Embedding [Mo3S13]2− clusters into the micropores of a covalent organic framework for enhanced stability and photocatalytic hydrogen evolution

Fabrication of an Organic/Inorganic Hybrid TpPa-1-COF/ZnIn2S4 S-Scheme Heterojunction for Boosted Photocatalytic Hydrogen Production

“…From the high-resolution XPS spectrum of C 1s (Figure 2b), three peaks of the COF/ZIS-20% sample appear at 284.9, 286.4, and 288.9 eV, which can be ascribed to the C− C/C�C, C−N, and C�O bonds in TpPa-1-COF, respectively. 7 As depicted in Figure 2c, the peaks attributed to C�O bonds and the end aldehyde groups are presented in the samples of TpPa-1-COF and COF/ZIS-20%, whereas the peaks at 533.4 and 532.0 eV in the sample of ZnIn 2 S 4 can be specified as signals for hydroxyl and adsorbed water, respectively. 19 From Figure S2, the high-resolution N 1s XPS spectrum of the bare TpPa-1-COF shows an intense peak at 400.1 eV, which could be ascribed to C−NH x groups belonging to the skeleton vibration of TpPa-1-COF, 52 while COF/ZIS-20% exhibits a relatively lower peak at 400.1 eV due to the introduction of another phase of ZnIn 2 S 4 .…”

“…According to Figure a, TpPa-1-COF shows C, N, and O elements, whereas ZnIn 2 S 4 and COF/ZIS-20% display the feature peaks of C, S, O, N, Zn, and In elements. From the high-resolution XPS spectrum of C 1s (Figure b), three peaks of the COF/ZIS-20% sample appear at 284.9, 286.4, and 288.9 eV, which can be ascribed to the C–C/CC, C–N, and CO bonds in TpPa-1-COF, respectively . As depicted in Figure c, the peaks attributed to CO bonds and the end aldehyde groups are presented in the samples of TpPa-1-COF and COF/ZIS-20%, whereas the peaks at 533.4 and 532.0 eV in the sample of ZnIn 2 S 4 can be specified as signals for hydroxyl and adsorbed water, respectively .…”

“…A covalent organic framework (COF) is a new kind of porous organic crystalline material formed by strong covalent bonding of organic monomers, which has been applied in the field of photocatalysis. − Our previous studies have demonstrated that a two-dimensional (2D) β-ketoenamine-linked COF (TpPa-1-COF) with remarkable chemical stability could be employed to anchor Pt single atoms or embed [Mo 3 S 13 ] 2– nanoclusters into its micropores to boost the photocatalytic hydrogen evolution. , Besides that, COF has inherent good light absorption and can be used to form a heterostructure with other semiconductors with energy band matching, thus promoting the separation process of photogenerated electrons and holes. − Moreover, previous studies have shown that the π-stacking skeleton structure in COF provides a clear carrier transport path for itself, and the synergistic effect of the inherent large surface area, adjustable porosity, and diverse structures makes COF an interesting platform for designing efficient heterojunctions. − …”

“…photocatalytic hydrogen evolution 6,7. Besides that, COF has inherent good light absorption and can be used to form a heterostructure with other semiconductors with energy band matching, thus promoting the separation process of photogenerated electrons and holes.8−13 Moreover, previous studies have shown that the π-stacking skeleton structure in COF provides a clear carrier transport path for itself, and the synergistic effect of the inherent large surface area, adjustable porosity, and diverse structures makes COF an interesting platform for designing efficient heterojunctions.14−17 Recently, metal sulfides as inorganic semiconductors have attracted more and more research interest from some scholars for their special electronic and optical properties for photocatalysis.…”

Green and Fast Strategies for Energy‐Efficient Preparation of the Covalent Organic Framework TpPa‐1

“…An average value of 3.3 Å was calculated (Table S2) which was in accord-ance with other TpPa-1 d-spacing PXRD measurements in the literature. [33] Microwave-assisted synthesis was developed under hydrothermal conditions analogously to conventional oven heating. It should be noted that with this type of heating, which is more efficient than conventional heating, the use of water as a solvent is unusual in the literature for COF synthesis.…”