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Developing suitable catalysts capable of receiving injected electrons and possessing active sites for hydrogen evolution reaction (HER) is the key to building an efficient dye-sensitized system for hydrogen production. Fe3S4 is generally regarded as an inferior HER catalyst among the metal sulfide family, mainly due to its weak surface adsorption toward H atoms. In this work, we demonstrate a facile metal-organic framework-derived method to synthesize uniform Fe3S4 nanorods and active them for HER by Ni doping. Our experimental results and theoretical calculations reveal that Ni doping can greatly modify the electronic structure of Fe3S4 nanorods, improving their electron conductivity and optimizing their surface adsorption energy toward H atoms. Sensitized by a commercial organic dye (eosin-Y), 1%Ni-doped Fe3S4 nanorods display a high H2 production rate of 3240 μmol gcat-1 h-1 with an apparent quantum yield of 12% under 500 nm wavelength, which is significantly higher than that of pristine Fe3S4 and even higher than that of 1% Pt-deposited Fe3S4. The working mechanism of this dye-sensitized system is explored, and the effect of Ni-doping concentration has been studied. This work presents a facile strategy to synthesize metal-doped sulfide nanocatalysts with greatly enhanced activity toward photocatalytic H2 production.

Improving the reaction selectivity and activity for challenging substrates such as nitroaromatics bearing two reducible functional groups is important in industry, yet remains a great challenge using traditional metal nanoparticle based catalysts. In this study, single metal atom doped M-C2N catalysts were theoretically screened for selective hydrogenation of 3-nitrostyrene to 3-vinylaniline with H2 as the H-source. Among 20 M-C2N catalysts, the non-noble Mn-C2N catalyst was found to have excellent reaction selectivity. Importantly, due to the solid frustrated Lewis pair sites in the pores of Mn-C2N, a low H2 activation energy is achieved on high-spin Mn-C2N and the rate-determining step for the hydrogenation reactions is the H diffusion from the metal site to the N site. The unraveled mechanism of the hydrogenation of 3-nitrostyrene using Mn-C2N enriches the applications of Mn based catalysts and demonstrates its excellent properties for catalyzing the challenging hydrogenation reaction of substrates with two reducible functional groups.

It is well-known that functional groups should greatly affect the electronic properties of the metal cluster-encapsulated metal–organic frameworks and thus change their catalytic properties; howeve...