轮型二十核铜取代多金属氧酸盐催化剂: 光催化制氢的机理和稳定性研究

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

催化学报 ›› 2022, Vol. 43 ›› Issue (2): 442-450.DOI: 10.1016/S1872-2067(21)63840-8

轮型二十核铜取代多金属氧酸盐催化剂: 光催化制氢的机理和稳定性研究

冯业芹, 秦琳, 张峻豪, 符方玉^#(), 李慧杰, 相华, 吕红金^*()

北京理工大学化学与化工学院, 原子分子簇科学教育部重点实验室, 北京 102488

收稿日期:2021-03-30 接受日期:2021-03-30 出版日期:2022-02-18 发布日期:2021-05-20
通讯作者: 符方玉,吕红金
基金资助:
国家自然科学基金(21871025);国家自然科学基金(21831001);国家自然科学基金(22001016);国家海外高层次人才引进计划青年项目;北理工高层次人才科研启动计划项目;中国博士后科学基金(2020TQ0038)

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

Yeqin Feng, Lin Qin, Junhao Zhang, Fangyu Fu^#(), Huijie Li, Hua Xiang, Hongjin Lv^*()

MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China

Received:2021-03-30 Accepted:2021-03-30 Online:2022-02-18 Published:2021-05-20
Contact: Fangyu Fu, Hongjin Lv
Supported by:
This work was supported by the National Natural Science Foundation of China(21871025);This work was supported by the National Natural Science Foundation of China(21831001);This work was supported by the National Natural Science Foundation of China(22001016);the Recruitment Program of Global Experts (Young Talents);BIT Excellent Young Scholars Research Fund;the China Postdoctoral Science Foundation(2020TQ0038)

摘要/Abstract

摘要：

能源危机和环境污染已成为影响全人类的严峻问题, 太阳能驱动水分解制备清洁可再生的氢能是解决以上问题的有效途径之一, 因此, 近年来环境友好的光驱动制氢方式受到广泛关注. 现阶段太阳能驱动水分解体系的研究热点和难点在于研发高催化活性且廉价的非贵金属催化剂. 作为具有较大应用潜力的多电子转移催化剂, 廉价过渡金属取代的多金属氧酸盐因其合成策略丰富多样, 原子结构明晰以及物化性质可调, 越来越多地被用于催化水分解的研究中. 其结构中的缺位多酸配体具有可逆的电子存储能力, 因而可被用作多电子存储海绵, 而过渡金属中心则可以作为催化活性位点, 这种特殊的协同工作机制可有效促进催化反应中的电荷分离并延长电子的寿命, 更利于催化还原反应的发生. 虽然目前文献中有较多关于廉价3d过渡金属取代的多金属氧酸盐水还原催化剂的报道; 然而, 现阶段基于廉价过渡金属铜取代的多金属氧酸盐在光驱动分解水制氢领域的研究较少. 这主要受制于理论计算得出的传统结论: 氢原子在铜原子上的氢吸附吉布斯自由能比较高, 可能会导致铜基催化剂具有比较低的产氢活性.
本文合成了轮型二十核铜取代多金属氧酸盐水还原催化剂K₁₂Li₁₃[Cu₂₀Cl(OH)₂₄(H₂O)₁₂(P₈W₄₈O₁₈₄)]·22H₂O (K₁₂Li₁₃-Cu₂₀P₈W₄₈), 然后通过简单的阳离子交换制备了其四丁基铵盐(TBA-Cu₂₀P₈W₄₈), 红外表征结果表明, 阳离子交换能够完整地保持其阴离子结构. 利用[Ir(ppy)₂(dtbbpy)][PF₆]作为光敏剂, 三乙醇胺(TEOA)为牺牲试剂和TBA-Cu₂₀P₈W₄₈为催化剂构筑光催化体系, 反应5 h后产氢转化数达到~2892, 120 h后高达~13400. 此外, 稳态和瞬态荧光猝灭光谱表明, 激发态的光敏化剂既可以被TBA-Cu₂₀P₈W₄₈氧化型猝灭, 也可以被TEOA还原型猝灭, 其中后者占主导. 稳定性测试实验结果表明, 在光催化过程中, TBA-Cu₂₀P₈W₄₈分子催化剂上有Cu离子缓慢解离到反应溶液中, 但其光催化产氢的主要催化活性物种仍具备分子催化剂的骨架结构.
本文不仅对多核铜基分子化合物能够高效地催化光驱动产氢提供有利证明, 而且为探索更多廉价铜取代多金属氧酸盐在太阳能转化领域的应用提供了参考.

关键词: 多金属氧酸盐, 二十核铜取代, 光催化产氢, 光催化机理, 稳定性研究

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

冯业芹, 秦琳, 张峻豪, 符方玉, 李慧杰, 相华, 吕红金. 轮型二十核铜取代多金属氧酸盐催化剂: 光催化制氢的机理和稳定性研究[J]. 催化学报, 2022, 43(2): 442-450.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63840-8

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

图/表 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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轮型二十核铜取代多金属氧酸盐催化剂: 光催化制氢的机理和稳定性研究

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

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