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Bismuth-Polyoxocation Coordination Networks: Controlling Nuclearity and Dimension-Dependent Photocatalysis
Mehran Amiri1, Alice Lulich1, Nan-Chieh Chiu1
1Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States.
ACS Applied Materials & Interfaces
|March 28, 2023
Summary
This study reveals how solvent polarity controls bismuth node nuclearity in metal-organic frameworks (MOFs), enabling new materials for photocatalysis. These bismuth-based MOFs demonstrate efficient hydrogen generation without co-catalysts.
Area of Science:
- Materials Science
- Inorganic Chemistry
- Nanotechnology
Background:
- Bismuth (Bi) nodes are less common in metal-organic frameworks (MOFs) compared to other metals, despite Bi's non-toxicity and potential in catalysis.
- Understanding factors that control node formation is crucial for designing novel MOFs with tailored properties.
- Solvent effects in MOF synthesis are often secondary to linker choice, but this may differ for systems with intrinsic electronic properties like Bi.
Purpose of the Study:
- To investigate the influence of solvent polarity on the nuclearity and topology of bismuth-based coordination networks.
- To synthesize and characterize a new family of bismuth-sulfonate/carboxylate coordination networks.
- To evaluate the photocatalytic activity of these novel bismuth materials for hydrogen generation.
Main Methods:
- Single-crystal X-ray diffraction was used to determine the structures of eleven bismuth coordination networks.
- In situ small-angle X-ray scattering (SAXS) was employed to study the formation mechanism of a Bi38-DDBS framework.
- X-ray photoelectron spectroscopy (XPS) and UV-vis spectroscopy were used for band gap determination and electronic structure analysis.
Main Results:
- Bismuth node nuclearity (Bix, where x = 1-38) was found to be strongly dependent on solvent polarity, with larger nuclearity nodes forming in polar solvents.
- The solvent plays a dominant role in defining node topology, attributed to the weak node-linker interactions arising from the Bi3+ lone pair.
- Synthesized materials demonstrated photocatalytic hydrogen generation without co-catalysts, with performance linked to Bi content and light absorption properties, including in situ formation of Bi0 nanoparticles.
Conclusions:
- Solvent polarity is a key factor in controlling bismuth node assembly in coordination networks, offering a new synthetic strategy.
- The synthesized bismuth coordination networks show promise as efficient, co-catalyst-free photocatalysts for hydrogen production.
- In situ generated bismuth species (Bi0) under UV-vis irradiation enhance photocatalytic activity, suggesting a pathway for improved material performance.
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