通过调整氢安息香中间体的吸附方向精确控制 Cα-H 键活化或 O-H 键活化,实现苄醇与去氧安息香或安息香的特定光催化 C-C 偶联

IF 13.1 1区 化学 Q1 CHEMISTRY, PHYSICAL
Zongyang Yue, Guanchu Lu, Wenjing Wei, Yanan Deng, Luxi Yang, Shibo Shao, Xianfeng Chen, Yi Huang, Jianhua Qian* and Xianfeng Fan*, 
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引用次数: 0

摘要

苄醇 (BA) 是一种主要的生物质衍生物,可通过光催化 C-C 偶联反应进一步转化为脱氧安息香 (DOB) 和安息香 (BZ),作为工业应用的高价值产品。光催化过程包含两个反应步骤,即(1)BA 与氢化安息香(HB)中间产物的 C-C 偶联,以及(2)HB 脱水生成 DOB 或 HB 脱氢生成 BZ。我们发现 DOB 或 BZ 的生成主要取决于 HB 中 Cα-H 或 O-H 键的活化。本研究精心设计了相结 CdS 光催化剂和 Ni/CdS 光催化剂,通过调整 HB 在光催化剂表面的吸附取向来精确控制 HB 中 Cα-H 或 O-H 键的活化。将 HB 中的 Cα-H 基团定向到 CdS 表面后,1.39 eV 的 Cα-H 键解离能 (BDE) 低于 2.69 eV 的 O-H 键解离能 (BDE),从而提高了 DOB 的选择性。相反,在 Ni/CdS 光催化剂上,HB 中的 O-H 基团朝向光催化剂表面。O-H 键形成 BZ 的 BDE 为 1.11 eV,低于 Cα-H 键形成 DOB 的 BDE(1.33 eV),从而提高了 BZ 的选择性。因此,在可见光照射 9 小时后,CdS 光催化剂可将 BA 完全转化为 80.4% 的 DOB,而 0.3% Ni/CdS 光催化剂仅在 5 小时后就可将 BA 完全转化为 81.5% 的 BZ。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Specific Photocatalytic C–C Coupling of Benzyl Alcohol to Deoxybenzoin or Benzoin by Precise Control of Cα–H Bond Activation or O–H Bond Activation by Adjusting the Adsorption Orientation of Hydrobenzoin Intermediates

Benzyl alcohol (BA) is a major biomass derivative and can be further converted into deoxybenzoin (DOB) and benzoin (BZ) as high-value products for industrial applications through photocatalytic C–C coupling reaction. The photocatalytic process contains two reaction steps, which are (1) the C–C coupling of BA to hydrobenzoin (HB) intermediates and (2) either dehydration of HB to DOB or dehydrogenation of HB to BZ. We found that generation of DOB or BZ is mainly determined by the activation of Cα–H or O–H bonds in HB. In this study, phase junction CdS photocatalysts and Ni/CdS photocatalysts were elaborately designed to precisely control the activation of Cα–H or O–H bonds in HB by adjusting the adsorption orientation of HB on the photocatalyst surfaces. After orienting the Cα–H groups in HB on the CdS surfaces, the Cα–H bond dissociation energy (BDE) at 1.39 eV is lower than the BDE of the O–H bond at 2.69 eV, therefore improving the selectivity of the DOB. Conversely, on Ni/CdS photocatalysts, the O–H groups in HB orient toward the photocatalyst surfaces. The BDE of the O–H bonds is 1.11 eV to form BZ, which is lower than the BDE of the Cα–H bonds to the DOB (1.33 eV), thereby enhancing the selectivity of BZ. As a result, CdS photocatalysts can achieve complete conversion of BA to 80.4% of the DOB after 9 h of visible light irradiation, while 0.3% Ni/CdS photocatalysts promote complete conversion of BA to 81.5% of BZ after only 5 h. This work provides a promising strategy in selective conversion of BA to either DOB or BZ through delicate design of photocatalysts.

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来源期刊
ACS Catalysis
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.
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