Bifunctional Cobalt‐Doped ZnIn₂S₄ Hierarchical Nanotubes Endow Noble‐Metal Cocatalyst‐Free Photocatalytic H₂ Production Coupled with Benzyl Alcohol Oxidation

Abstract

Noble metals are widely used as cocatalysts to enhance the performance of photocatalysts, while large‐scale applications of noble metals are restricted due to their scarcity and high cost. In this context, it is an urgent task to design efficient noble‐metal cocatalyst‐free photocatalysts. Herein, the rational design and self‐sacrificial template‐assisted synthesis of cobalt‐doped ZnIn2S4 hierarchical nanotubes (Co‐ZIS HNTs) are presented that can act as a bifunctional photocatalyst for H2 evolution and benzaldehyde production. Comprehensive experimental results indicate that the Co‐ZIS HNTs can lead to the enhanced separation and transfer efficiency of photoinduced carriers. As a result, the Co‐ZIS HNTs exhibit a 1.93 times higher H2 evolution rate than undoped ZnIn2S4 microspheres (ZIS MSs) without any cocatalysts. Impressively, the Co‐ZIS HNTs show remarkable bifunctial photocatalytic activity toward both H2 evolution and benzyl alcohol oxidation. The extraordinary production rates of H2 and benzaldehyde are 2823.7 and 2769.0 μmol h−1 g−1, which are 7.44 and 7.60 times higher than that of bare ZIS MSs under visible light, respectively. This work not only proposes a promising strategy to devise highly active cocatalyst‐free photocatalysts, but also illustrates the potential for H2 evolution coupled with add‐valued products.

Biosafety Photooxidation Strategy of Levofloxacin Driven by Manganese‐Doped Indium Zinc Sulfide

“…On this basis, by combining the XRD pattern and XPS results, it can be determined that Mn ions are successfully doped into ZIS. Compared with pristine ZIS (Figure S3), the binding energies of Zn 2p XPS spectra and In 3d XPS spectra shift to higher values and S 2p XPS spectra shift to a lower value for ZIS‐4% (Figure 3), indicating that the electronic structures and chemical interactions between elements in ZIS‐4% have changed after the doping of Mn [18a] . The intensity and binding energy of S 2p in ZIS‐4% are weaker and lower compared with ZIS, which is due to low‐coordination S [14b] …”

Photoreforming of polyester plastics into added-value chemicals coupled with H2 evolution over a Ni2P/ZnIn2S4 catalyst

“…35 The spectra of S 2p display two distinct single peaks at 161.7 eV (S 2p 3/2 ) and 162.9 eV (S 2p 1/2 ). 34 When ZnIn 2 S 4 was hybridized with Ni 2 P, the binding energy of the Zn 2p clearly shifted toward high energy. Similar shifts can also be observed in the In 3d and S 2p high-resolution spectra.…”

“…As for pristine ZnIn 2 S 4 , two peaks located at 1021.8 and 1044.8 eV are assigned to Zn 2p 3/2 and Zn 2p 1/2 , respectively. 34 Peaks at binding energy of 444.9 eV and 452.5 eV belong to In 3d 5/2 and In 3d 3/2 , respectively. 35 The spectra of S 2p display two distinct single peaks at 161.7 eV (S 2p 3/2 ) and 162.9 eV (S 2p 1/2 ).…”

Latest Progress on Photocatalytic H2 Production by Water Splitting and H2 Production Coupled with Selective Oxidation of Organics over ZnIn2S4-Based Photocatalysts

“…170 After visible light illumination for 4 h, the optimal 0.5% Au/ZnIn 2 S 4 nanosheets yielded H 2 (326.68 μmol) and benzaldehyde (352.04 μmol) simulta- neously. Henceforth, lots of ZnIn 2 S 4 -based dual-functional photocatalysts have been developed to fulfill H 2 production with simultaneous oxidation of benzyl alcohol with high selectivity and good stability, such as Co-doped ZnIn 2 S 4 nanotubes, 171 Ni-loaded ZnIn 2 S 4 flowers, 172 Ni 12 P 5 /ZnIn 2 S 4 with Zn vacancies, 173 Ni 12 P 5 /O-doped ZnIn 2 S 4 , 174 and Ni X -B/ ZnIn 2 S 4 . 175 Because of the superior separation efficiency of charge carriers and high redox capacity of the left photoexcited electrons and holes induced by the Z-scheme heterojunction, ZnIn 2 S 4 -based direct Z-scheme heterostructures, including CeO 2 /ZnIn 2 S 4 composite, 176 phosphomolybdic acid (HPM) cluster-incorporated ZnIn 2 S 4 (HPM/ZIS) nanosheets, 177 WO 3 /ZnIn 2 S 4 1D/2D composite, 178 and the O-ZnIn 2 S 4 / TiO 2−x S-scheme heterojunction, 179 all exhibit good activity for concurrent H 2 generation and selective oxidation of benzyl alcohol.…”