Band engineering of Cu2+ doped In2xZn3(1−x)S3 solid solution with high photocatalytic activity for H2 production under visible light

ZnIn2S4‐Based Photocatalysts for Energy and Environmental Applications

“…Hence, with the rapid development of the modification research on ZnIn 2 S 4 photo catalyst, many researchers have endeavored to introduce metals or nonmetals into ZnIn 2 S 4 . Doping candidates include tran sitionmetal (copper (Cu), [71][72][73] molybdenum (Mo), [74,75] nickel (Ni), [76][77][78] iron (Fe), [79,80] cobalt (Co), [79,81] manganese (Mn), [79] chromium (Cr), [79] ), alkalineearth metal (calcium (Ca), stron tium (Sr), and barium (Ba)), [82] rareearth metal (lanthanum (La), cerium (Ce), gadolinium (Gd), erbium (Er) or yttrium (Y)), [83] as well as silver (Ag), [84][85][86] samarium (Sm), [87] ruthe nium (Ru), [27] oxygen (O), [40,88] and nitrogen (N), [88,89] among others (Figure 8).…”

“…In addition, a series of rare earth ions (Y 3+ , Er 3+ , Gd 3+ , Ce 3+ , or La 3+ ) doped ZnIn 2 S 4 photocatalysts was prepared by Zhu et al [83] The photocatalytic H 2 evolution performances of these prepared samples were studied, and the results showed that the H 2 evolution efficiency increased by 106%, 69%, 61%, 53%, and 46% after doping with 2.0 wt% of La 3+ , Ce 3+ , Er 3+ , Gd 3+ , and Y 3+ , respectively. In addition, some other cation doping ZnIn 2 S 4 photocatalysts have recently been reported, such as Cudoped ZnIn 2 S 4 for H 2 evolution, [71,72] Modoped ZnIn 2 S 4 for coupling of amines to imidazoles [74] and H 2 evolution, [75] Ni doped ZnIn 2 S 4 for H 2 evolution [76,78] and photoelectrochemical water splitting, [77] Fedoped ZnIn 2 S 4 for 2,4,6tribromophenol degradation, [80] Agdoped ZnIn 2 S 4 for H 2 evolution [84][85][86] Sm doped ZnIn 2 S 4 for Rhodamine B and methyl orange degra dation, [87] and Rudoped ZnIn 2 S 4 for coproduction of diesel precursors and H 2 from lignocellulosederived methylfurans. [27] Up until now, despite extensive research on the modification of ZnIn 2 S 4 photocatalyst via doping engineering, the enacted role of dopants in photocatalytic reaction remains controversial, owing to the possible existence of negative effects of dopants originating from them acting as the recombination centers for photogenerated carriers.…”

l-Cystine-assisted hydrothermal synthesis of Mn1−xCdxS solid solutions with hexagonal wurtzite structure for efficient photocatalytic hydrogen evolution under visible light irradiation

“…Especially when x ¼ 0.05-0.1, the discrete levels as mentioned above play as a trapping center for photoexcited electrons, thus decreasing the photocatalytic ability for H 2 evolution. 18,49…”

“…Designing photocatalysts by making solid solutions with tunable electronic structure has been proven to be an effective strategy to increase visible light absorption and promote the separation of photogenerated e À /h + pairs as well as the charge transport. In the past few years, a number of multi-component solid solutions, such as ZnO : GaN, 1 Cd-ZnGeON, 2 GaZnInON, 3 Zn 1+x GeO x -N 2 , 4 BaTa 1Àx Zr x O 2+x N 1Àx , 5 Na x La 1Àx TaO 1+2x N 2À2x , 6 Cd 1Àx Zn x S, 7 Zn 1Àx Cu x S, 8 Zn m In 2 S 3+m , 9 (AgIn) x Zn 2(1Àx) S 2 , 10 (CuIn) x Zn 2(1Àx) S 2 , 11 (CuIn) x Cd 2(1Àx) S 2 , 12 ZnS-In 2 S 3 -Ag 2 S, 13 ZnS-In 2 S 3 -CuS, 14 Cd 0.1 Sn x -Zn 0.9À2x S, 15 (ZnS) x (CuInS 2 ) 1Àx , 16 ZnS-CuInS 2 -AgInS 2 , 17 Cu 2+ -In 2x Zn 3(1Àx) S 3 , 18 La 2x Ga 2y In 2(1ÀxÀy) O 3 , 19 (Cu x Ag 1Àx ) 2 ZnSnS 4 , 20 In(OH) y S z : Zn, 21 Zn 1Àx Cd x In 2 S 4 , etc., [22][23][24] have been extensively studied owing to their controllable band structures and excellent performance for photocatalytic water reduction to hydrogen under visible light irradiation. Among these different solid solutions, the ternary Mn-Cd-S alloyed system, formed by combining MnS (wide band gap) and CdS (narrow band gap), has also received a great deal of attention recently because of its unusual magneto-optical properties as well as potential applications in diluted magnetic semi-conductors and especially photocatalysis.…”

Water Splitting By Photocatalytic Reduction

“…As shown in Table 6.2, the metal sulfide solid solutions doped by Cu [147,148], Ni [149,150], Ag [151], Sn [152], and Bi [153] ions have been found to exhibit higher photocatalytic activity for hydrogen production than the undoped ones. It is believed that the impurity levels in the forbidden band created by doping can enhance the visible light response and accommodate the photogenerated charge carriers, thus leading to the enhanced hydrogen evolution.…”