Highly Dispersive Ni@C and Co@C Nanoparticles Derived from Metal-Organic Monolayers for Enhanced Photocatalytic CO2 Reduction.

The metal/carbon composites prepared by direct pyrolysis of metal-organic frameworks (MOFs) are regarded as ideal catalysts. However, conventional MOFs show a three-dimensional bulk structure. For bulk MOF-derived catalysts, most active metal sites are confined in the interior and not fully utilized. In this work, metal-organic monolayers (MOLs) are used as the starting precursors to prepare carbon-wrapped metal nanoparticles, which are further employed as catalysts for photocatalytic CO2 reduction. The as-prepared Ni-MOLs and Co-MOLs have an ultrathin thickness of ∼1 nm. It is interestingly found that their derived Ni@C and Co@C nanoparticles are highly dispersive and connected with each other like a piece of paper. As compared with bulk MOF-derived counterparts, MOL-derived catalysts increase the accessibility of active metal sites, which can accelerate electron transfer from photosensitizers to Ni@C and Co@C nanoparticles. In this way, the catalytic activity can be greatly improved. Besides, the magnetic nature of Ni@C and Co@C nanoparticles enables the easy separation and recycling of catalysts. It is expected that this work will provide instructive guidelines for the rational design of MOL-derived catalysts.

Boosting the Loading of Metal Single Atoms via a Bioconcentration Strategy.

Increasing the mass loading of transition metal single atoms coordinated with nitrogen in carbon-based materials (M-N-C) is still challenging. Herein, inspired by the bioconcentration effect in the living body, a biochemistry strategy for the synthesis of Fe-N-C single atoms is demonstrated. Through introducing ferrous glycinate into the growth of fungus, the Fe atoms are bioconcentrated in hyphae. The highly dispersed Fe-N-C single atoms in hyphae-derived carbon fibers (labeled as Fe-N-C SA/HCF) are prepared by the pyrolysis of Fe-riched hyphae. In the bioconcentration process, the uptake of Fe ions by hyphae promotes the secretion of glutathione and ferritin, which provides additional coordination sites for Fe ions. Accordingly, the mass content of Fe in bioconcentrated Fe-N-C SA/HCF reaches 4.8%, which is 5.3 times larger than that of the sample prepared by the conventional pyrolysis process. The present bioconcentration strategy is further extended to the preparation of Co, Ni, and Mn single atoms. Owing to the high content of Fe-N-C single atoms, Fe-N-C SA/HCF shows the onset potential (Eonset ) of 0.931 V versus reversible hydrogen electrode (RHE) and half-wave potential (E1/2 ) of 0.802 V versus RHE in oxygen reduction reaction measurements, which is comparable to the commercial Pt/C catalysts.