CIESC Journal ›› 2020, Vol. 71 ›› Issue (8): 3625-3632.DOI: 10.11949/0438-1157.20200357
• Catalysis, kinetics and reactors • Previous Articles Next Articles
Zhipeng LI(),Shengli NIU(),Kuihua HAN,Chunmei LU
Received:
2020-04-07
Revised:
2020-05-07
Online:
2020-08-05
Published:
2020-08-05
Contact:
Shengli NIU
通讯作者:
牛胜利
作者简介:
厉志鹏(1995—),男,硕士研究生,基金资助:
CLC Number:
Zhipeng LI, Shengli NIU, Kuihua HAN, Chunmei LU. Molecular simulation of the effect of doping modification on the adsorption properties of calcium-aluminum-based composites ester exchange catalysts[J]. CIESC Journal, 2020, 71(8): 3625-3632.
厉志鹏, 牛胜利, 韩奎华, 路春美. 掺杂改性对钙铝基复合物酯交换催化剂吸附性能影响的分子模拟[J]. 化工学报, 2020, 71(8): 3625-3632.
分子 | 键 | 键长/ nm | |
---|---|---|---|
本文 | 文献[ | ||
甲醇 | O—H | 0.097 | 0.096 |
C—O | 0.143 | 0.143 | |
C—H1/2/3 | 0.109/0.110/0.110 | 0.110/0.110/0.110 | |
乙酸甲酯 | C—O1/2 | 0.144/0.136 | 0.143/0.136 |
C—C | 0.150 | 0.150 | |
CO | 0.122 | 0.122 | |
C—H1/2/3 | 0.109/0.109/0.109 | 0.109/0.109/0.109 | |
C—H4/5/6 | 0.109/0.110/0.110 | 0.109/0.109/0.109 |
Table 1 Bond length of methanol and methyl acetate
分子 | 键 | 键长/ nm | |
---|---|---|---|
本文 | 文献[ | ||
甲醇 | O—H | 0.097 | 0.096 |
C—O | 0.143 | 0.143 | |
C—H1/2/3 | 0.109/0.110/0.110 | 0.110/0.110/0.110 | |
乙酸甲酯 | C—O1/2 | 0.144/0.136 | 0.143/0.136 |
C—C | 0.150 | 0.150 | |
CO | 0.122 | 0.122 | |
C—H1/2/3 | 0.109/0.109/0.109 | 0.109/0.109/0.109 | |
C—H4/5/6 | 0.109/0.110/0.110 | 0.109/0.109/0.109 |
掺杂方式 | 掺杂结合能(kJ/mol) | |||
---|---|---|---|---|
Ca, M=0 | Ca, M=Zn | Ca, M=La | Ca, M=Mg | |
Ca 取代 Al3c-1, M 取代 Al5c-1 | 215.03 215.03 | 969.33 | 151.23 | 652.17 |
Ca 取代 Al3c-1, M 取代 Al4c-1 | 982.20 | 284.34 | 688.67 | |
Ca 取代 Al4c-1, M 取代 Al3c-1 | 294.06 294.06 | 1037.07 | 310.07 | 728.05 |
Ca 取代 Al4c-1, M 取代 Al5c-1 | 893.98 | 228.42 | 721.49 | |
Ca 取代 Al5c-1, M 取代 Al4c-1 | 214.50 214.50 | 970.12 | 242.60 | 676.59 |
Ca 取代 Al5c-1, M 取代 Al3c-1 | 960.15 | 213.98 | 643.25 |
Table 2 Dopant incorporation energy of catalysts surface under different conditions
掺杂方式 | 掺杂结合能(kJ/mol) | |||
---|---|---|---|---|
Ca, M=0 | Ca, M=Zn | Ca, M=La | Ca, M=Mg | |
Ca 取代 Al3c-1, M 取代 Al5c-1 | 215.03 215.03 | 969.33 | 151.23 | 652.17 |
Ca 取代 Al3c-1, M 取代 Al4c-1 | 982.20 | 284.34 | 688.67 | |
Ca 取代 Al4c-1, M 取代 Al3c-1 | 294.06 294.06 | 1037.07 | 310.07 | 728.05 |
Ca 取代 Al4c-1, M 取代 Al5c-1 | 893.98 | 228.42 | 721.49 | |
Ca 取代 Al5c-1, M 取代 Al4c-1 | 214.50 214.50 | 970.12 | 242.60 | 676.59 |
Ca 取代 Al5c-1, M 取代 Al3c-1 | 960.15 | 213.98 | 643.25 |
Fig.3 Top view of doped catalyst structure surfaces (O atoms are red, Al atoms are pink, Ca atoms are green, Mg atoms are yellow, Zn atoms are black and La atoms are blue)
吸附位置 | H—O键长/nm | H—M键长/nm | 吸附能/ (kJ/mol) |
---|---|---|---|
钙催化剂表面 | 0.140 | 0.107 | -137.051 |
钙锌催化剂表面 | 0.151 | 0.103 | -164.094 |
钙镧催化剂表面 | 0.149 | 0.104 | -136.001 |
钙镁催化剂表面 | 0.148 | 0.105 | -158.318 |
Table 3 Bond length and adsorption energy of methanol absorbed on catalyst surfaces
吸附位置 | H—O键长/nm | H—M键长/nm | 吸附能/ (kJ/mol) |
---|---|---|---|
钙催化剂表面 | 0.140 | 0.107 | -137.051 |
钙锌催化剂表面 | 0.151 | 0.103 | -164.094 |
钙镧催化剂表面 | 0.149 | 0.104 | -136.001 |
钙镁催化剂表面 | 0.148 | 0.105 | -158.318 |
吸附位置 | CO键长/nm | 吸附能/(kJ/mol) |
---|---|---|
钙催化剂表面 | 0.123 | -120.640 |
钙锌催化剂表面 | 0.123 | -135.102 |
钙镧催化剂表面 | 0.128 | -149.694 |
钙镁催化剂表面 | 0.122 | -100.801 |
Table 4 Bond length and adsorption energy of methyl acetate absorbed on Ca-M catalyst surfaces
吸附位置 | CO键长/nm | 吸附能/(kJ/mol) |
---|---|---|
钙催化剂表面 | 0.123 | -120.640 |
钙锌催化剂表面 | 0.123 | -135.102 |
钙镧催化剂表面 | 0.128 | -149.694 |
钙镁催化剂表面 | 0.122 | -100.801 |
吸附位置 | H—O键长/nm | 吸附能/(kJ/mol) |
---|---|---|
钙铝催化剂表面 | 0.097 | -105.020 |
钙铝锌催化剂表面 | 0.098 | -122.873 |
钙铝镧催化剂表面 | 0.098 | -147.816 |
钙铝镁催化剂表面 | 0.098 | -259.662 |
Table 5 Bond length and adsorption energy of methanol absorbed on Ca-Al-M catalyst surfaces
吸附位置 | H—O键长/nm | 吸附能/(kJ/mol) |
---|---|---|
钙铝催化剂表面 | 0.097 | -105.020 |
钙铝锌催化剂表面 | 0.098 | -122.873 |
钙铝镧催化剂表面 | 0.098 | -147.816 |
钙铝镁催化剂表面 | 0.098 | -259.662 |
吸附位置 | Mulliken电荷/e | ||||||
---|---|---|---|---|---|---|---|
H(O-H) | O | C | H1 | H2 | H3 | 总计 | |
纯甲醇 | 0.253 | -0.507 | 0.145 | 0.029 | 0.029 | 0.050 | 0 |
钙铝催化剂表面 | 0.327 | -0.601 | -0.018 | 0.105 | 0.115 | 0.119 | 0.047 |
钙铝锌催化剂表面 | 0.379 | -0.623 | -0.029 | 0.100 | 0.110 | 0.126 | 0.063 |
钙铝镧催化剂表面 | 0.405 | -0.635 | -0.024 | 0.108 | 0.113 | 0.124 | 0.091 |
钙铝镁催化剂表面 | 0.353 | -0.596 | -0.051 | 0.111 | 0.115 | 0.121 | 0.053 |
Table 6 Mulliken atomic charge populations for methanol adsorption on Ca-Al-M catalyst surfaces
吸附位置 | Mulliken电荷/e | ||||||
---|---|---|---|---|---|---|---|
H(O-H) | O | C | H1 | H2 | H3 | 总计 | |
纯甲醇 | 0.253 | -0.507 | 0.145 | 0.029 | 0.029 | 0.050 | 0 |
钙铝催化剂表面 | 0.327 | -0.601 | -0.018 | 0.105 | 0.115 | 0.119 | 0.047 |
钙铝锌催化剂表面 | 0.379 | -0.623 | -0.029 | 0.100 | 0.110 | 0.126 | 0.063 |
钙铝镧催化剂表面 | 0.405 | -0.635 | -0.024 | 0.108 | 0.113 | 0.124 | 0.091 |
钙铝镁催化剂表面 | 0.353 | -0.596 | -0.051 | 0.111 | 0.115 | 0.121 | 0.053 |
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