国家纳米科学中心唐智勇团队报道了在预先筛选负载型催化剂上控制甲烷光氧化制甲酸。相关研究成果发表在2024年6月4日出版的《美国化学会杂志》。

高效的甲烷光氧化制甲酸（HCOOH）已成为一种可持续的方法，可以同时产生增值化学品和利用可再生能源。然而，持续的挑战在于实现HCOOH形成的高产率和选择性，这主要是由于甲烷活化后调节中间转化和解吸的复杂性。

该文中，研究人员采用第一性原理计算作为综合指导工具，发现通过精确控制贵金属助催化剂上的O₂活化过程，和含碳中间体在金属氧化物载体上的吸附强度，可以微调甲烷光氧化产物的选择性。具体而言，包含Pd纳米颗粒和单斜WO₃（Pd/WO₃）的双功能催化剂，将具有最佳的O₂活化动力学和中间氧化/脱附屏障，从而促进HCOOH的形成。

实验证明，在室温下使用分子O₂的全光谱光照射下，Pd/WO₃催化剂实现了4.67 mmol gcat^–1 h^–1的非凡HCOOH产率和62%的高选择性。值得注意的是，这些结果显著优于在相同条件下运行的最先进的光催化系统。

附：英文原文

Title: Steering Photooxidation of Methane to Formic Acid over A Priori Screened Supported Catalysts

Author: Yuheng Jiang, Yingying Fan, Xiaolong Liu, Jun Xie, Siyang Li, Kefu Huang, Xiaoyu Fan, Chang Long, Lulu Zuo, Wenshi Zhao, Xu Zhang, Juehan Sun, Peng Xu, Jiong Li, Fan Dong, Ting Tan, Zhiyong Tang

Issue&Volume: June 4, 2024

Abstract: Efficient methane photooxidation to formic acid (HCOOH) has emerged as a sustainable approach to simultaneously generate value-added chemicals and harness renewable energy. However, the persistent challenge lies in achieving a high yield and selectivity for HCOOH formation, primarily due to the complexities associated with modulating intermediate conversion and desorption after methane activation. In this study, we employ first-principles calculations as a comprehensive guiding tool and discover that by precisely controlling the O2 activation process on noble metal cocatalysts and the adsorption strength of carbon-containing intermediates on metal oxide supports, one can finely tune the selectivity of methane photooxidation products. Specifically, a bifunctional catalyst comprising Pd nanoparticles and monoclinic WO3 (Pd/WO3) would possess optimal O2 activation kinetics and an intermediate oxidation/desorption barrier, thereby promoting HCOOH formation. As evidenced by experiments, the Pd/WO3 catalyst achieves an exceptional HCOOH yield of 4.67 mmol gcat–1 h–1 with a high selectivity of 62% under full-spectrum light irradiation at room temperature using molecular O2. Notably, these results significantly outperform the state-of-the-art photocatalytic systems operated under identical condition.

DOI: 10.1021/jacs.4c03083

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c03083