Chemistry of a catalyst surface during catalysis is crucial for a fundamental understanding of mechanism of a catalytic reaction performed on the catalyst in the gas or liquid phase. Due to the pressure- or molecular density-dependent entropy contribution of gas or liquid phase of the reactants and the potential formation of a catalyst surface during catalysis different from that observed in an ex situ condition, the characterization of the surface of a catalyst under reaction conditions and during catalysis can be significant and even necessary for understanding the catalytic mechanism at a molecular level. Electron-based analytical techniques are challenging for studying catalyst nanoparticles in the gas or liquid phase although they are necessary techniques to employ. Instrumentation and further development of these electron-based techniques have now made in situ/operando studies of catalysts possible. New insights into the chemistry and structure of catalyst nanoparticles have been uncovered over the last decades. Herein, the origin of the differences between ex situ and in situ/operando studies of catalysts, and the technical challenges faced as well as the corresponding instrumentation and innovations utilized for characterizing catalysts under reaction conditions and during catalysis, are discussed. The restructuring of catalyst surfaces driven by the pressure of reactant(s) around a catalyst, restructuring in reactant(s) driven by reaction temperature and restructuring during catalysis are also reviewed herein. The remaining challenges and possible solutions are briefly discussed.

The peroxidase-like catalytic activity of gold nanoclusters (Au-NCs) is quite low around physiological pH, which greatly limits their biological applications. Herein, we found heparin can greatly accelerate the peroxidase-like activity of Au-NCs at neutral pH. The catalytic activity of Au-NCs toward the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) oxidation by HO was 25-fold increased in the presence of heparin at pH 7. The addition of heparin not only accelerated the initial catalytic rate of Au-NCs but also prevented the Au-NCs from catalyst deactivation. This allows the sensitive colorimetric detection of heparin at neutral pH. In the presence of heparinase, heparin was hydrolyzed into small fragments, weakening the enhancement effect of catalytic activity. On the basis of this phenomenon, the colorimetric determination of heparinase in the range from 0.1 to 3 μg·mL was developed with a detection limit of 0.06 μg·mL. Finally, the detection of heparin and heparinase activity in diluted serum samples was also demonstrated.

Drug-resistant pathogenic bacteria as a worldwide health threat calls for valid antimicrobial agents and tactics in clinical practice. Positively charged materials usually achieve antibacteria through binding and disrupting bacterial membranes via electrostatic interaction, however, they also usually cause hemolysis and cytotoxicity. Herein, we engineered negatively charged sulfur quantum dots (SQDs) as an efficient broad-spectrum antibiotic to kill drugresistant bacteria in vitro and in vivo. The SQDs can destroy the bacterial membrane system and affect their metabolism due to the intrinsic antibacterial activity of elemental sulfur and catalytic generation of reactive oxygen species, which exhibit effective therapeutic effect on subcutaneously implanted infection model induced by representative pathogenic Methicillin-resistant Staphylococcus aureus and Pseudomonas aeruginosa. Plus, the negatively charged surface makes the SQDs have excellent hemocompatibility and low toxicity, which all highlight the critical prospect of the SQDs as a potent biocompatible antibacterial agent in clinical infection therapy.

A metal−organic framework (MOF) [Cu(PDA)-(DMF)] was synthesized under mild mixed solvothermal conditions. It is constructed by 1,10-phenanthroline-2,9-dicarboxylic acid (H 2 PDA) and Cu 2+ ions. The complex exhibits high peroxidase-like activity and can catalytically oxidize the colorless substrate 3,3′,5,5′tetramethylbenzidine to a blue product in the presence of H 2 O 2 . However, the peroxidase-like activity of [Cu(PDA)(DMF)] can be potently inhibited in the presence of dopamine. Based on this phenomenon, the colorimetric detection of dopamine was demonstrated with good selectivity and high sensitivity. [Cu(PDA)(DMF)] showed good stability and robust catalytic activity, which has been employed in the detection of dopamine in human urine and pharmaceutical samples.

In this study, we found that Pb-induced aggregation can greatly accelerate the peroxidase-like activity of Au nanoclusters (Au-NCs). The catalytic activities of Au-NCs toward peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) oxidation in the presence of HO are nearly 10-fold increased after the Pb-induced aggregation. Based on this finding, a simple and reliable colorimetric method for Pb detection was developed.