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Coordination Mode Engineering of Ce-Based Frameworks to Tune Photocatalytic Hydrogen Evolution
Shi-Qing Wang1, Zhao-Feng Qiu2, Yu Wu3
1Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China.
None:
The coordination mode and multinuclear metal center can modulate the band gap (Eg) of metal-organic frameworks (MOFs), which is critical for photocatalytic reactions. Herein, three Ce-MOFs of Ce-1, Ce-2, and Ce-3 were synthesized with full, partial, and noncoordination of the bipyridyl moiety in the 2,2'-bipyridine-5,5'-dicarboxylate (bpdc2-) ligand, respectively. These MOFs were employed to explore their photocatalytic hydrogen evolution performance. With Pt nanoparticles as cocatalysts, the hydrogen evolution rate of Ce-3 reaches 12.99 μmol h-1, which is 3.61 times that of Ce-1. Both experimental results and density functional theory (DFT) calculations demonstrate that the uncoordinated bipyridyl unit influences the photocatalytic efficiency. The more uncoordinated bipyridyl units correspond to smaller Eg. Additionally, the oxygen and/or carboxylate bridged multinuclear Ce-centers in the MOFs facilitate an efficient ligand-to-metal charge transfer (LMCT). The insights from this study provide a strategic guideline for engineering coordination modes in MOFs to enhance their photocatalytic hydrogen production capacity.
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