Metal-free nanozymes are designed to function as peroxidase or catalase, controllable by pH conditions. Using first-principles density functional theory (DFT) calculations, we propose that heteroatomic doping of N and B to fullerene is promising to form active sites for catalyzing oxygenate intermediates for H2O2 decomposition. In neutral pH with bare surfaces, both N- and B-doped fullerenes show peroxidase-like catalytic activity rather than a catalase-like one. The presence of water, at neutral pH, drives peroxidase-like catalysis on the B-doped fullerene with marginal energy, in which the B atom functions as a strong electrophile that firmly adsorbs OH* and promotes O-O chemical bond dissociation. Interestingly, acidic, and basic environments tune their selectivity toward peroxidase- and catalase-like catalytic activity, respectively, mediated by pre-adsorbed H* and OH*. The DFT calculations demonstrate the applicability of N- and B-doped fullerenes by showing significantly decreased dissociation energy barriers of H2O2 into 2OH during the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). We believe that the results can provide a useful guide for designing highly active and selective carbon-based nanozymes toward H2O2 decomposition.
|Journal||Applied Surface Science|
|Publication status||Published - 2022 Oct 1|
Bibliographical noteFunding Information:
This research was supported by the Global Frontier Program through the Global Frontier Hybrid Interface Materials (GFHIM) of National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (Project No. 2013M3A6B1078882), and Creative Materials Discovery Program through the NRF funded by the Ministry of Science and ICT (Project No. 2021M3D1A102240823). This work was also supported by the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government (MOTIE) (20214000000090, Fostering human resources training in advanced hydrogen energy industry)
© 2022 Elsevier B.V.
All Science Journal Classification (ASJC) codes
- Condensed Matter Physics
- Physics and Astronomy(all)
- Surfaces and Interfaces
- Surfaces, Coatings and Films