Highly uniform ruthenium (Ru) nanoparticles over N-doped carbon (Ru@CN) was designed and confirmed as a promising candidate for the hydrogen evolution reaction (HER) over a wide pH range.

Developing novel and efficient catalysts is always an important theme for heterogeneous catalysis from fundamental and applied research points of view. In the past, carbon materials were used as supports for numerous heterogeneous catalysts because of their fascinating properties including high surface areas, tunable porosity, and functionality. Recently, the newly emerging N-doped carbon-supported metal catalysts have arguably experienced great progress and brought the most attention over the last decades in view of the fact that nitrogen doping can tailor the properties of carbon for various applications of interest. Compared with pristine carbon-supported metal catalysts, these catalysts normally show superior catalytic performance in many heterogeneous catalytic reactions because of the introduced various metal–support interactions from N doping. In this Perspective, we focus on the fabrication methods for N-doped carbon-supported metal catalysts and the catalytic application of these fascinating catalysts in several industrially relevant reactions, including hydrogenation, dehydrogenation, oxidation, and coupling. Notably, we try to elucidate the structure–activity correlations obtained from theoretical calculation, extensive characterization, and observed catalytic performances, thereby providing guidance for the rational design of advanced catalysts for heterogeneous catalysis.

The earth-abundant nanohybrids Co 0 /Co 3 O 4 @N-doped carbon nanotubes were fabricated via an efficient thermal condensation of D-glucosamine hydrochloride, melamine and Co(NO 3 ) 2 ·6H 2 O. The hybrids furnish excellent catalytic activity and perfect chemoselectivity (>99%) for a wide range of substituted nitroarenes (21 examples) under relatively mild conditions. The high catalytic performance and durability is attributed to the synergistic effects between each component, the unique structure of graphene layers-coated Co 0 and the electronic activation of doped nitrogen. Density functional calculations indicate that the inner Co 0 core and N species on the carbon shell can significantly decrease the dissociation energies of H 2 , giving evidence of the ability of carbon shell in the hybrids to H 2 activation. These results open up an avenue to design more powerful low-cost catalysts for industrial applications.

The layered Fe-doped alpha-type cobalt hydroxide (α-Co4Fe(OH)x) nanosheet exhibited superior activity towards the oxygen evolution reaction and the correlation between the Fe content and activity could be plotted as a volcano curve.

RuPd alloy nanoparticles (3.6 nm) uniformly dispersed on N-doped carbon (RuPd/CN) was prepared via a simple ultrasoundassisted coreduction method. The RuPd/CN is highly active, selective, and stable in the hydrogenation of benzoic acid to cyclohexanecarboxylic acid under mild conditions with a TOF up to 2066 h −1 . It was found that the bimetallic RuPd/CN catalyst exhibited a substantially enhanced activity in comparison with the monometallic catalysts (Ru/CN and Pd/CN). The reason for the higher performance of the RuPd/CN catalyst is considered to be the increased Ru 0 /Ru n+ ratio induced by the electronic interaction between Ru and Pd, as evidenced by various characterizations. Notably, the different phenomenon of activity platform on different catalysts ascribed to the effect of hydrogen pressure was newly observed and further explained by first-principle studies. Moreover, the factors influencing the adsorption modes of BA, especially the configuration of the carboxyl group, have been investigated preliminarily in first-principle studies, giving a distinct insight from the former work. The reason the carboxyl group in benzoic acid does not undergo hydrogenation, which results in superior selectivity (>99%), is also revealed by a comparison of the thermodynamics of hydrogenation and dissociation of the carboxyl group.