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[Display omitted] • The ML-Pd@Au NRs catalyst shows super-high HER activity and ultra-low overpotential under irradiation. • Au NRs not only adjust the electronic structure and lattice strain of Pd but also offer plasmonic hot charge carriers. • The method to synthesize the single atomic layer Pd@Au NRs catalyst is simple, gentle, and accurate. The development of efficient catalysts with low energy consumption has always been a key issue for sustainable hydrogen energy. Here, we report a catalyst comprising a single atomic Pd layer deposited on Au nanorods (ML-Pd@Au NRs) that shows a super-high HER activity and ultra-low overpotential under localized surface plasmon resonance condition. The Au NR plays triple determining roles in HER performance via adjusting the electronic structure and lattice strain of Pd that effectively reduces the adsorption energy of H-adatoms, eliminating the penetration of H adatoms in multilayer Pd crystal that decreases the H adatoms diffusion kinetics, and providing high energetic hot charge carriers under near-IR light irradiation that decreases the activation energy and onset potential of HER. The single atomic Pd layer on Au NRs ensures the hot electron transfer as the main dissipation pathway of the plasmonic hot charge carriers for HER. Thus, under near-IR light irradiation, HER on ML-Pd@Au NRs occurs with a high mass activity of 17.47 mA mg−1 at 100 mV and a very low overpotential of 13 mV at 10 mA cm−2, which are superior to the commercial Pd/C and commercial Pt/C catalysts under the same conditions. [ABSTRACT FROM AUTHOR]

[Display omitted] • A metal doping strategy is proposed for N 2 activation. • Ca2+-doped UiO-66 is synthesized. • The Ca2+ doping fortifies the electron transfer from active sites to N 2. • The diamino ligand incorporating fortifies the electron generation and separation. • Photocatalytic NH 3 yield reaches 759.3 μmol h−1 g−1 under full spectrum. Photocatalytic NH 3 synthesis from N 2 is a clean and sustainable approach, however, the efficiency of this process is low due to the difficult activation of N N triple bonds. Herein, we propose a metal-doping strategy to facilitate the interfacial charge transfer for promoting the photocatalytic NH 3 yield. Ca2+ with low electronegativity was doped in UiO-66-NH 2 , a kind of Zr-based MOFs, to increase the electron donor capacity of Zr active sites. The X-ray photoelectron spectroscopy (XPS) spectra and density functional theory (DFT) calculations show that the Ca2+ doping enhances the electron density of Zr active sites. Moreover, the diamino ligand is incorporated to tune the bandgap structure of MOFs to expand its light absorption range. By adjusting the ratio of metals and organic ligands, the optimal photocatalyst UN(Zr-0.30Ca)-4 reaches a high NH 3 evolution rate of 759.3 μmol g−1 h−1 under full spectrum. This study may provide some inspiration for the design of advanced photocatalysts for diverse chemical reduction reactions. [ABSTRACT FROM AUTHOR]