Triazine COF-supported single-atom catalyst (Pd1/trzn-COF) for CO oxidation 三嗪-共价有机框架材料负载的单原子催化剂Pd1/trzn-COF催化CO氧化的理论研究

Chen，Yin Juan1,2; Zhuo，Hong Ying2; Pan，Yuan1; Liang，Jin Xia3; Liu，Chen Guang1; Li，Jun2,3

2021

10.1007/s40843-021-1662-8

Science China-Materials   影响因子和分区

2095-8226

2199-4501

Single-atom catalysts (SACs) with well-defined and specific single-atom dispersion on supports offer great potential for achieving both high catalytic activity and selectivity. Covalent organic frameworks (COFs) with tailor-made crystalline structures and designable atomic composition is a class of promising supports for SACs. Herein, we have studied the binding sites and stability of Pd single atoms (SAs) dispersed on triazine COF (Pd/trzn-COF) and the reaction mechanism of CO oxidation using the density functional theory (DFT). By evaluating different adsorption sites, including the nucleophilic sp C atoms, heteroatoms and the conjugated π-electrons of aromatic ring and triazine, it is found that Pd SAs can stably combine with trzn-COF with a binding energy around −5.0 eV, and there are two co-existing dynamic Pd/trzn-COFs due to the adjacent binding sites on trzn-COF. The reaction activities of CO oxidation on Pd/trzn-COF can be regulated by the anion-π interaction between a + δ phenyl center and the related −δ moieties as well as the electron-withdrawing feature of imine in the specific complexes. The Pd/trzn-COF catalyst is found to have a high catalytic activity for CO oxidation via a plausible tri-molecular Eley-Rideal (TER) reaction mechanism. This work provides insights into the d-π interaction between Pd SAs and trzn-COF, and helps to better understand and design new SACs supported on COF nanomaterials.

CO oxidation covalent organic frameworks Pd loading single-atom catalysts

EI

中文

其他

20212210416132

Atoms ; Binding energy ; Binding sites ; Catalyst activity ; Catalyst selectivity ; Catalytic oxidation ; Density functional theory ; Design for testability ; Oxidation

Precious Metals:547.1 ; Biochemistry:801.2 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Atomic and Molecular Physics:931.3

2-s2.0-85106421555

Scopus

1.State Key Laboratory of Heavy Oil Processing,College of Chemical Engineering,China University of Petroleum (East China),Qingdao,266580,China
2.Department of Chemistry,Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education,Tsinghua University,Beijing,100084,China
3.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China

Chen，Yin Juan,Zhuo，Hong Ying,Pan，Yuan,等. Triazine COF-supported single-atom catalyst (Pd1/trzn-COF) for CO oxidation 三嗪-共价有机框架材料负载的单原子催化剂Pd1/trzn-COF催化CO氧化的理论研究[J]. Science China-Materials,2021,64:1939-1951.

Chen，Yin Juan,Zhuo，Hong Ying,Pan，Yuan,Liang，Jin Xia,Liu，Chen Guang,&Li，Jun.(2021).Triazine COF-supported single-atom catalyst (Pd1/trzn-COF) for CO oxidation 三嗪-共价有机框架材料负载的单原子催化剂Pd1/trzn-COF催化CO氧化的理论研究.Science China-Materials,64,1939-1951.

Chen，Yin Juan,et al."Triazine COF-supported single-atom catalyst (Pd1/trzn-COF) for CO oxidation 三嗪-共价有机框架材料负载的单原子催化剂Pd1/trzn-COF催化CO氧化的理论研究".Science China-Materials 64(2021):1939-1951.