Controlled preparation and application of glutathione capped gold and platinum alloy nanoclusters with high peroxidase-like activity

doi:10.1016/j.jmst.2021.08.074

Abstract

Abstract:

In the present study, we have prepared glutathione capped gold and platinum alloy nanoclusters (Au-PtNCs) in a controlled way by employing the hydrothermal method and optimized through adjusting the ratio of raw materials, reaction temperature, and time. Compared with the corresponding monometallic gold and platinum nanoclusters, the alloy nanoclusters' catalytic activity is improved dramatically in the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H₂O₂. And the maximum velocity is calculated to be 106 × 10^-8 M · s^-1 for TMB as substrate, being much better than that of other reported metallic nanoclusters and nanoparticles. Further study shows that the high catalytic activity mainly attributes to the synergistic effect of gold and platinum. Besides, they have been applied to determine H₂O₂ in the presence of TMB, which shows high sensitivity with a limit of detection (LOD) at 100 nM. The proposed method has been used to determine H₂O₂ in milk and contact lens solutions, which shows very good recovery and exhibits high practical application potential. Therefore, the present study provides a new type of alloy nanoclusters with high peroxidase-like activity, which will inspire more research interests on doping and alloying with Pt to improve the catalytic activity of metal nanoclusters.

Key words: Alloy nanoclusters, Hydrothermal method, Catalytic activity, Synergistic effect, Platinum

Yan-Cai Gao, Chong Wang, Chun-Xia Zhang, Hong-Wei Li, Yuqing Wu. Controlled preparation and application of glutathione capped gold and platinum alloy nanoclusters with high peroxidase-like activity[J]. J. Mater. Sci. Technol., 2022, 109: 140-146.

Figures/Tables 5

Fig. 1. (A) Time-dependent UV-visible absorption spectra of TMB and H2O2 in the presence of Au-PtNCs1 (10 μg·mL-1). (B) Typical absorbance changes of 1.0 mM TMB at 652 nm in the absence (green) and presence of 10 μg·mL-1 Au-PtNCs1 (Black), 30 mM H2O2 (Blue), and both of 10 μg·mL-1 AuNCs and 30 mM H2O2 (Red), respectively. (C) Typical absorbance changes of 1.0 mM TMB at 652 nm in the presence of different amount of Au-PtNCs1 (0, 5, 10, 15, 20, 30 μg·mL-1). (D) The corresponding catalytic activity changes of C. (The concentrations of TMB and H2O2 are 1.0 and 30 mM, respectively).

Fig. 2. Steady-state kinetic analysis of the Au-PtNCs2 (10 μg∙mL-1) in the presence of 30 mM H2O2 and different concentrations of TMB, respectively.

Scheme 1. Schematic illustration of Au-PtNCs as an optimal catalyst for the oxidation of TMB in the presence of H2O2.

Fig. 3. (A) UV-visible absorption spectra of Au-PtNCs in aqueous solution. (B) Typical TEM image of Au-PtNCs with the strong catalytic ability (Inset is the enlarged image and the statistic size distributions). (C, D) The XPS spectra of gold and platinum in Au-PtNCs, respectively.

Table 1. Parameters for the application of Au-PtNCs2 (10 μg·mL-1) and TMB (1.0 mM) and potassium permanganate titration to the determination of H2O2 in milk (No. 1-3) and contact lens solutions (No. 4-6).

No.	Detected (μM)	Added (μM)	TMB- Au-PtNCs2 system			Potassium permanganate titration
No.	Detected (μM)	Added (μM)	Found (μM)	RSD (n = 3,%)	Recovery (%)	Found (μM)	RSD (n = 3,%)	Recovery (%)
1	< 0.10	30	29.3 ± 0.41	1.4	97.67	28.8 ± 0.98	3.4	96.0
2	< 0.10	60	60.8 ± 1.40	2.3	101.33	58.1 ± 2.50	4.3	98.83
3	< 0.10	80	81.1 ± 1.46	1.8	101.38	78.4 ± 3.06	3.9	98.0
4	< 0.10	30	30.4 ± 0.64	2.1	101.33	28.9 ± 1.21	4.2	96.33
5	< 0.10	60	60.9 ± 1.34	2.2	101.50	58.4 ± 1.87	3.2	97.33
6	< 0.10	80	79.1 ± 1.90	2.4	98.88	78.7 ± 1.42	1.8	98.38

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