Calcination‐regulated Microstructures of Donor‐Acceptor Polymers towards Enhanced and Stable Photocatalytic H₂O₂ Production in Pure Water

Abstract

Regulating molecular structure of donoracceptor (D-A) polymer is a promising strategy to improve photoactivity. Herein, a porous nanorod-like D-A polymer is synthesized via a strategy of supramolecular chemistry combined with subsequent calcination treatment. This polymer consists of benzene rings (D) and triazine (A) that are linked by amido bond (À CONHÀ ). À CONHÀ further partially cracks into cyano groups (À C�N) (A) under calcination. The ratio of benzene to triazine could be tuned to adjust the À C�N content by varying the calcination atmosphere. Such regulation of molecular structure could modulate the band structure of D-A polymer and endow it with unique porous nanorod-like morphology, leading to the achievement of two-electron oxygen reduction and twoelectron water oxidation and the improvement of exciton splitting, O 2 adsorption and activation. These merits synergistically ensure a highly efficient and stable photocatalytic H 2 O 2 production in pure water.

Unveiling the Dynamic Evolution of Single-Atom Co Sites in Covalent Triazine Frameworks for Enhanced H2O2 Photosynthesis

“…Figure a,b shows the time-dependent DRIFTS spectra of Co SA /Tr-CTF and Co SA /Py-CTF under visible light irradiation and O 2 saturation conditions. After 30 min of dark O 2 saturation, both spectra display obvious peaks corresponding to O 2 absorption at 820–858 cm –1 . , This is attributed to the chemisorption process of O 2 on the photocatalyst surface, where the Co single-atom serves as the primary active site. Subsequent monitoring at 10 min intervals following light exposure reveals a gradual decrease in *O 2 peaks for both Co SA /Tr-CTF and Co SA /Py-CTF, indicating O 2 involvement in photocatalytic H 2 O 2 generation.…”

“…Figure6a,b shows the time-dependent DRIFTS spectra of Co SA /Tr-CTF and Co SA /Py-CTF under visible light irradiation and O 2 saturation conditions. After 30 min of dark O 2 saturation, both spectra display obvious peaks corresponding to O 2 absorption at 820−858 cm −1 12,36. This is attributed to the chemisorption process of O 2 on the photocatalyst surface, where the Co single-atom serves as the primary active site.…”

Hydrochar-Supported NiFe2O4Nanosheets with a Tailored Microstructure for Enhanced CO2Photoreduction to Syngas

“…There is a high demand for renewable energy and associated development strategies in addition to the conventional technologies for achieving energy conservation and emission reduction. Solar-driven CO 2 reduction has garnered significant attention in recent years. − However, despite substantial efforts made to develop high-efficiency photocatalysts for CO 2 reduction, sunlight utilization and quantum efficiency are too poor to meet the requirements of practical application. − To fulfill the crucial mission of CO 2 photoreduction toward artificial photosynthesis using solar energy, further enhancement in CO 2 photoconversion efficiency is inevitable but highly challenging. It has been reported that employing cocatalysts represents an effective approach to enhancing the catalytic activity of the CO 2 photoreduction. − Cocatalysts can facilitate the transport of photoinduced charge carriers and activate CO 2 molecules to reduce the energy barrier for CO 2 reduction, both significantly contributing to elevated efficiency in photocatalytic CO 2 reduction. , Although there are extensive investigations on noble metals and complex coordination compounds as highly efficient cocatalysts, their utilization is limited due to scarcity and high cost.…”

Unraveling Rigidified Superexchange Couplings in Organic Donor–Acceptor Polymers for Boosting the Photocatalytic Reduction of Nitrate

“…22 Intramolecular charge separation and migration occur via larger dipole moment and superexchange (SE) coupling in the opposite way to electron affinity. 23,24 In fact, SE coupling plays an important role in intramolecular charge transfer. 25,26 However, most of the D−A-based PDI dimers with flexible geometries and complex compositions (such as DAA, ADA, or AAD) show rotational disorder and reorganization energy loss.…”