Potassium‐Ion‐Assisted Regeneration of Active Cyano Groups in Carbon Nitride Nanoribbons: Visible‐Light‐Driven Photocatalytic Nitrogen Reduction

As a metal‐free nitrogen reduction reaction (NRR) photocatalyst, g‐C₃N₄ is available from a scalable synthesis at low cost. Importantly, it can be readily functionalized to enhance photocatalytic activities. However, the use of g‐C₃N₄‐based photocatalysts for the NRR has been questioned because of the elusive mechanism and the involvement of N defects. This work reports the synthesis of a g‐C₃N₄ photocatalyst modified with cyano groups and intercalated K⁺ (mCNN), possessing extended visible‐light harvesting capacity and superior photocatalytic NRR activity (NH₃ yield: 3.42 mmol g^?1 h^?1). Experimental and theoretical studies suggest that the ‐C≡N in mCNN can be regenerated through a pathway analogous to Mars van Krevelen process with the aid of the intercalated K⁺. The results confirm that the regeneration of the cyano group not only enhances photocatalytic activity and sustains the catalytic cycle, but also stabilizes the photocatalyst.     

Tuning Thiol‐Based Self‐Assembled Monolayer Chemistry on a Gold Surface towards the Synthesis of Biochemical Fuel

A proton gradient across a lipid membrane is required for the production of biochemical fuel. Much effort has been devoted to reactions involving proton production in biomimetic assembled architectures under mild conditions. Herein, we explored thiol‐based self‐assembled monolayer chemistry on a naked gold surface for the production of biochemical fuel. Protons are generated when alkanethiols self‐assemble on a gold surface, and the proton yield can be tuned by the choice of thiol and by variation of the procedure used for the deposition of gold. Consequently, the proton gradient across a lipid membrane above the gold surface can be modulated to vary the production rate of biochemical fuel performed by lipid‐embedded motor proteins. Our work presents evidence that a simple and efficient abiotic chemical reaction in a well‐defined biohybrid system can convert unnatural chemicals, namely alkanethiols, into bioenergy molecules, a finding that has a great potential in biofuel‐driven catalysis and devices.