Enhancing direct hydroxylation of benzene to phenol on Fe₁/PMA single-atom catalyst: a comparative study of H₂O₂vs. O₂-assisted reactions

Bashir, Beenish1,2,3; Talib, Shamraiz Hussain4,5; Khan, Muhammad Ajmal3; Mohamed, Sharmarke4,5; Qurashi, Ahsanulhaq4,5; Xiao, Hai1,2; Li, Jun1,2,6

2024-05-01

10.1039/d4ma00238e

MATERIALS ADVANCES   影响因子和分区

2633-5409

In this study, systematic first-principles calculations were carried out to ascertain the optimal single-atom catalyst (SAC) among the 3d-transition metals (TM1 = Fe-1, Co-1, Ni-1, Cu-1, and Zn-1) anchored on a phosphomolybdic acid (PMA) cluster for efficient benzene oxidation to phenol, which is otherwise challenging at ambient temperature. Strong binding due to substantial charge transfer between Fe-1 and PMA, and the adsorption energies of H2O2 and O-2 oxidants enabled significant bonding within the Fe-1/PMA cluster, facilitating enhanced catalytic performance compared to that of 3d-TM1 (Co-1, Ni-1, Cu-1, and Zn-1). The Fe-1/PMA cluster demonstrated enhanced reactivity towards H2O2 supported by lower activation barriers and rate-determining steps for H2O2 (0.84 and 0.67 eV) compared to O-2 (1.02 and 0.66 eV). The spontaneous dissociation of H2O2 on Fe-1/PMA, in contrast to O-2, is a crucial step to initiate iron-oxo (Fe-1-O) active site formation, easing benzene to phenol oxidation at ambient temperature. Thus, the proficient coordination environment of Fe-1 atoms as SACs adsorbed on the PMA cluster is found to influence catalytic performance, especially in the case of H2O2. The proposed mechanism is reminiscent of hydrocarbon hydroxylation in enzymatic processes, establishing Fe-1/PMA as an environmentally friendly, heterogeneous and non-noble metal green catalyst for electrocatalytic phenol production.

ESCI

英语

通讯

National Natural Science Foundation of China["22033005","21903047"] ; National Natural Science Foundation of China[22388102] ; NSFC Center for Single-Atom Catalysis[2020B121201002]

Materials Science

Materials Science, Multidisciplinary

WOS:001229639100001

ROYAL SOC CHEMISTRY

Web of Science

1.Tsinghua Univ, Dept Chem, Minist Educ, Beijing 100084, Peoples R China
2.Tsinghua Univ, Engn Res Ctr Adv Rare Earth Mat, Minist Educ, Beijing 100084, Peoples R China
3.George Mason Univ, Dept Chem & Biochem, 4400 Univ Dr, Fairfax, VA 22030 USA
4.Khalifa Univ Sci & Technol, Ctr Catalysis & Separat, POB 127788, Abu Dhabi, U Arab Emirates
5.Khalifa Univ Sci & Technol, Dept Chem, Abu Dhabi 127788, U Arab Emirates
6.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Bashir, Beenish,Talib, Shamraiz Hussain,Khan, Muhammad Ajmal,et al. Enhancing direct hydroxylation of benzene to phenol on Fe₁/PMA single-atom catalyst: a comparative study of H₂O₂vs. O₂-assisted reactions[J]. MATERIALS ADVANCES,2024.

Bashir, Beenish.,Talib, Shamraiz Hussain.,Khan, Muhammad Ajmal.,Mohamed, Sharmarke.,Qurashi, Ahsanulhaq.,...&Li, Jun.(2024).Enhancing direct hydroxylation of benzene to phenol on Fe₁/PMA single-atom catalyst: a comparative study of H₂O₂vs. O₂-assisted reactions.MATERIALS ADVANCES.

Bashir, Beenish,et al."Enhancing direct hydroxylation of benzene to phenol on Fe₁/PMA single-atom catalyst: a comparative study of H₂O₂vs. O₂-assisted reactions".MATERIALS ADVANCES (2024).