B/g-C3N4 for Selectively Regulating Oxygen-Guided Photocatalytic Oxidation of Cinnamaldehyde to Benzaldehyde: Effects of Boron Sources

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-01-02 DOI:10.1021/acscatal.4c05427

Xuan Luo, Bingbing Li, Tongming Su, Xinling Xie, Zuzeng Qin, Hongbing Ji

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Abstract

Natural benzaldehyde, an important spice-type flavor component and raw pharmaceutical material, is scarcely due to the escalating demand and consumer preference for natural foods. To mitigate this issue, the present study aimed to investigate the oxygen-driven selective oxidation of cinnamaldehyde to benzaldehyde under visible light. K₂B₄O₇·4H₂O and KBH₄ were used as boron sources to modify the g-C₃N₄ photocatalyst for regulating the cinnamaldehyde conversion rate and benzaldehyde selectivity. A series of characterization techniques revealed improvements in the photocatalytic performance of the modified catalysts─that is, g-C₃N₄ doped with boron derived from K₂B₄O₇·4H₂O or KBH₄ (BCN or KBCN, respectively; 10% or 25% increase in cinnamaldehyde conversion rate, 11% or 34% increase in benzaldehyde selectivity). These enhancements were due to the doped boron and the generated nitrogen vacancy. Moreover, the abilities of BCN and KBCN to adsorb oxygen and cinnamaldehyde improved. The conjugated aldehyde group and planar molecular structure of cinnamaldehyde are critical to the selective oxidation of the >C═C< unit to obtain the aldehyde. The mechanism underlying the photocatalytic action of KBCN was established, and the reasons for the superior photocatalytic performance of KBCN compared with that of BCN were determined. Essentially, the reducible boron source─KBH₄─produced a radical boron site on the surface of g-C₃N₄, which collided with ^•O₂^– to generate another vital oxygen species ¹O₂. Subsequently, the electrons transferred to the surface of KBCN could be captured by the adsorbed oxygen molecules to regenerate ^•O₂^–. Furthermore, the hole produced on the catalyst surface during visible-light illumination promoted its reaction with ^•O₂^– by obtaining an electron from the >C═C< unit of cinnamaldehyde. Overall, this study paves the way for future applications and research on the selective oxidation of the >C═C< group in α,β-unsaturated carbonyl compounds.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.