Tuning the Active Sites of Atomically Thin Defective Bi₁₂O₁₇Cl₂ via Incorporation of Subnanometer Clusters

Abstract

The introduction of subnanometer clusters as active sites on the surface of photocatalysts for efficiently tuning the selectivity and activity of the photocatalyts is still a challenge. Herein, the subnanometer Ag/AgCl clusters were incorporated on atomically thin defective Bi12O17Cl2 nanosheets via rebinding with unsaturated Cl atoms. Benefiting from the surficial Bi vacancies (VBi) and Bi–O vacancies (VBi–O) in this atomically thin architecture, the local atomic arrangement was tuned so that the subnanometer Ag/AgCl clusters were successfully incorporated. An enhancement of photocatalytic activity for NO removal was achieved in which the activity is 3 times higher than that of Bi12O17Cl2 and 1.8 times higher than that of defective Bi12O17Cl2. The substitution of the active sites from surficial VBi and VBi–O to be subnanometer Ag/AgCl clusters enables a tunable redox potential and different reaction mechanisms in NO removal. Moreover, the selectivity of the photoinduced redox reaction on NO oxidation and CO2 reduction was achieved via introducing an extra energy level.

Dopant and Defect Doubly Modified CeO2/g-C3N4 Nanosheets as 0D/2D Z-Scheme Heterojunctions for Photocatalytic Hydrogen Evolution: Experimental and Density Functional Theory Studies

“…Moreover, other CeO 2 /g-C 3 N 4 composites have also been studied. − Although several unexpected developments have been achieved in these studies, CeO 2 nanodots doubly modified with dopants and OVs integrated with g-C 3 N 4 nanosheets (CNNS) to construct the 0D/2D Z-scheme heterostructure and its application in PHE have not been explored. 0D nanodots with a smaller size could decrease the diffusion length of charge carriers, promoting the separation of charge carriers. ,,− Good dispersion on the fully exposed 2D g-C 3 N 4 could create numerous intimate heterojunction interfaces, which would offer more separation and migration pathways for photogenerated charge carriers to ensure that they can be separated more efficiently and quickly. ,, Therefore, anchoring 0D nanodots on 2D nanosheets to form 0D/2D heterojunctions has the potential to improve the PHE performance. Moreover, theoretical calculations, especially density functional theory (DFT) calculation research, have an important value in analyzing the electronic structural properties, work functions, and the charge transfer at the interface of composite heterojunctions. , The combination of theoretical calculations and experiments to complement each other has become the current trend.…”

Experimental and Theoretical Advances on Single Atom and Atomic Cluster‐Decorated Low‐Dimensional Platforms towards Superior Electrocatalysts

“…There is no doubt that the existence of defects on the support provides the possibility for the anchoring of metal atoms. Zhu et al [78] obtained a special structure of coexistence of Ag and AgCl ACEs by photo-induced reduction of Ag + adsorbed on the surface of defective Bi 12 O 17 C l2 nanosheets (BOC-D). Unsaturated Cl atoms due to the existence of vacancies (V Bi and V BiO ) on BOC-D nanosheets can strongly interact with Ag, resulting in Ag embedded in BOC-D lattice and partially replacing V Bi and V BiO .…”

“…Adapted with permission. [ 78 ] Copyright 2021, American Chemical Society. C) Synthetic schematic diagram of Pt/DG ACEs and corresponding HAADF‐STEM image via SEED.…”

“…B) Ag/AgCl-BOC-D nanosheets, formation mechanism of Ag/AgCl ACEs, and corresponding HAADF-STEM image. Adapted with permission [78]. Copyright 2021, American Chemical Society.…”

Simultaneous photocatalytic tetracycline oxidation and chromate reduction via a jointed synchronous pathway upon Z-scheme Bi12O17Cl2/AgBr: insight into intermediates and mechanism

“…19 Moreover, B 12 possesses the conduction band position that is negative enough to reduce O 2 into ˙O 2 − and Cr( vi ) into Cr( iii ). 20 These characteristics guarantee its unique and preferable photocatalytic ability, such as selective oxidization, 21 organic pollutant mineralization, 22 NO removal, 23 Cr( vi ) reduction, 24 and most importantly, simultaneous reduction and oxidization. 25 Nevertheless, the narrow bandgap inevitably restrains the separation of photo-induced charge carriers and reduces its redox potentials, thus creating a solid motivation to modify the photocatalyst for actual degrading applications.…”