Four new dual-functional electro-catalysts formed from small molybdenum clusters and Cu-pyridyl complexes. Issue 43 (18th October 2019)

• Record Type: Journal Article
• Authors: Zhou, Wanli; Liu, Ping; Zheng, Yanping; Liu, Xuekun; Zhang, Yong; Yuan, Gang; Peng, Jun
• Is Part Of: Dalton transactions. Volume 48:Issue 43(2019)
• Page Start: 16350
• Page End: 16357
• Publication Date: 2019-10-18
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt03560e
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Four new isopolymolybdates-based organic–inorganic hybrids decorated with Cu-pyridyl complexes were prepared by using one-pot methods. Compounds 1–4 display discrepant dual-functional electro-catalytic activities toward reduction of nitrite and oxidation of ascorbic acid. Abstract : By changing N-heterocyclic ligands in the same Mo7 /Cu/N-ligand reaction systems, four new organic–inorganic hybrids based on isopolymolybdates, [Cu2 (tpy)2 (β-Mo8 O26 )0.5 (γ-Mo8 O26 )0.5 ]·0.25H2 O (1 ), [Cu2 (tpy)2 (H2 O)2 (β-Mo8 O26 )] (2 ), [Cu(bpy)(Mo3 O10 )]·H2 O (3 ), and [Cu(bpy)(H2 O)(β-Mo8 O26 )0.5 ]0.5 (4 ) (tpy = 2, 2′:6′, 2′′-terpyridine and bpy = 2, 6-bis(pyrazol-1-yl) pyridine), were prepared using hydrothermal methods at different pH values. X-ray structural analysis shows that compound 1 has a 1D {-β-[Mo8 O26 ]-Cu2 -γ-[Mo8 O26 ]} n straight chain structure with mixed β-[Mo8 O26 ] and γ-[Mo8 O26 ] polyoxoanions; compound 2 possesses a 3D supramolecular structure based on [Cu(tpy)] 2+ motifs and β-[Mo8 O26 ] clusters; and compound 3 has a 1D chain structure built from [Cu(bpy)] 2+ and [Mo3 O10 ] 2− units. In compound 4, [β-Mo8 O26 ] clusters are linked by [Cu(bpy)] 2+ motifs to give rise to a 2D sheet structure including {(β-Mo8 O26 )4 Cu4 } 8-membered rings. Cyclic voltammograms of compounds 1–4 display discrepant dual-functional electro-catalytic activities toward the reduction of nitrite and the oxidation of ascorbic acid in acidic solution. Electrocatalytic tests indicate that the [Mo3 O10 ] 2− -based organic–inorganic hybrid exhibits better electro-catalytic performances than [Mo8 O26 ] 4− -type hybrids towards oxidation and reduction.