Newly-modeled graphene-based ternary nanocomposite for the magnetophotocatalytic reduction of CO<sub>2</sub> with electrochemical performance

doi:10.1007/s11705-022-2166-y

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (10) : 1438-1459 https://doi.org/10.1007/s11705-022-2166-y

RESEARCH ARTICLE

Newly-modeled graphene-based ternary nanocomposite for the magnetophotocatalytic reduction of CO₂ with electrochemical performance

Zambaga Otgonbayar¹, Kwang Youn Cho², Chong-Hun Jung³, Won-Chun Oh^1,⁴(

)

¹. Department of Advanced Materials Science & Engineering, Hanseo University, Seosan-Si 31962, Korea
². Korea Institutes of Ceramic Engineering and Technology, Jinju-Si 660031, Korea
³. Decommissioning Technology Research Division, Korea Atomic Energy Research Institute, Daejeon 305-600, Korea
⁴. Anhui International Joint Research Center for Nano Carbon-based Materials and Environmental Health, College of Materials Science and Engineering, Anhui University of Science & Technology, Huainan 232001, China

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Abstract

The development of CO₂ into hydrocarbon fuels has emerged as a green method that could help mitigate global warning. The novel structured photocatalyst is a promising material for use in a photocatalytic and magneto-electrochemical method that fosters the reduction of CO₂ by suppressing the recombination of electron−hole pairs and effectively transferring the electrons to the surface for the chemical reaction of CO₂ reduction. In our study, we have developed a novel-structured AgCuZnS₂–graphene–TiO₂ to analyze its catalytic activity toward the selective evolution of CO₂. The selectivity of each nanocomposite substantially enhanced the activity of the AgCuZnS₂–graphene–TiO₂ ternary nanocomposite due to the successful interaction, and the selectivity of the final product was improved to a value 3 times higher than that of the pure AgCuZnS₂ and 2 times higher than those of AgCuZnS₂–graphene and AgCuZnS₂–TiO₂ under ultra-violet (UV)-light (λ = 254 nm) irradiation in the photocatalytic process. The electrochemical CO₂ reduction test was also conducted to analyze the efficacy of the AgCuZnS₂–graphene–TiO₂ when used as a working electrode in laboratory electrochemical cells. The electrochemical process was conducted under different experimental conditions, such as various scan rates (mV·s^–1), under UV-light and with a 0.07 T magnetic-core. The evolution of CO₂ substantially improved under UV-light (λ = 254 nm) and with 0.07 T magnetic-core treatment; these improvements were attributed to the facts that the UV-light activated the electron-transfer pathway and the magnetic core controlled the pathway of electron-transmission/prevention to protect it from chaotic electron movement. Among all tested nanocomposites, AgCuZnS₂–graphene–TiO₂ absorbed the CO₂ most strongly and showed the best ability to transfer the electron to reduce the CO₂ to methanol. We believe that our newly-modeled ternary nanocomposite opens up new opportunities for the evolution of CO₂ to methanol through an electrochemical and photocatalytic process.

Keywords ternary nanocomposite photocatalytic electrochemical CO₂ reduction UV-light magnetic core

Corresponding Author(s): Won-Chun Oh

About author:

Tongcan Cui and Yizhe Hou contributed equally to this work.

Online First Date: 30 June 2022 Issue Date: 17 October 2022

Cite this article:

Zambaga Otgonbayar,Kwang Youn Cho,Chong-Hun Jung, et al. Newly-modeled graphene-based ternary nanocomposite for the magnetophotocatalytic reduction of CO₂ with electrochemical performance[J]. Front. Chem. Sci. Eng., 2022, 16(10): 1438-1459.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2166-y
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I10/1438

Fig.1

Fig.2 (a) XRD pattern; (b) FTIR spectra; (c) photoluminescence (PL) spectra; (d) electrochemical impedance spectroscopy (EIS); (e) photocurrent; (f) quantum efficiency (η) value of the electrode; (g) reflectance spectra; (h) diffuse reflection spectroscopy (DRS); (i) Mott–Schottky plots; (j) Raman of AgCuZnS₂, AgCuZnS₂–graphene, AgCuZnS₂–TiO₂, AgCuZnS₂–graphene–TiO₂ nanocomposite.

Tab.1 The bandgap and the positions of the CB and VB

Fig.3 (a–c) TEM images, (d–f) SEM images, (g) EDX analysis result of the AgCuZnS₂, AgCuZnS₂–graphene, AgCuZnS₂–graphene–TiO₂ nanocomposite.

Fig.4 (a, b) HRTEM images, (c–f) particle size histogram of the AgCuZnS₂, AgCuZnS₂–graphene, AgCuZnS₂–graphene–TiO₂, AgCuZnS₂–TiO₂ nanocomposite.

Fig.5 (a) XPS survey spectra and the high-resolution XPS spectra of AgCuZnS₂–graphene–TiO₂, (b) Ag3d, (c) Cu2p, (d) Zn2p, (e) S2p, (f) C1s, (g) Ti2p, (h) O1s.

Fig.6 Photocatalytic CO₂R to methanol on as-prepared AgCuZnS₂, AgCuZnS₂–graphene, AgCuZnS₂–graphene–TiO₂, AgCuZnS₂–TiO₂ nanocomposite. (a) Scavenger effect under the UV-light irradiation (λ = 254 nm) for 48 h and (b) stability test under the UV-light irradiation (λ = 254 nm) for 288 h.

Fig.7 TOC analysis result of the methanol from photocatalytic CO₂R on AgCuZnS₂–graphene–TiO₂.

Fig.8 CV test of (a) AgCuZnS₂, (b) AgCuZnS₂–graphene, (c) AgCuZnS₂–graphene-TiO₂, (d) AgCuZnS₂–TiO₂ electrode in 0.04 mol·L^–1 NaHCO₃ electrolyte (–1.0 to 0.9 V vs Ag/AgCl) under different scan rates (10, 80, 100 mV·s^–1).

Fig.9 CV test of (a) AgCuZnS₂, (b) AgCuZnS₂–graphene, (c) AgCuZnS₂–graphene–TiO₂, (d) AgCuZnS₂–TiO₂ electrode in CO₂ electrolysis to methanol (–1.0 to 1.5 V vs Ag/AgCl) under different scan rates (10, 80, 100 mV·s^–1).

Fig.10 CV test of AgCuZnS₂, AgCuZnS₂–graphene, AgCuZnS₂–graphene–TiO₂, AgCuZnS₂–TiO₂ nanocomposite in CO₂ electrolysis to methanol under the UV-light irradiation (λ = 254 nm) and 0.07 T magnetic core (–1.0 to 1.5 V vs Ag/AgCl) under 100 mV·s^–1 scan rate.

Scheme1 Schematic representation of charge carrier dynamics in electrochemical CO₂R in 0.04 mol·L^–1 NaHCO₃ electrolyte.

Fig.11 Faradaic efficiency of the formed reduction product: (a) with 0.07 T magnetic core, (b) under the UV-light (λ = 254 nm) irradiation, (c) 100 mV·s^–1 scan rate, (d) 80 mV·s^–1 scan rate, and (e) 10 mV·s^–1 scan rate.

Tab.2 The functional group of the methanol (photocatalytic and electrochemical) from FTIR analysis

Scheme2 Schematic illustration of the (a) photocatalytic CO₂R with Z-scheme mechanism, (b) electrochemical CO₂ reduction, experiment setup with electrode preparation (by Doctor. Blade method).

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