A Semiconducting Bi₂O₂(C₄O₄) Coordination Polymer Showing a Photoelectric Response

Abstract

Owing to their efficient photoinduced electron/hole separation, inorganic semiconductors have been extensively considered as some of the most promising materials to convert solar light into electricity or chemical energy. Therefore, there is much interest on developing stable and photoactive materials. Bismuth oxides and, in particular, those built up of [Bi2O2] 2+ layers show an efficient charge separation and, thus, high photocatalytic activities. To explore possible synergetic effect of Bi metallic nodes and the electron-rich linker squarate, the Bi2O2(C4O4) or IEF-3 (IMDEA Energy Framework) was hydrothermally prepared and fully characterized. As determined from X-ray structure, [Bi2O2] 2+ layers are interconnected by squarate ligand, having the Bi local environment a pronounced effect of 6s 2 lone pair. IEF-3 shows a high thermal and chemical robustness under relevant industrial aggressive media. A large panel of physicochemical methods were applied to recognize IEF-3 as an UV-absorbing n-type semiconductor, showing a photocurrent response similar to α-Bi2O3, but offering further possibilities of tuning of to electrochemical properties by modification of the ligand. In such a manner, the well-known compositional and structural versatility of MOFs may be applied in a future for a fine tuning of covalently bonded semiconductor systems.

A Novel Porous Ti‐Squarate as Efficient Photocatalyst in the Overall Water Splitting Reaction under Simulated Sunlight Irradiation

“…Photocurrent generation is also a convincing evidence of the occurrence of photoinduced charge separation. [ 50 ] Thus, photoelectrodes of IEF‐11 were prepared by spreading a thin film of this material on transparent conductive fluorine‐doped tin oxide (FTO). The photoelectrode was illuminated in contact with 0.1 m tetrabutylammonium hexafluorophosphate (TB 4 PF 6 ) electrolyte using a Pt wire as counter electrode and Ag/AgCl as reference electrode in a single compartment cell (Figure S22, Supporting Information).…”

Plasma‐Induced Defects Enhance the Visible‐Light Photocatalytic Activity of MIL‐125(Ti)‐NH2 for Overall Water Splitting

“…Synthesis of MIL-125(Ti)-NH 2 :M IL-125(Ti)-NH 2 was prepared by a solvothermal method as previously reported. [16] Briefly,2 -aminoterephthalic acid (1.43 g, 7.9 mmol) was dissolved in anhydrous N,Ndimethylformamide (DMF,2 0mL) and, then, anhydrous methanol (5 mL) was added to the flask. The system was sonicated for 20 min and, then, transferred to aT eflon-lined autoclave (50 mL).…”

Bi(iii) MOFs: syntheses, structures and applications

“…The Babaryk group synthesized a MOF, Bi 2 O 2 (C 4 O 4 ) by the hydrothermal method using H 2 C 4 O 4 (square acid) recently, which was expressed as IEF-3. 90 The photochemical behavior of IEF-3 is similar to that of α-Al 2 O 3 , an N-type semiconductor that absorbs ultraviolet light. Electron enrichment of IEF-3 may be due to the electron donor behavior of square anions.…”