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In This Article

  • Summary
  • Abstract
  • Introduction
  • Protocol
  • Representative Results
  • Discussion
  • Acknowledgements
  • Materials
  • References
  • Reprints and Permissions

Summary

Presented here is a protocol for the synthesis of silver-palladium (Ag-Pd) alloy nanoparticles (NPs) supported on ZrO2 (Ag-Pd/ZrO2). This system allows for harvesting energy from visible light irradiation to accelerate and control molecular transformations. This is illustrated by nitrobenzene reduction under light irradiation catalyzed by Ag-Pd/ZrO2 NPs.

Abstract

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular transformations. This opens possibilities for the use of visible or near-IR light as a sustainable input to drive and control reactions when plasmonic nanoparticles supporting LSPR excitation in these ranges are employed as catalysts. Unfortunately, this is not the case for several catalytic metals such as palladium (Pd). One strategy to overcome this limitation is to employ bimetallic NPs containing plasmonic and catalytic metals. In this case, the LSPR excitation in the plasmonic metal can contribute to accelerate and control transformations driven by the catalytic component. The method reported herein focuses on the synthesis of bimetallic silver-palladium (Ag-Pd) NPs supported on ZrO2 (Ag-Pd/ZrO2) that acts as a plasmonic-catalytic system. The NPs were prepared by co-impregnation of corresponding metal precursors on the ZrO2 support followed by simultaneous reduction leading to the formation of bimetallic NPs directly on the ZrO2 support. The Ag-Pd/ZrO2 NPs were then used as plasmonic catalysts for the reduction of nitrobenzene under 425 nm illumination by LED lamps. Using gas chromatography (GC), the conversion and selectivity of the reduction reaction under the dark and light irradiation conditions can be monitored, demonstrating the enhanced catalytic performance and control over selectivity under LSPR excitation after alloying non-plasmonic Pd with plasmonic metal Ag. This technique can be adapted to a wide range of molecular transformations and NPs compositions, making it useful for the characterization of the plasmonic catalytic activity of different types of catalysis in terms of conversion and selectivity.

Introduction

Among the several applications of metal nanoparticles (NPs), catalysis deserves special attention. Catalysis plays a central role in a sustainable future, contributing to less energy consumption, better utilization of raw materials, and enabling cleaner reaction conditions1,2,3,4. Thus, progress in catalysis can provide tools for enhancing the atomic efficiency of chemical processes, making them cleaner, more economically viable, and more environmentally friendly. Metal NPs encompassing silver (Ag), gold (Au) or copper (Cu) can display inter....

Protocol

1. Synthesis of Ag-Pd/ZrO2 NPs

NOTE: In this procedure, the Pd mol% in Ag-Pd corresponded to 1%, and the Ag-Pd loading on ZrO2 corresponded to 3 wt.%.

  1. Place 1 g of ZrO2 powder in a 250 mL beaker.
  2. Add 50 mL of an AgNO3 (aq) (0.0059 mol/L) and 9.71 mL of a K2PdCl4 (aq) (0.00031 mol/L) solutions to the beaker under vigorous magnetic stirring (500 rpm) at room temperature.
  3. Add 10 mL .......

Representative Results

Figure 1A shows digital photographs of the solid samples containing the pure ZrO2 oxide (left) and the Ag-Pd/ZrO2 NPs (right). This change in color from white (in ZrO2) to brown (Ag-Pd/ZrO2) provides the initial qualitative evidence on the deposition of Ag-Pd NPs at the ZrO2 surface. Figure 1B shows the UV-visible absorption spectra from the Ag-Pd/ZrO2 NPs (blue trace) as well as ZrO2 (.......

Discussion

The findings described in this method demonstrate that the intrinsic catalytic activity of Pd (or other catalytic but not plasmonic metal) can be significantly enhanced by LSPR excitation via visible-light irradiation in bimetallic alloyed NPs35. In this case, Ag (or another plasmonic metal) is capable of harvesting energy from visible-light irradiation via LSPR excitation. The LSPR excitation leads to the formation of hot charge carriers (hot electrons and holes) and localized heating.......

Acknowledgements

This work was supported by the University of Helsinki and the Jane and Aatos Erkko Foundation. S.H. thanks Erasmus+ EU funds for the fellowship.

....

Materials

NameCompanyCatalog NumberComments
2-Propanol (anhydrous, 99.5%)Sigma-Aldrich278475CAS Number 67-63-0
Aniline (for synthesis)Sigma-Aldrich8.22256CAS Number 62-53-3
Azobenzene (98%)Sigma-Aldrich424633CAS Number 103-33-3
EthanolHoneywell32221CAS Number 64-17-5
Hydrochloric acid (37%)VWRPRLSMC310066CAS Number 7647-01-0
L-Lysine (crystallized, ≥98.0% (NT))Sigma-Aldrich62840CAS Number 56-87-1
Nitric acid (65%)Merck100456CAS Number 7697-37-2
NitrobenzeneSigma-Aldrich8.06770CAS Number 98-95-3
Potassium hydroxideFisher10448990CAS Number 1310-58-3
Potassium tetrachloropalladate (II) (98%)Sigma-Aldrich205796CAS Number 10025-98-6
Silver nitrate (ACS reagent, ≥99.0%)Sigma-Aldrich209139CAS Number 7761-88-8
Sodium borohydride (fine granular for synthesis)Sigma-Aldrich8.06373CAS Number 16940-66-2
Zirconium (IV) oxide (nanopowder, <100 nm particle size (TEM))Sigma-Aldrich544760CAS Number 1314-23-4

References

  1. Dunn, P. J., Hii, K. K., Krische, M. J., Williams, M. T. . Sustainable Catalysis: Challenges and Pratices for the Pharmaceutical and Fine Chemical Industries. , (2013).
  2. Tzouras, N. V., Stamatopoulos, I. K., Papastavrou, A. T., Liori, A. A., Vougioukalakis, G. C. Sustainable metal catalysis in C-H activation.....

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