Synergic Delocalized‐Conjugate and Electron‐Deficient Effect and Mesoporous Channel Promote Photocatalytic Coupling H₂ Evolution with Benzyl‐Alcohol Oxidation

Abstract

Photocatalytic merging H2 evolution with benzyl‐alcohol (BA) oxidation offers a promising approach to producing H2 and value‐added chemicals due to water photocatalysis with a sluggish kinetic process and gas‐mixed H2/O2 gas security concern. Herein, incorporating electron‐deficient pyromellitic dianhydride into large π‐conjugate polymeric carbon nitride builds an effective in‐electric field (IEF). The resultant photocatalyst shows the dependence on the ratio of H2O and BA for H2 and benzaldehyde production, particularly the highest yield rate of H2 (13.87) and benzaldehyde (7.71 mmol h−1 g−1), 69.2% at 400 nm of internal quantum efficiency for H2‐evolution, and 2.15% of solar‐to‐hydrogen efficiency under simulated AM 1.5G irradiation. Mechanism analysis suggests that the strong driving force of effective IEF originates from the cooperating large delocalized π‐conjugate and electron‐deficient effect, which overwhelms the intrinsic binding energy of charge carrier to enhance its separation and migration efficiency dramatically. Moreover, extended light response and mesoporous channel in photocatalyst improve the absorption edge and tail, the n→π* transition, and mass transport of BA. In situ characterizations revealed that the enhanced H2 production is due to the releasing protons from BA oxidation via carbon‐centered radical‐mediated. These findings provide a novel strategy and deep understanding of photocatalytic coupling H2 with added‐value chemical production.

Construction of a Dual-Function Mo-ZIS@Ti for Photocatalytic Benzyl Alcohol Oxidation and Hydrogen Evolution Performance

“…They are fully utilizing photogenerated electrons and holes, thereby achieving the green economy goal of simultaneously producing H 2 and high value-added industrial products. For example, benzyl alcohol (BA) is used as a hole sacrificial agent to produce benzaldehyde (BAD) while obtaining green hydrogen. , BAD is an important chemical intermediate and industrial raw material, and the development of green and sustainable photocatalytic production technology is of great significance. − Therefore, it is extremely important to develop bifunctional catalysts favorable for photocatalytic hydrogen production and highly selective BA oxidation.…”

Nitric Acid‐Mediated Artificial Urea Photo‐Synthesis With N2 And CO2

“…Theoretically, the development of a one-pot urea synthesis approach utilizing nitrogen as feedstock and sustainable solar energy represents a groundbreaking strategy to overcome this challenge and begins to sprout growth. [9][10][11][12][13][14][15][16] However, the limited studies conducted thus far have been based on unidirectional gas phase co-reduction of two renowned inert molecules (N 2 and CO 2 ). [9][10][11][12] The disparity in physical properties, structure, and catalytic kinetics between N 2 and CO 2 poses stringent demands for the design of key catalysts, reaction control, mass transfer, and other aspects.…”