Solvated Electrons for Photochemistry Syntheses Using Conjugated Carbon Nitride Polymers

Abstract

Solvated electrons have attracted increasing research interest due to their strong reducing ability. However, the generation and utilization of solvated electrons in photocatalytic systems are rarely reported owing to the challenges in synthesis and their complex structures. Here, we present a photocatalytic system by accessing laboratory-scale concentrations of ammoniated electrons. Under visible light irradiation, ammoniated electrons are achieved by a cyanamide functionalized and potassium heptazine based melon polymer (PC-HM) in the presence of an electron donor, which are stable for days. This PC-HM can produce ammoniated electrons at room temperature to reduce dioxygen, thus enabling the production of H 2 O 2 coupled with the selective oxidation of alcohols under visible light illumination. This work presents the possibility to take advantage of ammoniated electrons for solar energy conversion in energy and advanced organic chemistry.

Emerging Concepts in Carbon Nitride Organic Photocatalysis

“…For K-PHI, three main preparation methods have been reported: 1) mechanochemical pretreatment of 5-aminotetrazole in LiCl/KCl eutectic mixture followed by calcination at 550°C; [100] 2) from dicyanamide, KSCN and potassium melonate penta-hydrated calcinated at 500°C or from trichloromelamine; [99l] 3) KSCN and LiCl calcinated at 550°C. [101] At the same time, alkali metal poly(heptazine imide)s (M-PHIs) are prepared via an ionothermal approach employing Na, K and Cs based salts. [100] Such cations compensate for negative charges of deprotonated amino functionalities, mediating the interaction between different layers and giving rise to a more ordered structure.…”

Ionic Carbon Nitrides in Solar Hydrogen Production and Organic Synthesis: Exciting Chemistry and Economic Advantages

“…Zheng and Quan generated a long‐lived radical of g‐C 3 N 4 modified with cyano‐groups (CCN) and followed by the addition of O 2 producing H 2 O 2 in the dark . Ou and Wang applied this feature of carbon nitrides for simultaneous alcohols dehydrogenation and H 2 O 2 production . Finally, Lotsch et al.…”

Visible‐Light‐Activated C−C Bond Cleavage and Aerobic Oxidation of Benzyl Alcohols Employing BiMXO5 (M=Mg, Cd, Ni, Co, Pb, Ca and X=V, P)

“…Thus, on photon absorption, the electron-hole separation occurs with the carriers becoming trapped in surface defect states. [51] Adsorption of the substrates occurs at those sites, which are also responsible for possible emissive recombination. The trapped electrons are transferred to surface adsorbed molecular oxygen, while the holes transfer to the surface adsorbed benzyl alcohol molecules.…”