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. 2022 Jul 13;14(27):30796-30801.
doi: 10.1021/acsami.2c05606. Epub 2022 Jun 17.

Polythiacalixarene-Embedded Gold Nanoparticles for Visible-Light-Driven Photocatalytic CO2 Reduction

Tina Skorjanc  1   2 , Khaja Mohaideen Kamal  3 , Ayesha Alkhoori  4 , Gregor Mali  3 , Abdul Khayum Mohammed  5 , Zouhair Asfari  6 , Kyriaki Polychronopoulou  4 , Blaž Likozar  3 , Ali Trabolsi  1   7 , Dinesh Shetty  5
Affiliations

Polythiacalixarene-Embedded Gold Nanoparticles for Visible-Light-Driven Photocatalytic CO2 Reduction

Tina Skorjanc et al. ACS Appl Mater Interfaces. .

Abstract

Metal nanoparticles are potent reaction catalysts, but they tend to aggregate, thereby limiting their catalytic efficiency. Their coordination with specific functional groups within a porous structure prevents their aggregation and facilitates the mass flow of catalytic starting materials and products. Herein, we use a thiacalix[4]arene-based polymer as a porous support with abundant docking sites for Au nanoparticles. The sulfur atoms bridging the phenolic subunits of thiacalix[4]arene serve as Lewis basic sites that coordinate Au atoms. Therefore, this approach takes advantage of the functional groups inherent in the monomer and avoids laborious postsynthetic modifications of the polymer. The presented system was tested for visible-light-driven photocatalytic CO2 reduction, where it showed adequate ability to generate 6.74 μmol g-1 CO over the course of 4 h, while producing small amounts of the CH4 product. This study aims to stimulate interest in the design and development of synthetically simpler porous polymer supports for various metal nanoparticles in catalytic and other applications.

Keywords: CO2 reduction; nanoparticles; photocatalysis; porous polymers; thiacalixarene.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Design and characterization of the SCX4+ polymer. (a) Synthetic scheme for the preparation of SCX4+ and the AuNPs@SCX4+ hybrid material; (b) FT-IR spectra of the starting materials and SCX4+; (c) CP/MAS 13C NMR spectrum of SCX4+ with signals assigned in panel (a); (d) N2 adsorption isotherms for SCX4+ and AuNPs@SCX4+.
Figure 2
Figure 2
Characterization of the AuNPs@SCX4+ hybrid material. (a) Powder XRD patterns of amorphous SCX4+ and crystalline AuNPs@SCX4+; (b) the size distribution of Au NPs in the hybrid material; (c) a TEM micrograph showing a uniform distribution of Au NPs throughout the polymer network; (d) HR-TEM micrograph with fringes corresponding to the (111) plane of the Au NPs.
Figure 3
Figure 3
Photocatalytic performance. (a) Visible-light-driven CO2 reduction under various reaction conditions; (b) generation of CO and CH4 by AuNPs@SCX4+ as a function of reaction time; c) recycling tests of AuNPs@SCX4+ on evolution of CO and CH4 by photocatalytic CO2 reduction (each cycle 4 h); (d) total consumed electron number (TCEN) as functions of photocatalyst quantity.
See this image and copyright information in PMC

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