完全暴露的铂簇催化剂能够实现多元醇向二元羧酸的级联氧化。

Fully exposed Pt cluster catalysts enable cascade oxidation of polyol to dicarboxylic acid.

作者信息

Yan Hao, Li Jie, Rao Zhiqiang, Liao Ying, Li Yaqian, Zhou Xin, Meng Fanchun, Li Lina, Zhang Bin, Qin Yong, Zhao Hui, Liu Yibin, Chen Xiaobo, Feng Xiang, Chen De, Yang Chaohe, Ma Ding

机构信息

State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao, China.

Beijing National Laboratory for Molecular Sciences, New Cornerstone Science Laboratory, College of Chemistry and Molecular Engineering, Peking University, Beijing, China.

出版信息

Nat Commun. 2025 Jul 31;16(1):7030. doi: 10.1038/s41467-025-62192-0.

DOI:10.1038/s41467-025-62192-0

PMID:40745176

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12314095/

Abstract

The polyol oxidation to dicarboxylic acid, a crucial value-accretive reaction, is still challenging due to the paradoxical relationship between efficient activation of C-H bond and rapid desorption of carboxylic acid. Herein, we break this contradiction by constructing fully exposed Pt cluster supported on hydroxyapatite (Pt/HAP) to promote two primary hydroxyl groups of polyol oxidation to dicarboxylic acid. Such fully exposed Pt cluster with an average Pt-Pt coordination number of ∼3.4 exhibits unique electronic properties between Pt single atom and nanoparticle Pt. Specifically, gradient charge distribution in fully exposed Pt cluster shows a special synergistic effect in the C-H bond activation. Moreover, the d-band centre of fully exposed Pt cluster moderately far from the Fermi level weakens the adsorption of C = O bond in dicarboxylic acid product. As a result, fully exposed Pt/HAP with better catalytic activity (turnover frequency: 619.1 h) shows nearly 10 times and 1.5 times of tartronic acid selectivity than Pt single atom and nanoparticle Pt catalysts, respectively. The system is also applicable to other polyol oxidation to dicarboxylic acids with noteworthy catalytic results.

摘要

多元醇氧化为二元羧酸是一个关键的增值反应，但由于C-H键的有效活化与羧酸的快速脱附之间存在矛盾关系，该反应仍然具有挑战性。在此，我们通过构建负载在羟基磷灰石上的完全暴露的铂簇（Pt/HAP）来打破这一矛盾，以促进多元醇氧化为二元羧酸的两个主要羟基。这种平均Pt-Pt配位数约为3.4的完全暴露的铂簇在铂单原子和纳米颗粒铂之间表现出独特的电子性质。具体而言，完全暴露的铂簇中的梯度电荷分布在C-H键活化中显示出特殊的协同效应。此外，完全暴露的铂簇的d带中心适度远离费米能级，削弱了二元羧酸产物中C=O键的吸附。结果，具有更好催化活性（周转频率：619.1 h⁻¹）的完全暴露的Pt/HAP对酒石酸的选择性分别比铂单原子和纳米颗粒铂催化剂高近10倍和1.5倍。该体系也适用于其他多元醇氧化为二元羧酸的反应，具有显著的催化效果。