TY  - JOUR
A1  - Gu, Sasa
A1  - Risse, Sebastian
A1  - Lu, Yan
A1  - Ballauff, Matthias
T1  - Mechanism of the oxidation of 3,3′,5,5′-tetramethylbenzidine catalyzed by peroxidase-like Pt nanoparticles immobilized in spherical polyelectrolyte brushes
BT  - a kinetic study
JF  - ChemPhysChem
N2  - Experimental and kinetic modelling studies are presented to investigate the mechanism of 3,3 ',5,5 '-tetramethylbenzidine (TMB) oxidation by hydrogen peroxide (H2O2) catalyzed by peroxidase-like Pt nanoparticles immobilized in spherical polyelectrolyte brushes (SPB-Pt). Due to the high stability of SPB-Pt colloidal, this reaction can be monitored precisely in situ by UV/VIS spectroscopy. The time-dependent concentration of the blue-colored oxidation product of TMB expressed by different kinetic models was used to simulate the experimental data by a genetic fitting algorithm. After falsifying the models with abundant experimental data, it is found that both H2O2 and TMB adsorb on the surface of Pt nanoparticles to react, indicating that the reaction follows the Langmuir-Hinshelwood mechanism. A true rate constant k, characterizing the rate-determining step of the reaction and which is independent on the amount of catalysts used, is obtained for the first time. Furthermore, it is found that the product adsorbes strongly on the surface of nanoparticles, thus inhibiting the reaction. The entire analysis provides a new perspective to study the catalytic mechanism and evaluate the catalytic activity of the peroxidase-like nanoparticles.
KW  - kinetics
KW  - nanoparticles
KW  - reaction mechanisms
KW  - spherical polyelectrolyte
KW  - brushes
KW  - UV
KW  - vis spectroscopy
Y1  - 2019
U6  - https://doi.org/10.1002/cphc.201901087
SN  - 1439-4235
SN  - 1439-7641
VL  - 21
IS  - 5
SP  - 450
EP  - 458
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Zhao, Yuhang
A1  - Opitz, Andreas
A1  - Eljarrat, Alberto
A1  - Kochovski, Zdravko
A1  - Koch, Christoph
A1  - Koch, Norbert
A1  - Lu, Yan
T1  - Kinetic study on the adsorption of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane on Ag nanoparticles in chloroform
BT  - implications for the charge transfer complex of Ag-F(4)TCNQ
JF  - ACS applied nano materials
N2  - In this study, the kinetics of the adsorption of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)TCNQ) on the surface of Ag nanoparticles (Ag NPs) in chloroform has been intensively investigated, as molecular doping is known to play a crucial role in organic electronic devices. Based on the results obtained from UV-visible (vis)-near-infrared (NIR) absorption spectroscopy, cryogenic transmission electron microscopy, scanning nanobeam electron diffraction, and electron energy loss spectroscopy, a two-step interaction kinetics has been proposed for the Ag NPs and F(4)TCNQ molecules, which includes the first step of electron transfer from Ag NPs to F(4)TCNQ indicated by the ionization of F(4)TCNQ and the second step of the formation of a Ag-F(4)TCNQ complex. The whole process has been followed via UV-vis-NIR absorption spectroscopy, which reveals distinct kinetics at two stages: the instantaneous ionization and the long-term complex formation. The kinetics and the influence of the molar ratio of Ag NPs/F(4)TCNQ molecules on the interaction between Ag NPs and F(4)TCNQ molecules in an organic solution are reported herein for the first time. Furthermore, the control experiment with silica-coated Ag NPs manifests that the charge transfer at the surface between Ag NPs and F(4)TCNQ molecules is prohibited by a silica layer of 18 nm.
KW  - Ag nanoparticles
KW  - F(4)TCNQ
KW  - phase transfer
KW  - kinetics
KW  - electron transfer
KW  - surface interaction
Y1  - 2021
U6  - https://doi.org/10.1021/acsanm.1c02153
SN  - 2574-0970
VL  - 4
IS  - 11
SP  - 11625
EP  - 11635
PB  - American Chemical Society
CY  - Washington
ER  -