Metal Single-Atom Cocatalyst on Carbon Nitride for the Photocatalytic Hydrogen Evolution Reaction: Effects of Metal Species

Single-atom (SA) catalysts exhibit high activity in various reactions because there are no inactive internal atoms. Accordingly, SA cocatalysts are also an active research fields regarding photocatalytic hydrogen (H-2) evolution which can be generated by abundant water and sunlight. Herein, it is investigated whether 10 transition metal elements can work as an SA on graphitic carbon nitride (g-C3N4; i.e., gCN), a promising visible-light-driven photocatalyst. A method is established to prepare SA-loaded gCN at high loadings (weight of approximate to 3 wt.% for Cu, Ni, Pd, Pt, Rh, and Ru) by modulating the photoreduction power. Regarding Au and Ag, SAs are formed with difficulty without aggregation because of the low binding energy between gCN and the SA. An evaluation of the photocatalytic H-2-evolution activity of the prepared metal SA-loaded gCN reveals that Pd, Pt, and Rh SA-loaded gCN exhibits relatively high H-2-evolution efficiency per SA. Transient absorption spectroscopy and electrochemical measurements reveal the following: i) Pd SA-loaded gCN exhibits a particularly suitable electronic structure for proton adsorption and ii) therefore they exhibit the highest H-2-evolution efficiency per SA than other metal SA-loaded gCN. Finally, the 8.6 times higher H-2-evolution rate per active site of Pd SA is achieved than that of Pd-nanoparticles cocatalyst.