单原子Pd催化剂活化分子氧用于肉桂醇氧化

doi:10.1016/S1872-2067(20)63651-8

催化学报 ›› 2020, Vol. 41 ›› Issue (12): 1812-1817.DOI: 10.1016/S1872-2067(20)63651-8

单原子Pd催化剂活化分子氧用于肉桂醇氧化

商庆浩^a,b, 唐南方^a, 齐海峰^a,b, 陈帅^a, 许国梁^a, 吴春田^a, 潘晓丽^a, 王晓东^a, 丛昱^a

a 中国科学院大连化学物理研究所中国科学院航天催化材料重点实验室, 辽宁大连 116023;
b 中国科学院大学, 北京 100049

收稿日期:2020-02-27 修回日期:2020-03-31 出版日期:2020-12-18 发布日期:2020-08-14
通讯作者: 丛昱, 唐南方
基金资助:
国家自然科学基金（21802134）；国家科技重大专项（2017-III-0005-0030）.

A palladium single-atom catalyst toward efficient activation of molecular oxygen for cinnamyl alcohol oxidation

Qinghao Shang^a,b, Nanfang Tang^a, Haifeng Qi^a,b, Shuai Chen^a, Guoliang Xu^a, Chuntian Wu^a, Xiaoli Pan^a, Xiaodong Wang^a, Yu Cong^a

a CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-02-27 Revised:2020-03-31 Online:2020-12-18 Published:2020-08-14
Supported by:
This work was supported by National Natural Science Foundation of China (21802134) and National Science and Technology Major Project of China (2017-III-0005-0030).

摘要/Abstract

摘要： 在温和条件下借助分子氧实现有机分子（包括醇类、糖类、碳烃化合物、CO等）的选择性氧化是现代化学中重要的研究课题.其中，在温和条件下高效的活化氧气一直被视为分子氧氧化反应的关键步骤和巨大挑战.一般而言，得益于适宜的配位结构、均一的活性金属中心和配体，有机金属催化剂在醇氧化反应中一直有着广泛的应用，但同时存在着难以分离和回收的问题.而与均相催化剂一样有着高原子利用率的单原子催化剂自其概念报道以来，在催化领域吸引了越来越多的注意力.愈来愈多的研究者也开始涉足研究单原子催化剂在分子氧氧化反应中的应用.尽管已经取得一些不错的结果，但分子氧的活化机制以及催化反应路径仍然有很多疑问有待揭示.
本文在富含不饱和五配位铝的氧化铝载体上分别负载了单原子分散和纳米颗粒的Pd，制备了相同负载量的Pd/Al₂O₃催化剂.其中单原子Pd₁/Al₂O₃催化剂表现出非常好的肉桂醇氧化活性，在80℃反应8h能达到92%肉桂醇转化率，其TOF值是纳米颗粒Pd/Al₂O₃催化剂的15.5倍，与类似反应条件下的其他文献报道的数值相当.我们还通过一系列表征提出了反应过程中具体的O₂的活化机理和进一步的整体反应路径.
XPS，XANES，CO-DRIFT等结果表明，Pd/Al₂O₃和Pd₁/Al₂O₃催化剂中Pd的价态迥然不同，结合二者催化活性的显著差异，我们推断部分还原的Pd^δ+正价态物种才是Pd₁/Al₂O₃催化剂中真正的活性中心.进一步结合²⁷Al NMR的表征结果发现，Pd₁/Al₂O₃催化剂中的Pd与富含不饱和五配位铝（Al_penta³⁺）的Al₂O₃之间形成强相互作用，从而导致其以单原子形式分散并具有独特的电子性质.为了揭示本工作中所涉及的具体的活化过程和反应机理，我们进行了原位紫外光谱和电子顺磁共振光谱表征，发现肉桂醇分子吸附到单原子Pd上后，生成了部分脱氢的中间产物，同时分子氧在单原子Pd上活化，形成了单线态氧活性物种（¹O₂）.
综合以上结果，我们推导出一个在Pd₁/Al₂O₃上进行的活化分子氧进行肉桂醇选择性氧化的分步反应路径.首先，肉桂醇分子吸附到单原子Pd上，发生电荷转移生成部分脱氢的中间产物，同时，分子氧也在Pd上活化，生成单线态氧物种¹O₂，然后和肉桂醇中间产物反应，生成目标产物肉桂醛.

关键词: 单原子催化, 钯, 醇氧化, 氧气活化, 金属载体相互作用

Abstract: Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging, with the activation of molecular oxygen (O₂) as a crucial capability of the catalysts. Herein, we demonstrate that an Al₂O₃-supported Pd single-atom catalyst leads to higher activity and selectivity compared to Pd nanoparticles for the oxidation of cinnamyl alcohol. The Al₂O₃ support used in this study is rich in coordinately unsaturated Al³⁺ sites, which are apt for binding to Pd atoms through oxygen bridges and present a distinct metal-support interaction (MSI). The suitable MSI then leads to a unique electronic characteristic of the Pd single atoms, which can be confirmed via X-ray photoelectron spectroscopy, normalized X-ray absorption near-edge structure, and diffuse reflectance Fourier transform infrared spectroscopy. Moreover, this unique electronic state is proposed to be responsible for its high catalytic activity. With the help of in-situ UV-vis spectra and electron spin resonance spectra, a specific alcohol oxidation route with O₂ activation mechanism is then identified. Active oxygen species behaving chemically like singlet-O₂ are generated from the interaction of O₂ with Pd₁/Al₂O₃, and then oxidize the partially dehydrogenated intermediates produced by the adsorbed allylic alcohols and Pd atoms to the desired alkenyl aldehyde. This work provides a promising path for the design and development of high-activity catalysts for aerobic oxidation reactions.

Key words: Single-atom catalysis, Palladium, Alcohol oxidation, Oxygen activation, Metal support interaction

商庆浩, 唐南方, 齐海峰, 陈帅, 许国梁, 吴春田, 潘晓丽, 王晓东, 丛昱. 单原子Pd催化剂活化分子氧用于肉桂醇氧化[J]. 催化学报, 2020, 41(12): 1812-1817.

Qinghao Shang, Nanfang Tang, Haifeng Qi, Shuai Chen, Guoliang Xu, Chuntian Wu, Xiaoli Pan, Xiaodong Wang, Yu Cong. A palladium single-atom catalyst toward efficient activation of molecular oxygen for cinnamyl alcohol oxidation[J]. Chinese Journal of Catalysis, 2020, 41(12): 1812-1817.

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单原子Pd催化剂活化分子氧用于肉桂醇氧化

A palladium single-atom catalyst toward efficient activation of molecular oxygen for cinnamyl alcohol oxidation

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