Research groups led by Prof. XIONG Yujie, Prof. LIU Dong and Prof. ZHANG Ning from the University of Science and Technology of China (USTC) developed a novel catalyst Au/BiOx-TiO2 for efficient, selective and stable photocatalytic light-driven oxidative coupling of methane (OCM). The study was published in Science Advances .
Producing value-added chemicals through OCM is a promising approach to alleviate energy issues. However, OCM requires strict reaction conditions due to its high reaction energy barrier. Compared with the anaerobic coupling of methane, the aerobic coupling of methane has a lower reaction barrier, yet it still faces challenges such as poor product selectivity and slow reaction rate. Therefore, it is necessary to design efficient catalysts and optimize reaction pathways to address issues of stability, selectivity and reactivity in OCM.
The group designed and synthesized a dual-site photocatalyst, Au/BiOx-TiO2, which is a composite system of BiO x clusters and Au nanoparticles. The BiO x clusters are uniformly distributed around the Au nanoparticles, tightly bound together. The synergistic effect of Au nanoparticles and BiOx clusters enables the activation of C-H bonds in CH 4 and the coupling of CH 3 at separate sites, preventing overoxidation of CH 4 at a single site. This significantly improves the selectivity for C 2+ products.
Using a self-designed flow reactor, the photocatalytic OCM achieved a CH 4 conversion rate of 20.8 mmol g −1 h −1 and a C 2 H 6 production rate of 9.6 mmol g −1 h −1 . The selectivity for C 2+ products exceeded 97%, with stability lasting up to 50 hours, outperforming many previously reported catalysts.
The group also verified mechanism of lattice oxygen participation in OCM based on in-situ spectroscopy and theoretical calculations. The lattice oxygen can effectively enhance the C-H activation, and introducing an appropriate amount of oxygen can replenish lattice oxygen via the Mars-Van Krevelen mechanism, achieving high selectivity and stability simultaneously.
This work highlights the importance of employing catalytic site engineering in chemical reaction and sheds lights on sustainable and energy- efficient CH 4 conversion.
Science Advances
Highly efficient, selective, and stable photocatalytic methane coupling to ethane enabled by lattice oxygen looping