Molybdenum Selenide/Porous Carbon Nanomaterial Heterostructures with Remarkably Enhanced Light-Boosting Peroxidase-like Activities.

Nanozymes have emerged as a fascinating nanomaterial with enzyme-like characteristics for addressing the limitations of natural enzymes. Nevertheless, how to improve the relatively low catalytic activity still remains challenging. Herein, a facile recrystallizing salt template-assisted chemical vapor deposition method was utilized to synthesize MoSe2/PCN heterostructures. This heterostructure displays remarkably enhanced light boosting peroxidase-like activities. Notably, the maximal reaction velocity of this heterostructure attains 17.81 and 86.89 µM min-1 [for o-phenylenediamine (OPD) and 3,3'5,5'-tetramethylbenzidine (TMB), respectively]. Moreover, various characterization means were performed to explore the mechanism deeply. It is worth mentioning that the photoinduced electrons generated by the heterostructure directly react with H2O2 to yield plentiful •OH for the effective oxidation of OPD and TMB. Therefore, this work offers a promising approach for improving peroxidase-like activity by light stimulation and actuating the development of enzyme-based applications.

A Graphene-Supported Single-Atom FeN5 Catalytic Site for Efficient Electrochemical CO2 Reduction.

Electrochemical conversion of CO2 into valued products is one of the most important issues but remains a great challenge in chemistry. Herein, we report a novel synthetic approach involving prolonged thermal pyrolysis of hemin and melamine molecules on graphene for the fabrication of a robust and efficient single-iron-atom electrocatalyst for electrochemical CO2 reduction. The single-atom catalyst exhibits high Faradaic efficiency (ca. 97.0 %) for CO production at a low overpotential of 0.35 V, outperforming all Fe-N-C-based catalysts. The remarkable performance for CO2 -to-CO conversion can be attributed to the presence of highly efficient singly dispersed FeN5 active sites supported on N-doped graphene with an additional axial ligand coordinated to FeN4 . DFT calculations revealed that the axial pyrrolic nitrogen ligand of the FeN5 site further depletes the electron density of Fe 3d orbitals and thus reduces the Fe-CO π back-donation, thus enabling the rapid desorption of CO and high selectivity for CO production.

Dual-Ion-Mode MALDI MS Detection of Small Molecules with the O-P,N-Doped Carbon/Graphene Matrix.

It is challenging to realize a dual-ion mode of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for detecting small molecules. Herein, graphene coated by porous amorphous carbon with P-O surface group and codoped by phosphorus and nitrogen (O-P,N-C/G) was synthesized from an aerogel formed by phytic acid, polyaniline, and electrochemically exfoliated graphene. The carbon material synthesized has the feature of large surface area (583 m2/g), good electrical conductivity, strong UV absorption, heteroatom doping, and surface functional groups suitable for laser- induced desorption/ionization. It was employed as a novel matrix suitable for both positive-ion and negative-ion modes in MALDI-TOF MS for the analysis of various small molecules including amino acids, small peptides, saccharides, drugs, and environmental pollutants, significantly outperforming control materials and a traditional CHCA (α-cyano-4-hydroxycinnamic acid) or 2,5-dihydroxybenzoic (DHB) matrix. Remarkably, the detection limit of the anticancer drugs (5-fluorouracil and ellagic acid) reaches 50 pmol. In addition, nice MALDI-TOF MS images can be mapped to detect mixed amino acids corresponding to homogeneous distribution of ion intensity. The monosaccharides and disaccharides can be distinguished by using the new matrix. Last but not least, it can be used to quantitatively detect glucose in human serum and soft drinks (glucose/fructose, 203.1 mM) without adding standards.