Oxygen Vacancy‐Rich Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ Long Afterglow Phosphor as a Round‐the‐Clock Catalyst for Selective Reduction of CO₂ to CO

Abstract

Solar‐driven CO2 conversion to fuels is a central technique for closing the anthropogenic carbon cycle, but to date is limited by the intermittent solar flux. To face this challenge, a catalyst is needed that can work well in both light and dark. Here, surface oxygen vacancies are created in a Sr2MgSi2O7:Eu2+,Dy3+ long‐afterglow phosphor with long‐time and high charge storage capacity (denoted as Vo‐SMSED) as both electron transfer station and active sites for molecule activation. The strong ability for oxygen vacancies to store and extract electrons from charge storage centers enables the Vo‐SMSED to work efficiently in both light and dark. As a result, Vo‐SMSED manifests nearly 100% selectivity for catalyzing CO2 reduction by H2O to CO with high light stability and over 3 h dark activity. These results demonstrate that creating the bifunctional sites as electron‐storing/extracting and molecule‐activating center is an efficient route to change the long‐lived charge into the highly active species for catalysis, thus making the long‐afterglow phosphors with high charge storage capacity a highly efficient round‐the‐clock photocatalyst.

Decoupled Artificial Photosynthesis

“…For instance, Lotsch et al demonstrated that highly reductive radicals with lifetimes longer than the diurnal cycle can be formed on a cyanamide-functionalized carbon nitride polymeric network under irradiation (Figure 5g). [48] Then, the trapped electrons were released for hydrogen production in the dark, thus [40] e) Ti-MIL-125-NH 2 with the formation of reductive Ti 3 + intermediate induced by the ligand-to-metal charge transfer (LMCT), [46] f) metal oxides with oxygen vacancies as the electron trapping sites, [47] Copyright 2022, Wiley-VCH GmbH, Weinheim, g) functionalized C x N y , [48] h) MOF confined Ru-bpy hybrids, [50] i) Cu-based metal complex that can store and release two electrons, [51] and j) POMs/Ru-bpy molecular dyad integrating the properties of photosensitizers and photocatalysts. [52] Copyright 2022, Nature Publishing Group.…”

“…d)-j) Typical decoupled photocatalytic systems that undergo light harvesting and charge transfer and separation processes under irradiation and produce chemicals or fuels in the dark. d) Conjugated organic polymer films (COPFs) bearing tautomer motifs and performing overall CO 2 splitting,[40] e) Ti-MIL-125-NH 2 with the formation of reductive Ti 3 + intermediate induced by the ligand-to-metal charge transfer (LMCT),[46] f) metal oxides with oxygen vacancies as the electron trapping sites,[47] Copyright 2022, Wiley-VCH GmbH, Weinheim, g) functionalized C x N y ,[48] h) MOF confined Ru-bpy hybrids,[50] i) Cu-based metal complex that can store and release two electrons,[51] and j) POMs/Ru-bpy molecular dyad integrating the properties of photosensitizers and photocatalysts [52]. Copyright 2022, Nature Publishing Group.…”

A brief review: the application of long afterglow luminescent materials in environmental remediation

“…Thus, the abundant CO 2 feedstock has driven researchers to achieve CO 2 chemical utilization. 67 Accordingly, CO 2 conversion using sunlight-driven photocatalysts is a crucial technique for closing the carbon cycle; however, intermittent solar flux is the bottleneck of catalysis. Thus, to address this, Pei et al successfully synthesized oxygen-deficient Vo-SMSED, possessing electron transfer paths and active sites.…”

Emerging heterostructured C3N4photocatalysts for photocatalytic environmental pollutant elimination and sterilization

“…[2][3][4][5][6] Furthermore, the photocatalysis method has been considered as a feasible means for harvesting light energy in chemical bonds through different photoexcited reactions, like organic pollutant oxidation, CO 2 reduction, H 2 O splitting, H 2 O 2 preparation and valued organics synthesis. [7][8][9][10][11][12][13][14][15] Over recent decades, a considerable number of semiconductors such as metal oxides, metal sulfides, and nitride materials have been exploited as photocatalysts for various photocatalytic reactions. [16][17][18][19][20] Among them, graphitic carbon nitride (g-C 3 N 4 ) possessing outstanding light-response ability has shown great promise because of its facile synthesis, tunable band gap structure, good chemical stability, and environmentally friendly properties.…”