First-Principles Study on Adsorption and Decomposition of NO<sub><i>x</i></sub> on Mo (110) Surface

Huang, Yunmi; Luo, Haijun; Dong, Changkun

doi:https://doi.org/10.1155/2021/3264737

Advances in Condensed Matter Physics

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Abstract Introduction Results and Discussion Conclusions Data Availability Conflicts of Interest Acknowledgments References Copyright Related Articles

Research Article | Open Access

Volume 2021 | Article ID 3264737 | https://doi.org/10.1155/2021/3264737

First-Principles Study on Adsorption and Decomposition of NO_x on Mo (110) Surface

Yunmi Huang,^1,2Haijun Luo,^1,2and Changkun Dong²

Academic Editor: Giuseppe Pellicane

Received03 Sept 2021

Revised22 Nov 2021

Accepted14 Dec 2021

Published30 Dec 2021

Abstract

Based on the density functional theory, the adsorption and decomposition of NO_x (x = 1, 2) on Mo (110) surface are studied with first-principles calculations. Results show that the stable structures of NO₂/Mo (110) are MoNO₂ (T, μ¹-N), MoNO₂ (H, μ³-N, O, O′), MoNO₂ (S, η²-O, O′), and MoNO₂ (L, η²-O, O′). The corresponding adsorption energies for the structures are −3.83 eV, −3.40 eV, −2.81 eV, and −2.60 eV, respectively. Besides, the stable structures of NO/Mo (110) are MoNO (H, μ¹-N), MoNO (H, μ²-N, O), and MoNO (H, η¹-N) with the corresponding adsorption energies of −3.75 eV, −3.57 eV, and −3.01 eV, respectively. N and O atoms are easily adsorbed at the hollow sites on Mo (110) surfaces, and their adsorption energies reach −7.02 eV and −7.70 eV, respectively. The preferable decomposition process of MoNO₂ (H, μ³-N, O, O′) shows that the first and second deoxidation processes need to overcome energy barriers of 0.11 eV and 0.64 eV, respectively. All these findings indicate that NO₂ is relatively easy to dissociate on Mo (110) surface.

1. Introduction

NO_x (x = 1, 2) gas widely exists in the process of industrial exhaust and automobile exhaust emission. It is a major cause of air pollution. It does not only cause a series of environmental problems, such as photochemical pollution, ozone layer destruction, haze, and other pollution but also causes considerable harm to human health. In order to reduce the harm of NO_x to humans and the environment, the removal and conversion of NO_x (adsorption, decomposition, desorption, etc.) had always been a hot research topic. Presently, the mechanism of transition metal surface and NO_x reaction is a hot topic in both experimental and theoretical simulation [1–11].

Molybdenum (Mo) and Mo-based catalysts exhibit excellent catalytic activity in many industrial areas, such as hydrodenitrogenation (HDN) [12–14] and hydrodesulfurization (HDS) of hydrocarbons, hydrogen evolution reaction (HER) [15–17], Fischer–Tropsch (F–T) synthesis [18, 19], and solid oxide fuel cell (SOFC) [20, 21]. Accordingly, a fundamental research focus on the interactions of nitrogen oxides with Mo and Mo-based surfaces is helpful to understand the reaction mechanism between them.

Some experimental studies research on the interaction between NO₂ and well-defined surfaces of Pt (111) [22–24], Ru (100) [25], Rh (111) [26], Ag (111) [27–29], Pd (111) [28, 30], and Au(111) [31, 32]. The results show that the NO₂ can be completely dissociated on Rh (111), Pd (111), Pt (111), Ru (100), and Ag (111), and it is adsorbed in the molecular form on Au (111). At the same time, these experiment results indicate that the interaction between NO₂ and metal surface can be generated by N atom or O atom.

Using the technologies of electron stimulated desorption ion angular distribution (ESDIAD), electron energy loss spectroscopy (EELS), temperature-programmed desorption (TPD), and low energy electron diffraction (LEED), the researchers analyzed the NO₂ [33], NO [34, 35], and N₂O [34] dissociative adsorption on Mo (100) and Mo (110). It indicates that NO₂ is easy to decompose to adsorbed NO + O at the temperature of 100∼150 K, while it is further decomposed into N₂ and O at the temperature of 250 K, showing Mo surface has the good catalytic ability for NO_x removal and conversion.

However, the theoretical calculations on the role of NO_x on transition metals surfaces and their alloys surfaces are still limited. Some basic problems in the experimental studies, such as the final adsorption structures and decomposition paths of NO_x on the surfaces of transition metals and their alloys, have not been fully understood. For such microscopic processes, the experimental tools are not feasible. The first-principles calculation based on the density functional theory as a powerful tool can be used to investigate the reaction mechanisms of NO_x with transition metals surfaces.

In this study, we report our findings about the adsorption and decomposition of NO_x on Mo (110) surface with first-principles calculations. The goal of this study is to find out the most possibly dissociative process and the most stable adsorption structure of NO_x on the Mo (110) surface.

2. Computational Method

The software used for the theoretical calculation is the Vienna ab initio simulation package (VASP) for total energy calculation based on the density functional theory [36–38]. The software package is a first-principles quantum mechanics and molecular dynamics composite package. It calculates the total energy and electronic structure with a plane wave as the basis function. All electron projector augmented wave (PAW) is used to deal with the interaction between ion real and valence electrons [39, 40]. This is because the paw method is more accurate than other pseudopotentials such as ultra-soft pseudopotential (USPP), so the paw pseudopotential provided by the VASP is used in this paper. A Methfessel–Paxton [41] electronic energy smearing of 0.2 eV is used in the self-consistent calculations. For the exchange-correlation energy function, the Perdew–Burke–Enzerhoff (PBE) functional and generalized gradient approximation (GGA) is used. Spin polarization and the correction of dipole moment are considered in the calculation process [42].

The surface structure of Mo (110) is simulated by a slab normal to Z direction. The repeated slab is composed of 7 layers of molybdenum (Mo) atoms, with 4 layers for the substrate in which the positions of Mo atoms are fixed. The other remaining 3 layers of Mo atoms can relax their positions to optimize the total energy of the system when other species of atoms or molecules are adsorbed on the outer surfaces of the layers. A vacuum region with a thickness larger than 10 Å is inserted between the adjacent crystal layers to avoid interference between the crystal layers.

The periodic supercell p (2 × 2) of the system is used to calculate the adsorption of NO₂, NO, N, and O. The self-consistent calculation is carried out according to the irreducible k-point automatically generated by the Monkhorst–Pack scheme [41]. To optimize the total energy of the whole system, k-point grid sizes of (21 × 21 × 21) and (4 × 4 × 1) are used alternatively. In the calculation, the cut-off energy of plane wave expansion is taken as 400 eV. By changing the sampling point density and cut-off energy in K space to test the convergence, these settings are sufficient to ensure the accuracy of the calculation.

There are four possible positions for the adsorption, namely top (T for short), long bridge (L for short), short bridge (S for short), and hole (H for short), as shown in Figure 1(a). The adsorption energy E_ads is defined by the following expression

(a)

(b)

In the abovementioned expression, E_(adsorbate ₊ _slab) is the total energy of the optimized system with atoms adsorbed. E_(slab) is the energy of the clean substrate surface and E_(adsorbate) is for the gas phase adsorbed by the substrate. According to this definition, the adsorption energy is negative, which means that the process is exothermic.

The surface energy σ is calculated using the equationwhere E_relax, E_unrelax, and E_bulk represent the relaxed surface total energy, unrelaxed surface total energy, and the bulk total energy, respectively. A and N represent the surface area of the slab and the number of atoms in the cell, respectively.

To study the decomposition of NO_x, the climbing image nudged elastic band (CI-NEB) [43, 44] is used to search the transition state (TS). In this way, the path between the TSs is determined with the minimum energy. Practicably, eight images are set between the initial state (IS) and the final state (FS) for searching and locating the minimum energy paths (MEPs) of the decomposition reaction.

3. Results and Discussion

3.1. Bulk Mo and Clean Mo (110) Surface

Before studying the NO_x adsorption, let us study the structure of bulk Mo and clean Mo (110) surface at first. After the optimization in the calculation, the lattice parameter of the crystal molybdenum with body-centered cubic (BCC) structure is 3.146 Å, which is in good agreement with the experimental results (∼3.15 Å) [45, 46] and other calculated data (∼3.16 Å) [47, 48]. The p (2 × 2)-layer crystal model of 7-layer Mo (110) is used to simulate the clean Mo (110) surface shown in Figure 1(b). It is found that the relaxation between the first and second layers, noted by Δd₁₂, and the relaxation between the second and third layers, noted by Δd₂₃, are −4.95% and 0.75%, respectively. The relaxation between the third and fourth layers is calculated to be Δd₃₄ = 0.26%, which is too small compared to Δd₁₂ and Δd₂₃ and can be ignored. The surface energy σ calculated for clean Mo (110) is 2.94 J/m² and the work function (W) is 4.57 eV, respectively. The data obtained above in this study are in good agreement with other reported values [49–52] and experimental measurements [53].

3.2. Gas-Phase NO₂ and NO Molecules

The gas-phase NO₂ and NO molecules are simulated. After optimization, the N–O bond length of the NO molecule is 1.172 Å. The bond length of the NO₂ molecule is 1.212 Å, and the angle of O–NO is 133.8°. Table 1 lists bond length, bond angle, asymmetric stretching ν_a, symmetric stretching ν_s, and bending frequencies ν_b. It can be seen that the calculated data in this paper are in good agreement with the experimental values.

3.3. N and O Atoms Adsorption on Mo (110) Surface

Generally, NO₂ molecules are decomposed to be NO, N, and O. In order to study the possible decomposition and adsorption process of NO₂ on the surface of Mo (110), it is necessary to understand many possible stable adsorption structures including NO₂/Mo (110), NO/Mo (110), N/Mo (110), and O/Mo (110). As discussed above, the four different adsorption sites, namely, T, S, L, and H, are considered. The symbols η and µ represent that the molecular plane of NOx is perpendicular and parallel to the substrate, respectively. The following definitions are the same.

At the same time, because of the symmetry of the molecular structure, it is also necessary to consider the possibility of multiple placements of adsorbed molecules during research. As shown in Figure 2, five adsorbed modes of NO₂ adsorption are considered. In this way, based on the detailed consideration of adsorption coordination and placement modes, all possible stable adsorption structures, including adsorption energies, stable adsorption sites, and adsorption geometries (bond length and bond angle) of NO, N, and O on Mo (110), are finally obtained.

First, let us consider the adsorption of N and O atoms on the Mo (110) surface. Figure 3 and Table 2 show that there are four adsorption structures of N adsorption on Mo (110) surface, namely, MoN (H, μ¹-N), MoN (L, μ¹-N), MoN (S, μ¹-N), and MoN (T, η¹-N). The corresponding adsorption energies are −7.02 eV, −6.98 eV, −6.16 eV, and −4.68 eV, respectively. It is found that the structure of MoN (H, μ¹-N) is the most stable, and MoN (T, η¹-N) is less than that of MoN (H, μ¹-N). The structures of MoN (H, μ¹-N) and MoN (L, μ¹-N) have the shortest average distances (h in Table 2) between the N atom and substrate. It can be concluded that, the closer the distance between the N atom and substrate, the stronger the binding.

Let us study the adsorption of O atoms on the Mo (110) surface. It can be seen from Figure 4 and Table 3 that MoO (H, μ¹-O) is the most stable structure. The adsorption energies of the four adsorption structures MoO (H, μ¹-O), MoO (L, μ¹-O), MoO (S, μ¹-O), and MoO (T, η¹-O) are calculated to be −7.71 eV, −7.57 eV, −7.02 eV, and −6.32 eV, respectively. These data show that the adsorptions are strong. The adsorption of N and O atoms on the Mo (110) surface behaves similar to the adsorption of N and O atoms on the W (111) surface and the Fe (111) surface [1, 2].

3.4. Adsorption of NO on Mo (110) Surface

In order to study the dissociation of NO₂ on the Mo (110) surface, it is very important to explore the interaction between NO and Mo (110). Similar to the abovementioned studies, four adsorption positions on the surface of Mo (110) are still used for NO adsorption. It can be seen from Figure 5 and Table 4 that NO/Mo (110) mainly has the following five structures: MoNO (H, μ¹-N), MoNO (T, η¹-O), MoNO (T, η¹-N), MoNO (H, μ²-N, O), and MoNO (H, η¹-N), where MoNO (H, μ¹-N) is the most stable structure, and its adsorption energy is −3.75 eV. The second and third stable structures are MoNO (H, μ²-N, O) and MoNO (H, η¹-N) with corresponding adsorption energies of −3.57 eV and −3.01 eV, respectively. From these structures, it is found that NO acts mainly through N atoms with Mo (110) surface.

3.5. Adsorption of NO₂ on Mo (110) Surface

NO₂ molecule has a curved structure, and the inner angle of O–N–O is 133.8°. Calculations show that NO₂ takes effect mainly through N atoms on the Mo (110) surface, which is similar to the adsorption of NO. According to Figure 6 and Table 5, NO₂/Mo (110) mainly has the following stable structures: MoNO₂ (T, μ¹-N), MoNO₂ (H, μ³-N, O, O′), MoNO₂ (S, η²-O, O′), MoNO₂ (L, η²-O, O′), MoNO₂ (T, η¹-O), MoNO₂ (T, η²-O, O′), MoNO₂ (L, η¹-N), and MoNO₂ (S, η¹-N). As can be seen from Figure 6, MoNO₂ (T, μ¹-N) and MoNO₂ (H, μ³-N, O, O′) are the most and second stable structures, and the adsorption energies are −3.83 eV and −3.40 eV, respectively. In both structures, NO₂ is obliquely adsorbed on the surface. MoNO₂ (S, η²-O, O′), and MoNO₂ (L, η²-O, O′) are also two stable structures with corresponding adsorption energies of −2.81 eV and −2.60 eV, respectively.

3.6. Deoxidation Process of NO₂ on Mo (110) Surface

Next, we will focus on the deoxidation process of NO₂ on Mo (110) surface. Generally, the interaction between NO₂ and Mo (110) surface is carried out according to the following steps: Step 1: NO_2(gas) ⟶ NO_{2 (ads)} Step 2: NO_{2 (ads)} ⟶ NO_(ads) + O_(ads) Step 3: NO_(ads) + O_(ads) ⟶ N_(ads) + 2O_(ads)

The climbing configuration elastic band method is used to study the decomposition process of NO₂ on Mo (110) surface. The CI-NEB method requires determining the initial and final states of the reaction. So in the deoxidation process of the first part (Step 2), the most stable structure of NO₂/Mo (110) is selected as the initial state, that is, MoNO₂ (T, μ¹-N), MoNO₂ (H, μ³-N, O, O′), and MoNO₂ (S, η²-O, O′) as the initial state of the first step deoxidation process, and the three structures are named LM1-1, LM1-2, LM1-3, respectively. In order to determine the structure of the final state NO_(ads) + O_(ads), it can be seen from the adsorption of NO and O on Mo (110) surface that they are the most stable structures at the hollow position. Therefore, NO was placed at the hollow position, and O was placed at the supercell p (2 × 2). After calculations, it is found that only one structure of LM2-1 is stable (the specific structure as shown in Figure 7). Figure 7 shows the possible potential energy surface (PES) of the first step deoxidation process constructed. Path 1: As shown in Figure 7(a), the most possible pathway of the first deoxidation process of NO₂ on Mo (110) surface starts from LM1-2 to LM2-1 via the transition states TS1 and TS1′. The heat release in the whole process is up to 2.79 eV. During this process, it needs to cross two transition states with energy barriers of 0.11 eV and 0.50 eV, respectively. The activated N–O bond length changes from 1.372 Å in the initial state to 1.419 Å in TS1, then extend to 2.709 Å in TS1′ and finally to be 2.741 Å in final state LM2-1. The bond angle of O–N–O changes from 113.7° in the initial state to 110.39° in TS1. The activated oxygen atom gradually crosses the short bridge position and finally reaches the hollow position. Path 2: Another possible pathway of the first deoxidation process is explored from LM1-3 to LM2-1. The heat release in the whole process reaches 3.38 eV. It needs to cross the transition states TS2 and TS2′. The potential barriers are 0.76 eV and 0.73 eV, respectively. The activated N–O bond length changes from 1.372 Å in the initial state to 1.419 Å in TS2, then extend to 2.709 Å in TS2′ and finally to be 2.741 Å in final state LM2-1. The bond angle of O–N–O changes from 113.2° in the initial state to 113.1° in TS2. The activated oxygen atom gradually moves from the top position to the hollow position. For the second deoxidation process (Step 3), the initial state is the final state of the previous step, namely, LM2-1 and LM2-2. For the determination of the final state, it is also necessary to determine the coadsorption of N and 2O. After calculation, it is found that there are two stable structures, namely, LM3-1 and LM3-2 (as seen in Figure 8). Path 3: Figure 8(a) is the potential energy surface of the second constructed deoxidation process in step 3. It can be seen from the figure that the process needs to experience the transition state of TS3 from LM2-1 to LM3-1. The heat release in the whole process is 2.13 eV and the height across the potential barrier is 0.66 eV. In this path, the N–O bond is broken and the atoms of oxygen and nitrogen are adsorbed at the hollow sites, respectively. Path 4: For the second deoxidation process of NO₂ on Mo (110) surface, NO(ads) + O(ads) ⟶ N(ads) + 2O(ads), another possible path from LM2-1 via the transition state of TS4 into LM3-2 is exothermic by 2.32 eV with the calculated barrier of 0.64 eV, as shown in Figure 8(b). In TS4, the N–O bond is elongated to be 1.83 Å. After the TS4, the dissociating oxygen crosses the top site, short bridge site, and finally adsorbs at the hollow site.

(a)

(b)

(a)

(b)

In summary, the preferable reaction pathway of NO₂(gas) + slab ⟶ LM1-2 ⟶ TS1 ⟶ LM2-1 ⟶ TS4 ⟶ LM3-2 is calculated to be exothermic by 5.11 eV, with the first, second deoxidation activation barriers of 0.11 eV, 0.64 eV, respectively. These results have shown that NO₂ molecule can dissociate completely on the perfect Mo (110) surface, which is in agreement with the experiment [33, 34]. It also indicates that Mo (1 1 0) surface exhibits good catalytic activity to decompose NOx as well as other gas, such as H₂S [54, 55].

4. Conclusions

Based on the density functional theory, the adsorption and decomposition of NO_x (x = 1, 2) on the Mo (110) surface were calculated by the first principle. The results show that the stable structures of NO₂/Mo (110) coordination are MoNO₂ (T, μ¹-N), MoNO₂ (H, μ³-N, O, O′), MoNO₂ (S, η²-O, O′), and MoNO₂ (L, η²-O, O′). The corresponding adsorption energies are −3.83 eV, −3.40 eV, −2.81 eV, and −2.60 eV, respectively. The stable structure of NO/Mo (110) are MoNO (H, μ¹-N), MoNO (H, μ²-N, O), and MoNO (H, η¹-N) and the corresponding adsorption energies are −3.75 eV, −3.57 eV, and −3.01 eV, respectively. N and O are easily adsorbed at the hollow site of the Mo (110) surface, and their adsorption energies are −7.02 eV and −7.70 eV. The study on the preferable decomposition process of NO_x (x = 1, 2) on Mo (110) shows that the potential barriers of the first and second deoxidation processes of MoNO₂ (H, μ³-N, O, O′) are 0.11 eV and 0.64 eV, respectively. All these findings indicate that the Mo (110) surface exhibits good catalytic activity to decompose NOx.

Data Availability

The raw/processed data required to reproduce these findings cannot be shared at this time as the data also forms part of an ongoing study.

Conflicts of Interest

The authors declare that they have no conflicts of interest.

Acknowledgments

This work was supported financially by the National Natural Science Foundation of China (Grant nos. 61620106006 and 61871292), and the scientific research project of Zhejiang Provincial Department of Education in 2020 (Grant No: Y202044305)

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Copyright © 2021 Yunmi Huang et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Advances in Condensed Matter Physics

First-Principles Study on Adsorption and Decomposition of NOx on Mo (110) Surface

Abstract

1. Introduction

2. Computational Method

3. Results and Discussion

3.1. Bulk Mo and Clean Mo (110) Surface

3.2. Gas-Phase NO2 and NO Molecules

3.3. N and O Atoms Adsorption on Mo (110) Surface

3.4. Adsorption of NO on Mo (110) Surface

3.5. Adsorption of NO2 on Mo (110) Surface

3.6. Deoxidation Process of NO2 on Mo (110) Surface

4. Conclusions

Data Availability

Conflicts of Interest

Acknowledgments

References

Copyright

First-Principles Study on Adsorption and Decomposition of NO_x on Mo (110) Surface

3.2. Gas-Phase NO₂ and NO Molecules

3.5. Adsorption of NO₂ on Mo (110) Surface

3.6. Deoxidation Process of NO₂ on Mo (110) Surface