Synthesis, structure and photocatalytic performance of {[Bi6(tza)5(NO3)2(OH)5O3]·H2O}n and its derivatives

Abstract

A polynuclear metal-organic framework, {[Bi6(tza)5(NO3)2(OH)5O3]·H2O}n (Htza=1H-tetrazole-1-acetic acid), was successfully synthesized and characterized, and its photocatalytic properties, along with those of its derivatives, were investigated. The crystal structure of the compound was determined to belong to the orthorhombic space group Pn ma, featuring a 3D framework comprising cage-like [Bi6(µ3-O)3(µ3-OH)5]7+ clusters. {[Bi6(tza)5(NO3)2(OH)5O3]·H2O}n demonstrated significant photocatalytic activity with UV light response within the pH range of 6.0–8.0 and a band gap energy of 3.32 eV. Under optimal conditions, a reduction in chemical oxygen demand (COD) and total organic carbon (TOC) (from 126.90 mg/L to 4.57 mg/L) clearly validated the efficient methyl orange degradation. The main active groups in the degradation process were h+, ·O2− and ·OH, and the catalyst demonstrated reusability for up to six cycles. Moreover, it was hydrolyzed to Bi2O2CO3 and BiOCl under alkaline (pH=9.0–11.0) and acidic (pH=1.0–5.0) conditions, respectively, thus serving as a valuable precursor. Notably, the Bi2O2CO3 and BiOCl derivatives exhibited higher catalytic activities than catalysts synthesized using alternative methods under the same experimental conditions. Therefore, within the pH range of 1.0–11.0, {[Bi6(tza)5(NO3)2(OH)5O3]·H2O}n, along with its in situ derivatives BiOCl and Bi2O2CO3, were highly efficient UV light-driven photocatalysts.