Molecular Level Modulation of Anthraquinone‐containing Resorcinol‐formaldehyde Resin Photocatalysts for H₂O₂ Production with Exceeding 1.2 % Efficiency

Abstract

Designing polymeric photocatalysts at the molecular level to modulate the photogenerated charge behavior is a promising and challenging strategy for efficient hydrogen peroxide (H 2 O 2 ) photosynthesis.Here, we introduce electron-deficient 1,4-dihydroxyanthraquinone (DHAQ) into the framework of resorcinolformaldehyde (RF) resin, which modulates the donor/ acceptor ratio from the perspective of molecular design for promoting the charge separation. Interestingly, H 2 O 2 can be produced via oxygen reduction and water oxidation pathways, verified by isotopic labeling and in situ characterization techniques. Density functional theory (DFT) calculations elucidate that DHAQ can reduce the energy barrier for H 2 O 2 production. RF-DHAQ exhibits excellent overall photosynthesis of H 2 O 2 with a solar-to-chemical conversion (SCC) efficiency exceeding 1.2 %. This work opens a new avenue to design polymeric photocatalysts at the molecular level for high-efficiency artificial photosynthesis.

Shear Stress Triggers Ultrathin-Nanosheet Carbon Nitride Assembly for Photocatalytic H2O2 Production Coupled with Selective Alcohol Oxidation

“…The peaks assigned to O 2 – * (1142 cm –1 ), OOH* (1217 cm –1 ), and HOOH* (1358 cm –1 ) intermediate species were observed, and the peak intensity increased gradually with increasing illumination time. It indicates that ASCN-3 undergoes a stepwise single-electron oxygen reduction process. , Oxygen is first absorbed on the catalyst surface to form *O 2 that further converts into *OOH intermediates by combining with protons. Subsequently, *OOH couples with another proton to generate *H 2 O 2 and then detaches from the catalyst surface to finally produce H 2 O 2 .…”

“…It indicates that ASCN-3 undergoes a stepwise single-electron oxygen reduction process. 61,62 Oxygen is first absorbed on the catalyst surface to form *O 2 that further converts into *OOH intermediates by combining with protons. Subsequently, *OOH couples with another proton to generate *H 2 O 2 and then detaches from the catalyst surface to finally produce H 2 O 2 .…”

Proton reservoirs in polymer photocatalysts for superior H2O2 photosynthesis

“…The different performances in H 2 O 2 photosynthesis among QAPs were likely due to the adjustment of the reaction pathway by hydroquinone units. 42 To focus on the reductive half reaction, a photoelectrochemical test was conducted. In linear sweep voltammetry (LSV) from 0 to À0.6 V (vs. Ag/AgCl) in air-saturated Na 2 SO 4 electrolyte (Fig.…”

Synergistic Promotion of the Photocatalytic Preparation of Hydrogen Peroxide (H2O2) from Oxygen by Benzoxazine and Si─O─Ti Bond

“…[11] Currently, the most commonly used photocatalysts for the photocatalytic synthesis of H 2 O 2 are inorganic materials, for instance TiO 2 /RF S-scheme heterojunctions, [12] Sn/Pd/Al 2 O 3 alloy catalysts, [13] and metal-organic frameworks. [14] Organic polymer as powder photocatalysts for H 2 O 2 production is flourishing development [7,15,16] in particularly donor-acceptor (D-A) polymer, [17] phenolic resins, [18] and other conjugated polymers. [19] The flexibility of organic polymers at the molecular level enhances their optoelectronic and surface catalytic properties, leading to improved reaction performance over time.…”