DFT study on the disproportionation of methylchlorosilane catalyzed by AlCl3/ZSM-5(4T)@MIL-53(Al) core-shell catalyst

doi:10.21203/rs.3.rs-1657823/v1

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DFT study on the disproportionation of methylchlorosilane catalyzed by AlCl3/ZSM-5(4T)@MIL-53(Al) core-shell catalyst

https://doi.org/10.21203/rs.3.rs-1657823/v1

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Dimethyldichlorosilane is one of the most widely used monomers in the organic silicon industry chain. In the preparation process, it can be obtained by exchanging functional groups through disproportionation reaction. In this research, the disproportionation mechanism catalyzed by ZSM-5(4T)@MIL-53(Al) and AlCl₃/ZSM-5(4T)@MIL-53(Al) core-shell catalysts was studied by using the density functional theory on the level of M06-2X/Def2-TZVP. The results showed that the two catalysts possessed different catalytic effect assigning to different acidic actives. The surface activity of ZSM-5(4T)@MIL-53(Al) core-shell catalyst modified by AlCl₃ became the Lewis acid center of Al-Cl bond, which had better disproportionation activity than that before modification. Energies, frequency vibrations and IRC calculations, bond orders, ELF and LOL analyses can verify the reaction mechanism proposed in this research.

core-shell catalyst

disproportionation reaction

density functional theory

ZSM-5

MIL-53(Al)

Generally, in the industrial chain of organosilicon, dimethyldichlorosilane ((CH₃)₂SiCl₂, M2) is one of the important monomers for the preparation of organosilicon materials [1–4]. To the best of our knowledge, the Rochow-Muller reaction is the most important strategy for the direct synthesis of M2 monomers. However, during the preparation of M2, methyltrichlorosilane (CH₃SiCl₃, M1), trimethylchlorosilane ((CH₃)₃SiCl, M3) and high boiling residue would be produced [5–7]. At this stage, based on the consideration of economy and environment, M1 and M3 with lower economic value can be used as raw materials to prepare M2 with higher economic value through disproportionation under certain catalysts. Therefore, this topic is of great significance to the treatment of chlorosilane residue, to understand the harmness of chlorosilane residue and the utilization of resources.

In recent years, metal-organic frameworks (MOFs), a new class of crystalline materials composed of metal ion clusters linked by organic ligands, have attracted extensive attention and become new catalytic materials attributing to their unique structure, atomic metal dispersion, and structural properties [8–10]. MIL-53(Al) is a three-dimensional topological material synthesized via the self-assembly reaction of inorganic AlO₄(OH)₂ and HOOC-C₆H₄-COOH organic ligands. It was widely used in the fields of catalysis, gas adsorption and conductivity with high thermal stability, high surface area, large pore volume and geometric control [11, 12]. AlCl₃, a Lewis acid catalyst, was outstanding in disproportionation of methylchlorosilane[13]. However, it is easy to sublimate when heated in the reaction process, which makes mixture separation more difficult [14]. The relevant studies had shown that the immobilization of AlCl₃ could alleviate sublimation and reduced the catalyst loss. Previously, we conducted disproportionation studies on AlCl₃/ZSM-5 catalysts of 3T ~ 24T clusters and AlCl₃/MIL-53(Al) catalysts [15, 16]. It indicated that ZSM-5, as a traditional solid acid catalyst, had both Brønsted acidic centers (Al-O-H bond) and Lewis acid centers on its surface. Besides, its special pore channels could provide a relatively wide surrounding for the reaction system [17–19]. At the same time, MIL-53(Al) provided a good attachment site in the process of disproportionation reaction, especially the Al-O-H acidic active center with strong catalytic activity, which was conducive to the forward progress of disproportionation reaction. Core-shell catalysts were widely used due to their unique interface effect and core-shell structure, it was possible to enhance the disproportionation activity. This research attempted to construct ZSM-5(4T)@MIL-53(Al) core-shell structure based on 4T cluster ZSM-5 with the modification of MIL-53(Al), subsequently loading with AlCl₃. The disproportionation reaction mechanism catalyzed by ZSM-5(4T)@MIL-53(Al) (abbreviation as Cat.) and AlCl₃/ZSM-5(4T)@MIL-53(Al) (abbreviation as Cat.^&) were studied by using density functional theory (DFT).

2.1 Calculation method

In this research, all structures of Cat. and Cat.^& involved in disproportionation reaction were geometrically optimized and relative vibrational frequencies were calculated by using DFT on the level of B3LYP/3-21G in Gaussian 09 software [20–24], and the transition state (TS) method was used to search for transition states. Frequency calculations and analyses showed that the torque constants of the structures involved, such as reactants, intermediates and disproportionated products, were positive, while the transition states had an only one negative virtual frequency. After the structure was determined, the M06-2X/Def2-TZVP hybrid functional method of Minnesota series was used to calculate the energy of each structure in the system, and the zero-point energy (ZPE) correction was considered at the same time. In order to deeply study and analyze the disproportionation activity of Cat.^&, the related bond order was analyzed. In detail, the Mayer bond order (MBO), Laplacian bond order (LBO) and Mulliken bond order (Mulliken overlap) were calculated via the Multiwfn software [25]. Then the electronic localization function (ELF) and localized orbital locator (LOL) were used to analyze the electronic localization state of the active site of Cat.^&[26–28].

2.2. Structural model

By consulting the Database of Zeolite Structures and Cambridge Crystal Database (CCDC), the ZSM-5 and MIL-53(Al) infrastructure models were extracted and fused with each other. The locally integrated structure of ZSM-5(4T)@MIL-53(Al) was simulated. Figure 1 showed the stable structures of Cat. and Cat.^& after full optimization calculation. It can be seen from Fig. 1(c) that Cat. is a fusion of ZSM-5(4T) (Fig. 1(a)) and MIL-53(Al) (Fig. 1(b)). It can be regarded as two parts: the upper part was fused by ZSM-5(4T) and MIL-53(Al), and a stable Al-O-Al-O four-membered ring structure was constructed. The lower part was mainly the residual partial configuration of MIL-53(Al). For Cat. modeling, the resulting dangling bonds can be saturated with H atoms, so the active sites of the structure were mainly concentrated on the hydroxyl H connected to each O atom in the upper half, namely the active bridged hydroxyl [29, 30].

Similarly, AlCl₃ loading was calculated for all active sites of Cat.. It was found that only one group of sites could be loaded well (as shown in Fig. 1(d)). AlCl₃ and active sites No. 3 and No. 5 of Cat. were close to each other. Thereafter, the relative Al and O atoms was bonding after the removing of HCl. Finally, the new Al-O-Al-O four membered ring and Al-O-Al-O-Al-O six-membered ring structure were formed. It was showed from the key geometric data of ZSM-5(4T)@MIL-53(Al) that the bond lengths of Al-O were 0.1721–0.1925 nm, which was very close to the value of 0.182-0.200 nm reported in the literature. The bond length data of C-O were 0.1286–0.1331 nm, which was consistent with the value of 0.123–0.139 nm reported in the literature [31]. Subsequently, the frequency calculation was carried out, and its stretching vibrational frequencies of O-H bonds (No. 1 ~ 5) were obtained as follows: 3656.23, 3696.49, 3616.75, 3549.88 and 3495.68 cm^− 1, compared with the experimental results (reported to be 3710 cm^− 1) [29], the relative error was only 0.36% ~ 5.78%, thus indicating that structural credibility of ZSM-5(4T)@MIL-53(Al).

Figure 1 Combined model and key atomic number of catalysts: (a) The basic structure of ZSM-5(4T); (b) The basic structure of MIL-53(Al); (c) Structure of ZSM-5(4T)@MIL-53(Al), key parameters and its five active sites (numbered 1–5). (d) Close-up structure and key parameters of AlCl₃/ZSM-5(4T)@MIL-53(Al). (bond length: nm, bond Angle: °)

3.1 ZSM-5(4T)@MIL-53(Al) core-shell catalyst

From the above model (Fig. 1(c)), it can be observed that Cat. had 5 active sites (marked by purple circles) locally. In order to avoid unnecessary repetition of similar reaction mechanism of each active site, this research mainly took active site 1 as an example to discuss the catalytic mechanism of disproportionation between M1 and M3 in order to prepare M2. The reaction equations of Cat. catalytic system was shown in Fig. 2(a), the corresponding reaction process and its key atomic numbers were shown in Fig. 2(b).

The disproportionation reaction was divided into two channels. In the first channel, Cat. and (CH₃)₃SiCl adsorbed each other and reacted assigning to intermolecular force, and the intermediate I1 and CH₄ were generated through the transition state TS1. Then, I1 continued to adsorbed with CH₃SiCl₃, when the intermediate II and (CH₃)₂SiCl₂ were formed through the transition state TS2. Finally, the intermediate II adsorbed with CH₄ though the transition state TS3, the reduced Cat. and (CH₃)₂SiCl₂ were formed. Thus, the production of main product (CH₃)₂SiCl₂ indicated that the first channel was the main reaction route.

In the second channel, Cat. and CH₃SiCl₃ adsorbed each other and reacted assigning to intermolecular force, and the intermediate III and CH₄ were generated through the transition state TS4. Then, III continued to adsorb with CH₃SiCl₃, and the intermediate IV and SiCl₄ were formed through the transition state TS5. Finally, the intermediate IV adsorbed with CH₄ though the transition state TS6, the reduced Cat. and Si(CH₃)₄ were formed. Thus, the by-product SiCl₄ and Si(CH₃)₄ indicated that the second channel was the side reaction route.

Figure 2 (a) The reaction equations of ZSM-5(4T)@MIL-53(Al) catalytic system. (b) The reaction process catalyzed by ZSM-5(4T)@MIL-53(Al) core-shell catalyst (No. 1 active site) and its key atomic numbers. Rx, TSx, Ix, and Px (x = 1–6) represent the reactant, the transition state, the intermediate, and the product, respectively. Cat. represents ZSM-5(4T)@MIL-53(Al) core-shell catalyst

Based on the reaction mechanism described in Fig. 2, geometric optimized calculations were performed for all reactants, products and transition states involved in the disproportionation reaction on all active sites of Cat. The virtual vibrational modes of transition states were obtained by vibrational frequency analysis. Furthermore, the structures of the transition states TSx(x = 1–6) were verified. The key parameters and virtual vibrational modes of transition states in Cat. system were shown in Fig. 3 (active site 1) and Fig.S1-S4 (active sites 2–5) in the supplementary material. Obviously, the atomic vibrations of the transition states in each step mainly came from relative atomic stretching vibrations such as O¹, H¹, Si¹, Si², Cl¹, Cl², C¹, and C², and each transition state had a simultaneous reaction to its corresponding trends in the vibrations of reactants and products. In detail, the key atomic vibrational directions of the magenta arrows tend to move towards the product, while those of the purple arrow tend to move towards the reactant. Combined with Fig. 2 and Fig. 3, take the main reaction step TS1 of disproportionation reaction catalyzed by Cat. as an example: during the reaction between Cat. with (CH₃)₃SiCl, the relatively low energy Si¹-C¹ bond of (CH₃)₃SiCl and O¹-H¹ bond of Cat. and (CH₃)₃SiCl broke apart and move away from each other, while the Brønsted acidic H¹ atom got closer and bonded with C¹ atom of the methyl group to form CH₄. The O¹ atom of catalyst and Si¹ atom groups were bonded to form intermediate I. Those were the product P1. Observing the reverse process of this step, starting from the transition state TS1, the Si¹ atom and C¹ atom in the methyl group gradually approached and bonded to form (CH₃)₃SiCl, and the H¹ atom combined with O¹ atom to bond and form Cat., those were the corresponding reactant R1. The analysis of other transition states was similar to TS1, and the results showed that the frequency vibrational directions and trends of all key atoms of the transition states were consistent with the aforementioned reaction mechanism. In summary, the reliability of the transition state can verify the credibility of the reaction mechanism.

Figure 3 The vibrational modes of the transition states of active site 1, its key atomic number and distance of each reactant, product and transition state

In order to further test the reliability of the transition state structure of each step, the intrinsic response coordinates (IRC) method, which could track both the forward and reverse directions of the transition state was used. Thus, IRC calculation was carried out for the transition state structure of each step. Figure 4 showed the variational tendency of the spacing of key atoms on active sites 1, 2 and 3 of Cat. along IRC. In addition, relative IRC analyses of active sites 4 and 5 were shown in Fig.S5 of supplementary materials. The capital letter S in English stood for the measure of IRC, and the positive and negative value ranges of S represented the regions of product and reactant, respectively. When S pointed to 0, it meant that the structure tended to transition state. It can be seen from the figure that the disproportionation reaction started from the reactants and passed through the transition state to generate the product, and the distance between the key atoms showed a trend of lengthening or shortening. It was consistent with the vibrational trends of the transition state in Fig. 3, which proved the correctness of the reaction mechanism.

Figure 4 Variation trend of key atom spacing along IRC in ZSM-5(4T)@MIL-53(Al) catalytic system; (a)-(f) represent the IRC of transition states TS1-TS6, respectively

The energy calculation of the disproportionated structure was carried out by using the M06-2X/Def2-TZVP hybrid functional method of the Minnesota series, and ZPE correction was used at the same time. Figure 5 and Table 1 are the reaction energy diagram of Cat (active sites 1–5) disproportionate synthesis on M2 and the numerical statistics table of the related activation energy. Taking active site 1 (indicated by the black line) as an example, the activation energy barrier data (¹Ea₁-¹Ea₆) of each step of the disproportionation reaction were: 122.76, 21.89, 152.14, 76.02, 20.32 and 112.55 kJ•mol^− 1, respectively. From the above numerical comparison, it can be seen that the largest activation energy barrier in the main reaction was the third step and its activation energy of the rate-determining step was 152.14 kJ•mol^− 1. Similarly, the activation energy of the rate-determining step of the side reaction was 112.55 kJ•mol^− 1. The rate-determining step energy barrier of the main reaction was larger than that of the side reaction, indicating that the active site 1 of Cat. mainly produces by-products. Other active sites (2–5) were analyzed in the same way as active site 1. From the above data, it can be seen that the activation energy barrier data of the active sites 1, 2, 3, 4, and 5 in the main reaction rate-determining step were 152.14, 118.06, 152.74, 162.69 and 185.31 kJ•mol^− 1 (marked in red in the table), the activation energy barrier data for the rate-determining step of the side reaction were 112.55, 122.85, 131.34, 162.47 and 157.62 kJ•mol^− 1 (in the table marked in blue). The rate-determining step activation energy of the main reaction at sites 1, 3, 4 and 5 were all larger than those of the side reactions, indicating that these sites had little competitive advantage in synthesizing the target product (CH₃)₂SiCl₂. However, the activation energy of the main reaction rate-determining step of the active site No. 2 was lower than that of the side reaction, and the active site No. 2 had a lower energy barrier than other sites. It was obvious that active site 2 was more conducive to the synthesis of M2 and showed a better disproportionation effect.

Table 1

Activation energy data of all active sites (1–5) of ZSM-5(4T)@MIL-53(Al) core-shell catalytic system and AlCl₃/ZSM-5@MIL-53(Al) catalytic system (kJ•mol^− 1)
Catalyst and Active Center		Cat.					Cat.^&
Catalyst and Active Center		No.1	No.2	No.3	No.4	No.5	Cat.^&
Activation energy (kJ•mol^− 1)	Ea₁	122.76	118.06	152.74	140.04	185.31	61.69
	Ea₂	21.89	20.37	30.66	33.53	100.74	86.92
	Ea₃	152.14	96.03	29.02	162.69	124.26	137.94
	Ea₄	76.02	82.28	12.65	162.47	64.79	41.66
	Ea₅	20.32	18.21	51.47	30.15	157.62	-
	Ea₆	112.55	122.85	131.34	136.51	101.64	-

Figure 5 Active sites (1–5) of ZSM-5(4T)@MIL-53(Al) core-shell catalyst and activation energy of AlCl₃/ZSM-5@MIL-53(Al) catalytic system

Table 1 Activation energy data of all active sites (1–5) of ZSM-5(4T)@MIL-53(Al) core-shell catalytic system and AlCl₃/ZSM-5@MIL-53(Al) catalytic system (kJ•mol^− 1)

3.2 AlCl₃/ZSM–5(4T)@MIL-53(Al) catalyst

The reaction equations of Cat.^& catalytic system were shown in Fig. 7(a). The disproportionation reaction was divided into two channels: main reaction and side reaction. In the first channel, Cat.^& and (CH₃)₃SiCl adsorbed each other and reacted assigning to intermolecular force, and the intermediate I^& and (CH₃)₂SiCl₂ were generated through the transition state TS1. Then, I^& continued to adsorb with CH₃SiCl₃ through the transition state TS2. The reduced Cat.^& and (CH₃)₂SiCl₂ were formed. Thus, the main product (CH₃)₂SiCl₂ indicated that the first channel was the main reaction route. In the second channel, Cat.^& and CH₃SiCl₃ adsorbed each other and reacted assigning to intermolecular force, and the intermediate I^& and CH₄ were generated through the transition state TS3. Finally, the intermediate I^& adsorbed with (CH₃)₃SiCl through the transition state TS4, the reduced Cat.^& and Si(CH₃)₄ were formed. Thus, the by-product SiCl₄ and Si(CH₃)₄ indicated that the second channel was the side reaction route.

Figure 7 (a) Reaction equations of AlCl₃/ZSM-5(4T)@MIL-53(Al) catalytic system. (b) Reaction process catalyzed by AlCl₃/ZSM-5(4T)@MIL-53(Al) catalyst and its key atomic numbers. Rx, TSx, Ix, and Px(x = 1–4) represent reactants, transition states, intermediates, and products, respectively. Cat.^& represents AlCl₃/ZSM-5(4T)@MIL-53(Al) core-shell catalyst

Based on the reaction flow diagram and its key atomic numbers of Cat.^& for disproportionation synthesis on M2 as shown in Fig. 7(b), the virtual frequency vibrational analysis of the disproportionation reaction was carried out. Figure 8 showed the imaginary frequency vibration of the transition state of the reaction channel and its key atomic numbers. It can be seen from the figure that the atomic vibrations of the transition states of the disproportionation steps mainly came from the relative atomic stretching vibrations such as Si¹, Si², Cl¹, Cl², C¹, C², Al^& and Cl^&. Taking TS1 as an example: Cat.^& and (CH₃)₃SiCl approached and interacted with each other, the Si¹-C¹ bond of (CH₃)₃SiCl and Al^&-Cl^& of the catalyst were broken respectively, and the C¹ atom of methyl group and Al^& atom were close to each other and formed a bond, resulting in the forming of the intermediate I^&. The Si¹ atom of (CH₃)₃SiCl and Cl^& atom were close to each other and formed a bond to generate the product (CH₃)₂SiCl₂. Those were the product P1. Observing the reverse process of this reaction and another vibrational direction of TS1, Si¹ and C¹ atoms were close to each other and form a bond, and Al^& and Cl^& atoms were close to each other and formed a bond. Those were the reactant R1. The vibrations of other transition states were also analyzed similarly. It was shown from the results that the distance between the key atoms increased or decreased with the reaction progresses, indicating that the reaction path was correct and each transition state was in the force constant matrix. There was positive frequency for all stable structure (reactants, products and intermediates) or only one imaginary frequency for each transition state, and the frequency vibrational direction and trend of key atoms were unified with the aforementioned reaction mechanism. Not only those above showed that the transition state structure was real and reliable, but also indicated that the reaction mechanism was credible.

Figure 8 The vibrational modes of the transition states of AlCl₃/ZSM-5(4T)@MIL-53(Al) catalyst, its key atomic numbers and distances of each reactant, product and transition state

In order to further test the reliability of the transition state structure of each step, the IRC method, which can track both the forward and reverse directions of the transition state was used. Thus, IRC calculation was carried out for the transition state structure of each step. The change trend of the spacing of important atoms of Cat.^& along IRC was shown in Fig. 9. It can be seen from the figure that disproportionation reaction started from the reactant and passed through the transition state to produce products, and its distance between key atoms tended to lengthen or shorten. That was consistent with the above virtual vibrational analysis and reaction mechanism, which proved the correctness of the reaction mechanism.

Figure 9 The variational trend of key atomic spacing along IRC in modified AlCl₃/ZSM-5(4T)@MIL-53(Al) catalytic system

The energy calculation of the structure involved in the Cat.^& catalytic system was carried out by using the M06-2X/Def2-TZVP hybrid functional method of the Minnesota series, and ZPE correction was used at the same time. Combined with Fig. 5 (the brown line) and Table 1, we can saw that the rate-determining step of the main reaction occurs in the second step of disproportionation, and its activation energy barrier datum was 86.92 kJ•mol^− 1. That was to say, the activation energy barrier of the rate-determining step in the main reaction was 86.92 kJ•mol^− 1. Similarly, the activation energy barrier of the rate-determining step in the side reaction was 137.94 kJ•mol^− 1. It was obvious that the activation energy of the rate-determining step in the side reaction was higher than that of the main reaction, indicating that the Cat.^& was beneficial to the disproportionation synthesis on M2. Compared with the activation energy data before loading (Fig. 6), the activation energy barrier value (86.92 kJ•mol^− 1) of the rate-determining step in the main reaction of Cat.^& catalytic system rate-determining step was the smallest. Moreover, the activation energy barrier difference value between the main reaction and side reaction was quite large, indicating that the main reaction of the disproportionation reaction involving the Cat.^& was more competitive, which made it easier to synthesize the target product (CH₃)₂SiCl₂ through a lower energy barrier and enhanced the difficulty in producing by-products at the same time.

In order to further study the activity of Cat.^&, the catalyst was analyzed in combination with bond order, LOL and ELF. After calculation by using the Multiwfn software, the MBO bond order of the Al^&-Cl^& bond of Cat.^& was 0.7114; the LBO bond order was 0.1984, and the Mulliken bond order was 0.3313. Figure 10 showed the ELF and LOL diagrams of Cat.^&. As shown in Fig. 10(a) (ELF), the orange-yellow inner core of the Cl^& atom indicated that its strong localization. The color gradually changed outward a very narrow blue, indicating that the orbital electrons of Cl^& atom inner layer the orbital could be shared. However, the outer orbital of the entire Cl^& atom was occupied by broad band orange and narrow band yellow, indicating that the valence orbital electrons of the outer layer were well localized. In addition, its electron-withdrawing characteristics were in line with Lewis acidic characters. Therefore, Cl^& atom could attract the electrons provided by the methyl group on the silane and reacted each other. The orange inner area of Al^& atom indicated its robust electron localization. Besides, the outer layer hue rapidly transformed to a broadband dark blue, indicating that its strong delocalization and electronic sharing with other atoms. From the region of Al^& and Cl^& atoms, it could be observed that the Al^&-Cl^& bond exhibited obvious polar and ionic bond characteristics.

LOL analysis in Fig. 10(b) was similar to the said ELF analysis. It could be seen from the figure that the lighting yellow center of the Cl^& atomic nucleus showed well localization. The color gradually changed outward a very narrow blue, indicating that the orbital electrons of Cl^& atom inner layer the orbital could be shared. However, the outer orbital of the entire Cl^& atom was occupied by broad band orange and narrow band yellow, indicating that the valence orbital electrons of the outer layer were well localized. In addition, its electron-withdrawing characteristics were in line with Lewis acidic characters. Therefore, Cl^& atom could attract the electrons provided by the methyl group on the silane and reacted each other. The light green inner area of Al^& atom indicated its weak electron localization. Besides, the outer layer hue rapidly transformed to a broadband dark blue, indicating that its strong delocalization and electronic sharing with other atoms. In summary, the catalytic activity of Cat.^& was further improved after loading AlCl₃. This can be well matched with the previous activation energy data and mechanism analysis.

Figure 10 ELF(a) and LOL(b) analyses of AlCl₃/ZSM-5(4T)@MIL-53(Al) catalyst

The mechanism of disproportionation of methylchlorosilane catalyzed by ZSM-5(4T)@MIL-53(Al) and AlCl₃/ZSM-5(4T)@MIL-53(Al) catalysts were investigated by using DFT:

(1) The theoretical calculation and analysis of the disproportionation reaction catalyzed by ZSM-5(4T)@MIL-53(Al) catalyst was systematically studied. The results showed that the active sites 1, 3, 4 and 5 were little conducive to the synthesis of the target product (CH₃)₂SiCl₂. Only, the No. 2 active site was slightly beneficial to the synthesis of (CH₃)₂SiCl₂.

(2) The activation energies of the rate-determining steps in the main and side reactions catalyzed by AlCl₃/ZSM-5(4T)@MIL-53(Al) catalyst were 86.92 kJ•mol^− 1 and 137.94 kJ• mol^− 1, respectively.

(3) AlCl₃/ZSM-5(4T)@MIL-53(Al) catalyst modified by AlCl₃ showed stronger disproportionation activity of methylchlorosilane in comparison with the untreated ZSM-5(4T)@MIL-53(Al) catalyst, which was more conducive to the disproportionation synthesis of the target product (CH₃)₂SiCl₂. The active site Al^&-Cl^& bond was not only relatively stable but also showed robust outer electron delocalization and obvious Lewis acidic characteristics.

Authors contribution Wenyuan Xu: conceptualization, methodology, and funding acquisition. Hongkun Huang: validation, formal analysis, and writing-original draft. Mengsha Shen: visualization. Junjie Fan: nvestigation. Yu Xu: investigation. Siqi Liu: investigation. Yan Wang: figure enhancement. Xi Chen: data curation. Mengyin Liao: writing-review and editing. Shaoming Yang: project administration.

Funding This work was supported by the National Natural Science Foundation of China (Nos. 22162010 and 21872049).

Code availability Supported by the Gaussian software package of Professor Hong Sanguo.

Data availability The datasets generated during and/or analyzed during the current study are not publicly available because it involves the completion of the national fund project, and the follow-up research will be further studied based on the above data. However, those are available from the corresponding author on reasonable request.

Conflict of interest the authors declare no competing interests.

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DFT study on the disproportionation of methylchlorosilane catalyzed by AlCl3/ZSM-5(4T)@MIL-53(Al) core-shell catalyst

Status:

Version 1

Abstract

Figures

1 Introduction

2 Calculation Method And Structural Model

2.1 Calculation method

2.2. Structural model

3 Results And Discussion

3.1 ZSM-5(4T)@MIL-53(Al) core-shell catalyst

3.2 AlCl₃/ZSM–5(4T)@MIL-53(Al) catalyst

4 Conclusion

Declarations

References

Supplementary Files

Status:

Version 1

DFT study on the disproportionation of methylchlorosilane catalyzed by AlCl3/ZSM-5(4T)@MIL-53(Al) core-shell catalyst

Status:

Version 1

Abstract

Figures

1 Introduction

2 Calculation Method And Structural Model

2.1 Calculation method

2.2. Structural model

3 Results And Discussion

3.1 ZSM-5(4T)@MIL-53(Al) core-shell catalyst

3.2 AlCl3/ZSM–5(4T)@MIL-53(Al) catalyst

4 Conclusion

Declarations

References

Supplementary Files

Status:

Version 1

3.2 AlCl₃/ZSM–5(4T)@MIL-53(Al) catalyst