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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B/g-C3N4选择性调节氧引导光催化氧化肉桂醛制苯甲醛：硼源的影响

天然苯甲醛是一种重要的香料型香料成分和原料药，随着人们对天然食品的需求和偏好的不断增加，天然苯甲醛的使用量也越来越少。为了解决这一问题，本研究旨在研究在可见光下，氧驱动肉桂醛选择性氧化成苯甲醛。以K2B4O7·4H2O和KBH4为硼源，对g-C3N4光催化剂进行改性，调节肉桂醛的转化率和苯甲醛的选择性。一系列表征技术表明，改性后的催化剂的光催化性能有所改善，即g-C3N4掺杂硼分别由K2B4O7·4H2O或KBH4 （BCN）或KBCN衍生；肉桂醛转化率提高10%或25%，苯甲醛选择性提高11%或34%)。这些增强是由于掺杂硼和产生的氮空位。此外，BCN和KBCN对氧和肉桂醛的吸附能力也有所提高。肉桂醛的共轭醛基团和平面分子结构对C = C<；单位得到乙醛。建立了KBCN光催化作用的机理，确定了KBCN光催化性能优于BCN的原因。从本质上讲，可还原硼源──KBH4──在g-C3N4表面产生了一个自由基硼位点，并与•O2 -发生碰撞，生成了另一种重要的氧物质1O2。随后，转移到KBCN表面的电子可以被吸附的氧分子捕获以再生•O2 -。此外，在可见光照射下在催化剂表面产生的空穴通过从>；C = C<；肉桂醛单位。总的来说，这项研究为C = C<；选择性氧化的未来应用和研究铺平了道路基团在α，β-不饱和羰基化合物。

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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.