N- and B-doped fullerene as peroxidase- and catalase-like metal-free nanozymes with pH-switchable catalytic activity: A first-principles approach
Abstract
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.
- Publication:
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Applied Surface Science
- Pub Date:
- October 2022
- DOI:
- 10.1016/j.apsusc.2022.153715
- Bibcode:
- 2022ApSS..59853715H
- Keywords:
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- First-principles;
- Nanozymes;
- Fullerene;
- Doping;
- pH-selectivity