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Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Linker Deficiency, Aromatic Ring Fusion, and Electrocatalysis in a Porous Ni8-Pyrazolate Network
Jieying Hu1, Xiangling Deng1, Hu Zhang1
1School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, 510006, Guangdong, People's Republic of China.
Abstract:
The cruciform linker molecule here features two designer functions: the pyrazole donors for framework construction, and the vicinal alkynyl units for benzannulation to form nanographene units into the Ni8-pyrazolate scaffold. Unlike the full 12 connections of the Ni8(OH)4(H2O)2 clusters in other Ni8-pyrazolate networks, significant linker deficiency was observed here, leaving about half of the Ni(II) sites capped by acetate ligands, which can be potentially removed to open the metal sites for reactivity. The crystalline Ni8-pyrazolate scaffold also retains the crystalline order even after thermal treatments (up to 300 °C) that served to partially graphitize the neighboring alkyne units. The resultant nanographene components enhance the electroactive properties of the porous hosts, achieving hydrogen evolution reaction (HER) activity that rivals that of topical nickel/palladium-enabled materials.
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