Energy funneling and charge separation in CdS modified with dual cocatalysts for enhanced H2 generation

doi:10.1016/S1872-2067(21)64009-3

Abstract

Abstract:

Anchoring molecular cocatalysts on semiconductors has been recognized as a general strategy to boost the charge separation efficiency required for efficient photocatalysis. However, the effect of molecular cocatalysts on energy funneling (i.e., directional energy transfer) inside semiconductor photocatalysts has not been demonstrated yet. Here we prepared CdS nanorods with both thin and thick rods and anchored the conjugated molecules 2-mercaptobenzimidazole (MBI) and cobalt molecular catalysts (MCoA) sequentially onto the surface of nanorods. Transient absorption measurements revealed that MBI molecules facilitated energy funneling from thin to thick rods by the electronic coupling between thin and thick nanorods, which is essentially a light-harvesting antenna approach to enhance the charge generation efficiency in the reaction center (here the thick rods). Moreover, MBI and MCoA molecules selectively extracted photogenerated holes and electrons of CdS nanorods rapidly, leading to efficient charge separation. Consequently, CdS/MBI/MCoA displayed 15 times enhanced photocatalytic H₂ evolution (1.65 mL) than pure CdS (0.11 mL) over 3 h of illumination. The amount of H₂ evolution reached 60 mL over 48 h of illumination with a high turnover number of 26294 and an apparent quantum efficiency of 71% at 420 nm. This study demonstrates a novel design principle for next-generation photocatalysts.

Key words: Energy funneling, Charge separation, CdS nanorods, Molecular cocatalyst, Photocatalytic H₂ generation

Meiyu Zhang, Chaochao Qin, Wanjun Sun, Congzhao Dong, Jun Zhong, Kaifeng Wu, Yong Ding. Energy funneling and charge separation in CdS modified with dual cocatalysts for enhanced H₂ generation[J]. Chinese Journal of Catalysis, 2022, 43(7): 1818-1829.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64009-3

https://www.cjcatal.com/EN/Y2022/V43/I7/1818

Figures/Tables 9

Fig. 1. Schematic illustration of the synthesis of CdS/MBI/MCoA.

Fig. 2. (a) XRD patterns of CdS, CdS/MBI and CdS/MBI/MCoA. (b) Raman spectra of CdS, CdS/MBI and CdS/MBI/MCoA. (c) UV-vis absorption spectra of CdS, CdS/MBI and CdS/MBI/MCoA. TEM images of CdS (d) and CdS/MBI (e,f). HRTEM images of CdS (g), CdS/MBI (h) and CdS/MBI/MCoA (i).

Fig. 3. High-resolution XPS spectra of the Cd 3d (a) and S 2p (b) for CdS and CdS/MBI. (c) High-resolution XPS spectra of Co 2p for CdS/MBI/MCoA and CoA. (d) Co K-edge XANES spectroscopy of the reference samples (CoO, CoA), CdS/CoA and CdS/MBI/MCoA. (e) The k3-weighted EXAFS in k-space for the reference samples (CoA), CdS/CoA and CdS/MBI/MCoA, respectively. (f) The Fourier transforms in R space for the reference samples (CoO, CoA), CdS/CoA and CdS/MBI/MCoA, respectively.

Fig. 4. (a) Transient absorption spectra of CdS at indicated delay times measured with 365?nm excitation. (b) Time-wavelength dependent TA color maps for CdS. (c) Transient absorption traces for CdS normalized to the B1 (490 nm) and B2 (500 nm) exciton bands. (d) Transient absorption spectra of CdS/MBI at indicated delay times measured with 365?nm excitation. (e) Time-wavelength dependent TA color maps for CdS/MBI. (f) Transient absorption traces for CdS/MBI normalized to the B1 (490 nm) and B2 (500 nm) exciton bands.

Fig. 5. (a) Transient absorption traces for CdS, CdS/MBI and CdS+(NH4)2SO3 probed at 575 nm. (b) Comparison of decay of normalized traces of CdS transient absorption at 490 nm (1s exciton bleach) and 575 nm (photoinduced absorption by the trapped hole). (c) Transient absorption spectra of CdS/MBI/MCoA at indicated delay times measured with 365?nm excitation. (d) Time-wavelength dependent TA color maps for CdS/MBI/MCoA. (e) Transient absorption traces for CdS, CdS/MBI/MCoA and CdS+BQ normalized to the 1s exciton bleach. (f) Schematic of charge transfer processes in CdS decorated with both MBI and MCoA.

Fig. 6. (a) Time courses of photocatalytic H2 evolution for CdS, CdS/MBI and CdS/MBI/MCoA over 3 h of illumination (0.1 mol/L (NH4)2SO3). (b) Time courses of photocatalytic H2 evolution in CdS/MBI/MCoA system under different concentrations of (NH4)2SO3 (0.3-0.7 mol/L) over 48 h of illumination. (c) The photocatalytic H2 evolution for CdS, Co/CdS, CdS+Co(NO3)2, CdS+CoA, CdS/MBI/MCoA and Pt/CdS after 3 h of illumination (0.1 mol/L (NH4)2SO3). (d) Cycling runs for photocatalytic hydrogen evolution activity under visible light (λ = 420 nm) over CdS/MBI/MCoA. Light source: LED lamp (λ = 420 nm); reaction solution: 30 mL of 0.1 mol/L (NH4)2SO3 solution, 5 mg catalyst.

Fig. 7. Photocurrent (a) and EIS (b) of CdS, CdS/MBI and CdS/MBI/MCoA. (c) Mott-Schottky plots of pure CdS at different frequencies. (d) LSV curves of CdS, CdS/MBI and CdS/MBI/MCoA.

Fig. 8. (a) Cyclic voltammogram of CdS/MBI/MCoA in VCH3CH2OH:VH2O = 1:1 solution. Scan rate: 100 mV/s; glass carbon electrode. (b) UV-vis diffuse reflection spectra of CdS (the inset is the band gap of CdS). (c) Calculated HOMO and LUMO of the MBI molecule. The molecule frontier orbitals are performed by Gaussian 16 under the level of B3LYP/6-31G* *. (d) Estimated band position of CdS, HOMO energy level of MBI and redox potential of Co2+/Co+ in CdS/MBI/MCoA.

Fig. 9. Schematic of charge transfer processes in CdS decorated with MBI and MCoA.

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Energy funneling and charge separation in CdS modified with dual cocatalysts for enhanced H₂ generation

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