Direct Z-Scheme Tannin–TiO2 Heterostructure for Photocatalytic Gold Ion Recovery from Electronic Waste

K. R. Kim, S. Choi, C. T. Yavuz, Y. S. Nam*
ACS Sustain. Chem. Eng., 8, 19, 7359–7370 (2020).
DOI: 10.1021/acsaem.0c00539

Precious-metal recovery from industrial wastewater has received considerable attention because of rapidly increasing amounts of electronic waste. Existing technologies have yet to be widely applied due to their high cost and low selectivity toward precious-metal ions. Herein, we report a direct Z-scheme tannin–TiO2 heterostructure for selective gold adsorption from electronic waste under solar irradiation. The tannin-coated TiO2 nanoparticles were prepared by a simple dipping method, and under light illumination, both tannin and TiO2 can serve as photosensitive components for the reduction of metal ions, with metal-to-ligand charge transfer from TiO2 to tannin extending the lifetime of the excited electrons. Moreover, no additional electron donors are required because the tannin layer scavenges the reactive oxygen species generated by the holes from the light-activated TiO2 surface. The heterostructure allows for the highly efficient photocatalytic recovery of gold ions, with 11 times higher adsorption capacity in the light compared to the dark. High selectivity toward gold ions was also demonstrated using a metal ion mixture including nine different metal ions that are commonly found in electronic waste. Our findings suggest that the Z-scheme heterostructure of polyphenol and semiconductor provides a promising photochemical pathway for efficient and selective metal ion recovery from electronic waste.
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Photochemically-enhanced Selective Adsorption of Gold Ions on Tannin-coated Porous Polymer Microspheres

J. Kim, K. R. Kim, Y. Hong, S. Choi, C. T. Yavuz, J. W. Kim*, Y. S. Nam*
ACS Appl. Mater. Interfaces, 11, 24, 21915-21925 (2019).
DOI: 10.1021/acsami.9b05197

Metal recovery from electronic waste and industrial wastewater has attracted increasing attention to recycle precious metals and inhibit the emission of hazardous heavy metals. However, the selective recovery of precious metals with a large quantity is still very challenging because wastewater contains a variety of different cations while precious metal ions are relatively scarce. Here, we introduce a simple method to selectively increase the adsorption of gold ions using tannin-coated porous polymer microspheres through photochemical reduction. Mesoporous poly(ethylene glycol dimethacrylate-co-acrylonitrile) microspheres with an average pore diameter of 13.8 nm were synthesized and used as an adsorbent matrix. Tannic acid (TA) was deposited onto the internal pores of the polymer matrix by simple immersion in an aqueous milieu. TA coatings increased the maximum number of adsorbed gold ions by 1.3 times because of the well-known metal ion chelation of TA. Under light illumination, the maximum number of adsorbed gold ions dramatically increased by 6.1 times. We examined two distinct mechanisms presumably involved in the enhanced adsorption: the photooxidation of TA and plasmon-induced hot electrons. Moreover, TA-coated microspheres exhibited remarkable selectivity for gold ions among competing metal ions commonly found in waste resources. This work suggests that the photochemically activated TA can serve as an excellent adsorbent for the selective and efficient recovery of gold ions from wastewater.
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