High-performance photocatalytic nonoxidative conversion of methane to ethane and hydrogen by heteroatoms-engineered TiO<sub>2</sub>.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 35589743.
- Also identified by DOI 10.1038/s41467-022-30532-z and PMC identifier 9119979.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Nonoxidative coupling of methane (NOCM) is a highly important process to simultaneously produce multicarbons and hydrogen. Although oxide-based photocatalysis opens opportunities for NOCM at mild condition, it suffers from unsatisfying selectivity and durability, due to overoxidation of CH<sub>4</sub> with lattice oxygen. Here, we propose a heteroatom engineering strategy for highly active, selective and durable photocatalytic NOCM. Demonstrated by commonly used TiO<sub>2</sub> photocatalyst, construction of Pd-O<sub>4</sub> in surface reduces contribution of O sites to valence band, overcoming the limitations. In contrast to state of the art, 94.3% selectivity is achieved for C<sub>2</sub>H<sub>6</sub> production at 0.91 mmol g<sup>-1</sup> h<sup>-1</sup> along with stoichiometric H<sub>2</sub> production, approaching the level of thermocatalysis at relatively mild condition. As a benchmark, apparent quantum efficiency reaches 3.05% at 350 nm. Further elemental doping can elevate durability over 24 h by stabilizing lattice oxygen. This work provides new insights for high-performance photocatalytic NOCM by atomic engineering.