Hadsadee Sarinya, Jungsuttiwong Siriporn, Zhang Rui-Qin, Rungrotmongkol Thanyada
Center of Excellence in Biocatalyst and Sustainable Biotechnology, Department of Biochemistry, Faculty of Science, Chulalongkorn University, Bangkok, 10330, Thailand.
Department of Chemistry and Center of Excellence for Innovation in Chemistry, Ubon Ratchathani University, Ubon Ratchathani, 34190, Thailand.
Sci Rep. 2022 Jun 21;12(1):10439. doi: 10.1038/s41598-022-14286-8.
P and N co-doped graphene (PNC-G with x = 1, 2, 3 and y = 0, 1, 2) is designed to enhance graphene reactivity with a synergistic effect of the P and N atoms for the CO oxidation reaction, focusing on the influence of the N dopant concentration on graphene. The calculated results indicate that increasing two or three coordinated N to P can facilitate charge transfer from the surface onto O molecules. However, the adsorbed O molecule breaks apart on PN-G surface, affecting CO oxidation performance. Furthermore, PNC-G exhibits excellent catalytic activity towards the oxidation of CO via the ER mechanism, which catalyzes CO oxidation with the rate-determining step of only 0.26 eV for the first and 0.25 eV for the second oxidation at 0 K. Additionally, the catalytic oxidation of PNC-G via Eley-Rideal mechanism prefers to occur at room temperature (298.15 K), with a rate-determining step of 0.77 eV. The reaction rates at 298.15 K is calculated to be 5.36 × 10 mol s. The rate constants are obtained according to harmonic transition state theory, which could be supportive for catalytic oxidation of CO on the experiment.
设计了P和N共掺杂的石墨烯（PNC-G，x = 1、2、3且y = 0、1、2），以通过P和N原子的协同效应增强石墨烯对CO氧化反应的反应活性，重点研究N掺杂浓度对石墨烯的影响。计算结果表明，增加二配位或三配位的N相对于P可促进电荷从表面转移到O分子上。然而，吸附在PN-G表面的O分子会分解，影响CO氧化性能。此外，PNC-G通过Eley-Rideal（ER）机制对CO氧化表现出优异的催化活性，在0 K时，其催化CO氧化的速率决定步骤对于第一次氧化仅为0.26 eV，对于第二次氧化为0.25 eV。此外，PNC-G通过Eley-Rideal机制的催化氧化更倾向于在室温（298.15 K）下发生，速率决定步骤为0.77 eV。计算得出298.15 K时的反应速率为5.36×10 mol s。根据谐振子过渡态理论获得速率常数，这可为实验中CO的催化氧化提供支持。
