化工学报 ›› 2021, Vol. 72 ›› Issue (3): 1382-1391.DOI: 10.11949/0438-1157.20200876
张芳芳1(),韩敏1,赵娟1,凌丽霞1(),章日光2,王宝俊2
收稿日期:
2020-07-03
修回日期:
2020-09-03
出版日期:
2021-03-05
发布日期:
2021-03-05
通讯作者:
凌丽霞
作者简介:
张芳芳(1993—),女,硕士研究生,基金资助:
ZHANG Fangfang1(),HAN Min1,ZHAO Juan1,LING Lixia1(),ZHANG Riguang2,WANG Baojun2
Received:
2020-07-03
Revised:
2020-09-03
Online:
2021-03-05
Published:
2021-03-05
Contact:
LING Lixia
摘要:
采用密度泛函理论(DFT)方法对单空缺石墨烯负载的Pd单原子(Pd/SVG)催化剂上H2还原NO的反应进行了研究,探究了Pd/SVG上NO还原生成N2和NH3的路径。在Pd/SVG上NO容易加氢形成HNO,需要的活化能为67.0 kJ·mol-1,显示了极高的催化活性。N2生成的有利路径为NO活化生成HNO后,HNO继续加氢生成中间体NH2O和NH2OH,然后NH2OH解离生成NH2和OH,生成的NH2中间体结合NO形成NH2NO,然后NH2NO异构化形成的NHNOH再经解离生成N2与H2O,这个过程中的决速步骤为NH2NO分子内氢转移生成NHNOH,能垒为144.3 kJ·mol-1。对于NH3的生成,从NO的活化到中间体NH2的形成与N2的形成过程相同,最后NH2加氢即可形成NH3,这个过程中的决速步骤为NH2O加氢生成NH2OH,能垒为86.4 kJ·mol-1。比较生成N2和NH3的决速步能垒可见,Pd/SVG催化剂上NO经H2还原更容易形成NH3。本研究为石墨烯负载型Pd基催化剂上H2还原NO的实验及工业应用提供理论参考。
中图分类号:
张芳芳, 韩敏, 赵娟, 凌丽霞, 章日光, 王宝俊. 单空缺石墨烯负载的Pd单原子催化剂上NO还原的密度泛函理论研究[J]. 化工学报, 2021, 72(3): 1382-1391.
ZHANG Fangfang, HAN Min, ZHAO Juan, LING Lixia, ZHANG Riguang, WANG Baojun. DFT study on reduction of NO over Pd atom anchored on single-vacancy graphene[J]. CIESC Journal, 2021, 72(3): 1382-1391.
图2 Pd/SVG上NO的活化势能图和对应的反应物、过渡态以及产物的构型
Fig.2 Potential energy diagram of NO activation with corresponding configurations of initial states, transition states and final states
Reaction | H | H′ | H″ | N | O | Q(H+N+O) |
---|---|---|---|---|---|---|
NON+O | -0.254 | -0.451 | -0.705 | |||
NO+HNOH | 0.298 | -0.164 | -0.306 | -0.172 | ||
NO+HHNO | -0.023 | -0.012 | -0.15 | -0.185 | ||
HNONH+O | 0.216 | -0.424 | -0.466 | -0.674 | ||
HNO+HNHOH | -0.138 | 0.196 | -0.011 | -0.298 | -0.251 | |
HNO+HNH2O | 0.037 | 0.203 | -0.1 | -0.384 | -0.244 | |
NH2ONH2+O | 0.203 | 0.198 | -0.516 | -0.512 | -0.627 | |
NH2ON+H2O | 0.338 | 0.264 | -0.505 | -0.574 | -0.477 | |
NH2O+HNH2OH | 0.093 | 0.229 | 0.244 | -0.127 | -0.461 | -0.022 |
表1 各基元反应过渡态结构中吸附物种各原子的Mulliken电荷以及整个吸附物种的电荷
Table 1 The Mulliken charge of each atom of the adsorbed species in the transition state structure of each elementary reaction and the charge of the entire adsorbed species
Reaction | H | H′ | H″ | N | O | Q(H+N+O) |
---|---|---|---|---|---|---|
NON+O | -0.254 | -0.451 | -0.705 | |||
NO+HNOH | 0.298 | -0.164 | -0.306 | -0.172 | ||
NO+HHNO | -0.023 | -0.012 | -0.15 | -0.185 | ||
HNONH+O | 0.216 | -0.424 | -0.466 | -0.674 | ||
HNO+HNHOH | -0.138 | 0.196 | -0.011 | -0.298 | -0.251 | |
HNO+HNH2O | 0.037 | 0.203 | -0.1 | -0.384 | -0.244 | |
NH2ONH2+O | 0.203 | 0.198 | -0.516 | -0.512 | -0.627 | |
NH2ON+H2O | 0.338 | 0.264 | -0.505 | -0.574 | -0.477 | |
NH2O+HNH2OH | 0.093 | 0.229 | 0.244 | -0.127 | -0.461 | -0.022 |
图3 Pd/SVG上NO还原的相关中间体解离加氢的势能图和对应的反应物、过渡态以及产物的构型
Fig.3 Potential energy diagram of related intermediates in the reduction of NO together with corresponding configurations of initial states, transition states and final states
图4 N2与H2O生成势能图及对应的反应物、过渡态及产物构型
Fig.4 Potential energy diagram of correlated reactions of the formation of N2 and H2O together with corresponding configurations of initial states, transition states and final states
图5 NH3生成的势能图及对应的反应物、过渡态、产物的构型
Fig. 5 Potential energy diagram of correlated reactions of the formation of NH3 together with corresponding configurations of initial states, transition states and final states
图6 N2与NH3生成的最优路径图及每一步基元反应的能垒(kJ·mol-1)和对应过渡态的虚频(cm-1)
Fig.6 The formation pathways of N2 and NH3 and the energy barrier (kJ·mol-1) for each elementary step and virtual frequency corresponding to the transition state(cm-1)
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