Unraveling the Origin of Photocatalytic Deactivation in CeO₂/Nb₂O₅ Heterostructure Systems during Methanol Oxidation: Insight into the Role of Cerium Species

Abstract

The study provides deep insight into the origin of photocatalytic deactivation of Nb 2 O 5 after modification with ceria. Of particular interest was to fully understand the role of ceria species in diminishing the photocatalytic performance of CeO 2 /Nb 2 O 5 heterostructures. For this purpose, ceria was loaded on niobia surfaces by wet impregnation. The as-prepared materials were characterized by powder X-ray diffraction, nitrogen physisorption, UV–visible spectroscopy, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and photoluminescence measurements. Photocatalytic activity of parent metal oxides (i.e., Nb 2 O 5 and CeO 2 ) and as-prepared CeO 2 /Nb 2 O 5 heterostructures with different ceria loadings were tested in methanol photooxidation, a model gas-phase reaction. Deep insight into the photocatalytic process provided by operando -IR techniques combined with results of photoluminescence studies revealed that deactivation of CeO 2 /Nb 2 O 5 heterostructures resulted from increased recombination of photo-excited electrons and holes. The main factor contributing to more efficient recombination of the charge carriers in the heterostructures was the ultrafine size of the ceria species. The presence of such highly dispersed ceria species on the niobia surface provided a strong interface between these two semiconductors, enabling efficient charge transfer from Nb 2 O 5 to CeO 2 . However, the ceria species supported on niobia exhibited a high defect site concentration, which acted as highly active recombination centers for the photo-induced charge carriers.

Earth-Abundant-Based Photocatalysts for Efficient and Selective H2 Production through Reforming of Formic Acid under Visible Light

“…Synthesis of Nb 2 O 5 : The Nb 2 O 5 was synthesized using the hydrothermal procedure described elsewhere . In a typical synthesis route, ammonium niobate­(V) oxalate hydrate (Sigma-Aldrich, C 4 H 4 NNbO 9 ·H 2 O, 99.99%) (9.0894 g, 30 mmol) was dissolved in 200 mL of deionized water.…”

“…Synthesis of Nb 2 O 5 : The Nb 2 O 5 was synthesized using the hydrothermal procedure described elsewhere. 25 In a typical synthesis route, ammonium niobate(V) oxalate hydrate (Sigma-Aldrich, C 4 H 4 NNbO 9 •H 2 O, 99.99%) (9.0894 g, 30 mmol) was dissolved in 200 mL of deionized water. Following 1 h of vigorous stirring, the pellucid solution was sealed in a Teflonlined stainless steel autoclave and heated for 24 h at 175 °C.…”