Photothermal Synergistic Catalysis over Defective Zn₃In₂S₆ for CO₂ Fixation

Abstract

Carbon dioxide (CO 2 ) cycloaddition not only produces highly valued cyclic carbonate but also utilizes CO 2 as C1 resources with 100% atomic efficiency. However, traditional catalytic routes still suffer from inferior catalytic efficiency and harsh reaction conditions. Developing multienergy-field catalytic technology with expected efficiency offers great opportunity for satisfied yield under mild conditions. Herein, Zn 3 In 2 S 6 with sulfur vacancies (S v ) was fabricated with the assistance of cetyltrimethylammonium bromide (CTAB), which is further employed for photothermally driven CO 2 cycloaddition first. Photoluminescence spectroscopy and photoelectrochemical characterization demonstrated its superior separation kinetics of photoinduced carriers induced by defect engineering. The temperature-programmed desorption (TPD) technique indicated its excellent Lewis acidity− basicity characters. Due to the combination of above merits from photocatalysis and thermal catalysis, defective Zn 3 In 2 S 6 -S v achieved a yield as high as 73.2% for cyclic carbonate at 80 °C under blue LED illumination within 2 h (apparent quantum yield of 0.468% under illumination of 380 nm monochromatic light at 36 mW•cm −2 ), which is 2.9, 2.0, and 6.9 times higher than that in dark conditions and those of pristine Zn 3 In 2 S 6 and industrial representative tetrabutylammonium bromide (TBAB) thermal-catalysis process under the same conditions, respectively. The synergistic reaction path of photocatalysis and thermal catalysis was discriminated by theoretical calculation. This work provides new insights into the photothermal synergistic catalysis CO 2 cycloaddition with defective ternary metal sulfides.

2D/2D ZIF-L-Derived Znδ+ (0 ≤ δ ≤ 2) and N Codoped Carbon Skeleton@ZnIn2S4 S-Scheme Heterojunction for Solar-Driven CO2 Cycloaddition

“…The previous research studies on photocatalytic CO 2 cycloaddition mainly focused on the utilization of light, utilizing the photothermal conversion effect of materials to thermally drive the CO 2 cycloaddition reaction. − There is still limited research on the role of photocatalysis, photogenerated electrons, and holes in cycloaddition reactions. Recently, Wu et al investigated the CO 2 cycloaddition of ZnIn 2 S 4 catalysts with highly exposed surface zinc sites under 80 °C blue light-emitting diode (LED) irradiation and proposed that photogenerated electrons will transfer to the epoxypropane molecule to form electron-rich transition states, promoting the ring opening of epoxypropane .…”

Multiobjective optimization of a g-C3N4/Cd-Zn3In2S6 heterojunction for high-efficiency photocatalytic hydrogen evolution

“…Zn 3 In 2 S 6 (ZIS), a common ternary sulfide, has been widely applied in photocatalytic hydrogen production, 19,20 photodegradation of pollutants, 21,22 and photoreduction of CO 2 23,24 due to its suitable band gap (2.2–2.6 eV), abundant active sites, and excellent chemical stability. However, pure ZIS suffers from poor photocatalytic efficiency due to its low separation rate of photogenerated carriers.…”