.21	*NH2 → *NH3	1.10	0.94
BDAC@Mo2C	Distal	−0.05	0.02	*NH2 → *NH3	0.90	0.74
	Alternating	−0.05	0.02	*NH2 → *NH3	0.90	0.74
BSAC@Mo2C–Movac	Distal	−0.72	−0.34	*NH2 → *NH3	0.57	0.41
	Alternating	−0.72	−0.34	*N–NH → *NH–NH	1.05	0.89
	Enzymatic	−1.38	−0.42	*NH2–*NH2 → *NH2	1.83	1.67
BSAC@Mo2C–Cdef	Distal	−0.88	0.30	*NH2 → *NH3	1.42	1.26
	Alternating	−0.88	0.30	*NH2 → *NH3	1.42	1.26
	Enzymatic	−1.23	−0.07	*NH2–*NH2 → *NH2	2.26	2.10

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While an exergonic adsorption of N₂ is essential for the feasible capture of N₂, it is not the only deciding factor for successful nitrogen reduction. There have been no accounts correlating dinitrogen adsorption to the efficacy of nitrogen reduction and the corresponding limiting potential. The exergonic free energy of N₂ follows the order B_SAC@Mo₂C–Mo_vac > B_SAC@Mo₂C–C_def > B_SAC@Mo₂C > B_DAC@Mo₂C, however the limiting potential of nitrogen reduction follows the order B_SAC@Mo₂C–C_def > B_SAC@Mo₂C > B_DAC@Mo₂C > B_SAC@Mo₂C–Mo_vac. In order to correlate the N₂ adsorption and the limiting potential, we probe into the electronic properties of the adsorbed N₂ and N_xH_y species via the Bader charges on the B atom and N atoms for all the B_cat@Mo₂C catalysts as shown in Fig. 5. The N-atoms are seen to be negatively charged on all the N_xH_y intermediates and tend to be more electron rich for subsequent reaction steps thereby making the protonation facile. While the differences in Bader charge on the N-atoms are minute for different catalysts, the charges on the B-atoms are prominent with less positive B-atoms on the B_DAC@Mo₂C, B_SAC@Mo₂C–Mo_vac and B_SAC@Mo₂C catalysts, followed by the B_SAC@Mo₂C–C_def catalyst. A highly positive B-atom on the corresponding N_xH_y intermediates would deplete the negative charge on the N-atom, thereby restricting the protonation steps as seen in the case of B_SAC@Mo₂C–C_def. Therefore, the B_SAC@Mo₂C–Mo_vac catalyst with strong N₂ chemisorption captures the dinitrogen molecule effectively and the electron deficient B-atom aids the protonation steps in the NRR, thus making it an attractive electrocatalyst with a limiting potential of 0.57 eV and an overpotential of 0.41 eV. In contrast, the relatively high limiting potential of 1.10 eV for B_SAC@Mo₂C in spite of the similar charges on the B-atoms can be accounted for by a less exergonic N₂ adsorption as compared to B_SAC@Mo₂C–Mo_vac. Additionally, B_DAC@Mo₂C with electron rich B-atoms shows a relatively higher limiting potential of 0.90 eV owing to its less exergonic N₂ adsorption. We further correlate our analogy to the first protonation step of the NRR, which is usually considered a crucial step in the NRR. It has been reported that a less endergonic or exergonic *N₂ → *N₂H step leads to a lower limiting potential for nitrogen reduction. Upon comparison of the free energies of the first protonation steps, the B_cat@Mo₂C catalysts with less endergonic free energies, i.e., B_SAC@Mo₂C–Mo_vac (−0.34 eV) and B_DAC@Mo₂C (0.02 eV) exhibit lower limiting potentials as compared to B_SAC@Mo₂C and B_SAC@Mo₂C–C_def. This analogy holds true only for the distal and alternating routes wherein N₂ has been adsorbed in the end-on mode. Our previous argument correlating N₂ adsorption free energies and Bader charges is in agreement with the analogy of first protonation energies, and therefore can give insightful information on the mutual correlation between the free energies of the adsorption and electronic properties that directly govern the limiting potentials of the NRR on B_cat@Mo₂C catalysts. Furthermore, the B_SAC@Mo₂C–Mo_vac catalyst with one Mo-vacancy is found to efficiently capture and accentuate the catalytic activity of the boron SAC with a very low overpotential of 0.41 eV for the NRR. This study provides an in-depth analysis of the electronic factors crucial for efficient N₂ adsorption and reduction, and proposes the B_SAC@Mo₂C–Mo_vac catalyst as a potential candidate for the NRR.

Fig. 5 Bader charges on N and B atom catalysts for N_xH_y intermediates involved in the free energy diagram for the NRR on all the B_cat@Mo₂C catalysts.

4 Conclusions

In summary, a detailed and systematic DFT investigation has been carried out to analyse the efficacy of N₂ adsorption and reduction on B_cat@Mo₂C monolayers. Our study identifies a metal-free boron anchored defective Mo₂C monolayer with superior electrocatalytic activity for the NRR at 0.41 eV on account of a more positive p-band center and the negative charge of boron SACs that implicitly stabilizes the intermediates along the energy profile of the NRR. The insights gained from this work can be implemented for further research towards the design of efficient B-atom based electrocatalysts for the nitrogen reduction reaction.

Author contributions

Ashakiran Maibam: calculation, methodology, investigation and analysis. Sailaja Krishnamurty and Manzoor Ahmad Dar: conceptualization and work design. All authors contributed equally to writing, reviewing and editing the manuscript.

Conflicts of interest

There are no conflicts of interest to declare.

Acknowledgements

A. M. acknowledges the CSIR for funding of the SRF (Senior Research Fellowship). M. A. D. acknowledges the Start-up research grant (SRG/2020/00654) from the SERB, India for financial support towards the completion of this work. The authors gratefully acknowledge the National Supercomputing Mission (NSM) for providing the computing resources of ‘PARAM Brahma’ at IISER Pune, which is implemented by C-DAC and supported by the Ministry of Electronics and Information Technology (MeitY) and the Department of Science and Technology (DST), Government of India.

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Footnote

† Electronic supplementary information (ESI) available. See DOI: 10.1039/d1ma00953b

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