期刊
ACS CATALYSIS
卷 11, 期 2, 页码 871-882出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.0c04673
关键词
molecular photocatalysis; carbon dioxide reduction; metal-organic frameworks; catalyst stabilization; photosensitizer; solar fuel production
资金
- German Research Foundation (DFG) Priority Program 1928 Coordination Networks: Building Blocks for Functional Systems
- research project MOFMOX [FI 502/43-1]
- Excellence Cluster 2089 e-conversion (Fundamentals of Energy Conversion Processes)
This study presents a novel approach to enhance photocatalytic CO2 reduction activity by embedding a molecular catalyst in a metal-organic framework. The ratio of immobilized catalyst to photosensitizer is crucial for improving reaction efficiency and determining optimal performance, while the research also reveals the impact of reaction environment on active sites and provides a future direction for increasing turnover numbers.
Herein, we report on a molecular catalyst embedding metal-organic framework (MOF) that enables enhanced photocatalytic CO, reduction activity. A benchmark photocatalyst fac-ReBr(CO)(3)(4,4'-dcbpy) (dcbpy = dicarboxy-2,2'-bipyridine) and photosensitizer Ru(bpy) 2 (5,5'-dcbpy)Cl-2 (bpy = 2,2'-bipyridine) were synergistically entrapped inside the cages of the nontoxic and inexpensive MIL-101-NH2 (Al) through noncovalent host-guest interactions. The heterogeneous material improved Re catalyst stabilization under photocatalytic CO2 reduction conditions as selective CO evolution was prolonged from 1.5 to 40 h compared to the MOF-free photosystem upon reactivation with additional photosensitizer. By varying ratios of immobilized catalyst to photosensitizer, we demonstrated and evaluated the effect of reaction environment modulation in defined MOF cages acting as a nanoreactor. This illustrated the optimal efficiency for two photosensitizers and one catalyst per cage and further led to the determination of ad hoc relationships between molecular complex size, MOF pore windows, and number of hostable molecules per cage. Differing from typical homogeneous systems, photosensitizer-and not catalyst-degradation was identified as a major performance-limiting factor, providing a future route to higher turnover numbers via a rational choice of parameters.
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