Dye‐Sensitized Cu₂XSnS₄ (X=Zn, Ni, Fe, Co, and Mn) Nanofibers for Efficient Photocatalytic Hydrogen Evolution

Abstract

The photocatalytic hydrogen evolution activities of low-cost and noble-metal-free Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofiber catalysts have been investigated using triethanolamine as an electron donor and eosin Y as a photosensitizer under visible-light irradiation. The rates of hydrogen evolution by Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofibers have been compared with each other and with that of the noble metal Pt. The hydrogen evolution rates for the nanofibers change in the order Cu2 NiSnS4 >Cu2 FeSnS4 >Cu2 CoSnS4 >Cu2 ZnSnS4 >Cu2 MnSnS4 (2028, 1870, 1926, 1420, and 389 μmol g(-1) h(-1) , respectively). The differences between the hydrogen evolution rates of the nanofibers could be attributed to their energy levels. Moreover, Cu2 NiSnS4, Cu2 FeSnS4 , and Cu2 CoSnS4 nanofibers show higher and more stable photocatalytic hydrogen production rates than that of the noble metal Pt under long-term irradiation with visible light.

Photocatalysis for Hydrogen Production and CO2 Reduction: The Case of Copper‐Catalysts

“…Ga incorporation replacing part of the In allowed adjusting the band gap shifting the CB edge and providing a larger driving force for catalyzing the water splitting reduction reaction . Cu 2 X SnS 4 (where X =Zn, Ni, Fe, Co, and Mn) materials have been also found active in H 2 evolution from water without the need of a co‐catalyst . The presence of Au NPs and the development Au/Cu 2 FeSnS 4 core‐shell nanostructures improved significantly H 2 production, a mechanism that was attributed to the LSPR effect induced by Au NPs …”

“…[61] Cu 2 XSnS 4 (where X = Zn, Ni, Fe, Co, and Mn) materials have been also found active in H 2 evolution from water without the need of a co-catalyst. [62] The presence of Au NPs and the development Au/Cu 2 FeSnS 4 core-shell nanostructures improved significantly H 2 production, a mechanism that was attributed to the LSPR effect induced by Au NPs. [53] 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 Copper sulfides have been also coupled with other SCs.…”

Multifunctional Copper‐Based Quaternary Chalcogenide Semiconductors Toward State‐of‐the‐Art Energy Applications

“…Gonce at el . from the same group has also investigated the photocatalytic hydrogen evolution rates of EY sensitized CM I TS (M I =Zn, Ni, Fe, Co and Mn) nanofibers under similar conditions . The hydrogen evolution rates for the nanofibers change in the order CNTS (2028 μmol g −1 h −1 ) > CCTS (1926 μmol g −1 h −1 ) > CFTS (1870 μmol g −1 h −1 ) > CZTS (1420 μmol g −1 h −1 ) >CMTS (389 μmol g −1 h −1 ).…”

Optimization of Cu2ZnSnS4 Absorber Layers via Sulfurization of Electrodeposited Cu-Zn-Sn Precursors for Photovoltaic Applications

“…Furthermore, cobalt and nickel can be co-electrodeposited from a citrate based solution owing to their suitable reduction potential in the Cu-Zn-Sn electrodeposition system as an alternative simple method to dope CZTS films [76,201,202]. Cobalt-containing Cu 2 Co x Zn 1-x SnS 4 and Cu 2 CoSnS 4 materials have been grown as nanofibers and nanorods before [198,203]; however, a low doping amount in CZTS films for the modification of CdS/CZTS band alignment has not been reported as yet. Nickel containing Cu 2 Ni x Zn 1-x SnS 4 and Cu 2 NiSnS 4 materials have been grown as a film, nanofiber and nanorods [198,199,203]; nevertheless none of these studies reported the photoelectrochemical or solar cell performance of these materials.…”

“…Cobalt-containing Cu 2 Co x Zn 1-x SnS 4 and Cu 2 CoSnS 4 materials have been grown as nanofibers and nanorods before [198,203]; however, a low doping amount in CZTS films for the modification of CdS/CZTS band alignment has not been reported as yet. Nickel containing Cu 2 Ni x Zn 1-x SnS 4 and Cu 2 NiSnS 4 materials have been grown as a film, nanofiber and nanorods [198,199,203]; nevertheless none of these studies reported the photoelectrochemical or solar cell performance of these materials. Cobalt containing CZTS films can be synthesized via sulfurization of co-electrodeposited Cu-Zn-Sn-Co metallic precursors on Mo substrate with varying compositional ratios for the optimization of band gap as well as band alignment for CdS/CZTS interface.…”