Wheel-shaped icosanuclear Cu-containing polyoxometalate catalyst: Mechanistic and stability studies on light-driven hydrogen generation

doi:10.1016/S1872-2067(21)63840-8

Abstract

Abstract:

In this paper, we report the synthesis and characterization of a wheel-shaped icosanuclear Cu-containing polyoxometalate (POM), K₁₂Li₁₃[Cu₂₀Cl(OH)₂₄(H₂O)₁₂(P₈W₄₈O₁₈₄)]·22H₂O (K₁₂Li₁₃-Cu₂₀P₈W₄₈). The resulting cation-exchanged tetrabutylammonium salt of the polyoxoanion Cu₂₀P₈W₄₈ (TBA-Cu₂₀P₈W₄₈) exhibits high efficiency for visible-light-driven H₂ production in the presence of an [Ir(ppy)₂(dtbbpy)][PF₆] photosensitizer and a triethanolamine electron donor. Under optimal conditions, the turnover number for H₂ production reaches ~2892 after 5 h of photocatalysis and thereafter continuously increases to ~13400 in a long-term 120 h reaction, representing the best performance among all reported transition-metal-substituted POM catalysts. Mechanistic studies confirm the existence of reductive and oxidative quenching processes, of which the reductive quenching pathway is dominant. Various stability tests demonstrate that the TBA-Cu₂₀P₈W₄₈ catalyst slowly dissociates Cu ions under turnover conditions; however, both the starting TBA-Cu₂₀P₈W₄₈ and its molecular decomposition products are dominant active species for efficient and long-term H₂ production.

Key words: Polyoxometalates, Icosanuclear copper substitution, Light-driven hydrogen production, Photocatalytic mechanism, Stability study

Yeqin Feng, Lin Qin, Junhao Zhang, Fangyu Fu, Huijie Li, Hua Xiang, Hongjin Lv. Wheel-shaped icosanuclear Cu-containing polyoxometalate catalyst: Mechanistic and stability studies on light-driven hydrogen generation[J]. Chinese Journal of Catalysis, 2022, 43(2): 442-450.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63840-8

https://www.cjcatal.com/EN/Y2022/V43/I2/442

Figures/Tables 7

Fig. 1. Polyhedral and ball-and-stick representations of the building blocks of polyoxoanion Cu20P8W48. (a) Polyhedral; (b) Ball-and-stick. Color code: WO6 (green octahedra), Cu (blue balls), O (red balls), Cl (bright green ball).

Fig. 2. Combined polyhedral/ball-and-stick illustration of K12Li13-Cu20P8W48. Color code: PO4 (red tetrahedra), Cu (blue balls), Cl (bright green ball), W (green balls), O (red balls). Protons associated with the oxygen atoms are omitted for simplicity.

Fig. 3. SEM images of the TBA-Cu20P8W48 sample and the corresponding EDX elemental maps of P, W, and Cu.

Fig. 4. Photocatalytic H2 evolution by different catalysts under otherwise identical conditions: LED light (450 nm), [Ir(ppy)2(dtbbpy)]+ (0.2 mM), TEOA (0.25 M), H2O (2 M), catalysts (5 μM), CH3CN/DMF (v/v = 1/3), H2O (2 M) deaerated with Ar/CH4 (v/v = 4/1).

Fig. 5. Photocatalytic H2 evolution as a function of different catalysts and control components (a), different concentrations of photosensitizer [Ir(ppy)2(dtbbpy)]+ (b), different concentrations of TBA-Cu20P8W48 catalyst (c), and different concentrations of TEOA (d). Standard conditions: LED light (450 nm), [Ir(ppy)2(dtbbpy)]+ (0.2 mM), TEOA (0.25 M), H2O (2 M), catalyst (5 μM), CH3CN/DMF (v/v = 1/3) deaerated with Ar/CH4 (v/v = 4/1).

Fig. 6. Emission quenching of excited state [Ir(ppy)2(dtbbpy)]+* (0.2 mM) by TBA-Cu20P8W48 (a) and TEOA (b) in 3 mL of CH3CN/DMF (v/v = 1/3) solution 450 nm excitation.

Fig. 7. Normalized luminescence decay kinetics of [Ir(ppy)2(dtbbpy)]+ (black curve) by TBA-Cu20P8W48 (blue curve) and TEOA (green curve). Conditions: 450 nm excitation, 0.2 mM [Ir(ppy)2(dtbbpy)]+, 0.25 M TEOA or 5 µM catalyst, CH3CN/DMF (v/v = 1/3). The red curves are obtained by a single-exponential fitting method.

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