In this work, the self-assembly behavior of cetyltrimethylammonium bromide (CTAB) on the surface of citrate-capped gold nanoparticles (AuNPs) in solution has been studied by UV–vis absorption spectroscopy, fluorescence probe techniques, ζ potentiometric methods, transmission electron microscopy, etc. The UV–vis spectra show that the color with the increase of CTAB for the mixture containing CTAB and a given amount of AuNPs changes from red to blue and then to red. The absolute value of ζ potential corresponding to this color change decreases initially and then increases. Specially, the reversible color change, from red to blue and then to red, could be observed only in the case of a gradual addition of a AuNP solution to a CTAB solution; however, this reversible change is not suitable for the mixture formed in a reverse order of mixing. The results from pyrene used as the fluorescence probe indicate that the features in the fluorescence spectrum (including fluorescence quenching, I1/I3, and the excimer) well correspond to those from the UV–vis spectrum mentioned above. Based on the experimental results, the mechanism of the assembly structure variation of CTAB on the surface of negatively charged AuNPs was proposed. For a given amount of AuNPs, the assembly structure of CTAB on the surface of AuNPs undergoes the transformation from a monolayer to a bilayer with the increase of CTAB. In the case of the concentration of CTAB far beyond its critical micelle concentration (CMC) and the higher ratio of CTAB and AuNPs, there is a possibility of the formation of an extra micellar structure only after the formation of a double-layer structure.
The composite microspheres of poly(acrylamide) microgels (PAM) surfacely covered with [3-(acryloylamino)propyl]dodecyldimethyl ammonium-tungstophosphate complexes (APDDAB-PWA) were synthesized by using an ion-exchange reaction between APDDAB located within the porous PAM microgels and PWA in aqueous solution. The morphology and component of the composite microspheres were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis, respectively. The results indicated that PAM/APDDAB-PWA composite microsphere with different hierarchical surface structures could be obtained by controlling the weight ratio of APDDAB to PAM microgels, cross-linking degree of PAM microgels, the amount of PWA reacted with APDDAB in PAM/APDDAB, and solvent-washing process. Although the surface morphologies of the composite microspheres in detail were different, a general feature was of the core-shell structure and the wrinkly surface covered with APDDAB-PWA particles. The formation of the wrinkly surface is attributed to the difference in shrink between inside and outside of PAM microgel frameworks, and the formation of APDDAB-PWA small particles originates from the reaction between APDDAB aggregation and PWA. This composite microsphere with PAM hydrogel core is suitable to store water-soluble substances, and the shell composed of the surfactant/Keggin-type polyoxometalate complexes is not only amphiphilic but also catalytic. Additionally, PAM/APDDAB-PWA composite microspheres with big size and APDDAB-PWA particles with small size make the composite microspheres not only easy for separation but also beneficial for catalysis. These properties have been verified by the application of PAM/APDDAB-PWA composite microspheres to the deep desulfurization of fuel oil. This material provides an example to construct microreactors with new structure used in diphase catalytic reaction.
9 January 2024 in Journal of Colloid and Interface Science
Constructing methods for cleaning stains on paper artworks that meet the requirements of preservation of cultural relics are still challenging. In response to this problem, a novel electrochemical cleaning method and the preparation of corresponding electrodes were proposed. For this purpose, the conductive graphene (rGO)/polyacryamide (PAM)/montmorillonite (MMT) composite hydrogel as cathode and PbO2-based material as anode were prepared and characterized. The electrochemical cleaning efficiencies of real sample and mimicking paper artifacts were evaluated, and the effects of the electrochemical cleaning on paper itself were detected. Based on the above experiments, the following results were obtained. The composite hydrogel with attractive mechanical properties is mainly based on the hydrogen bond interactions between PAM chains and MMT. The results of cleaning efficiency revealed that the black mildew stains together with the yellowish foxing stains were almost completely eliminated within 6 min at 8 mA/cm2, and various stains formed by tideline, foxing, organic dyes and drinks could be thoroughly removed at 4 mA/cm2 within 5 min. In addition, the proposed cleaning method has advantages in local selectivity, easy control of cleaning course, and reusability, which represents a potential utility of this approach.
In this paper, the effect of binder decay rather than a change in the pigments on the blurring of ancient wall paintings was researched. The simulated wall paintings were prepared by brushing an aqueous solution containing gelatine and ochre grains on the surface of cylindrical compressed soil samples. Then, the dried samples were calcined at 650 °C for 2 h to obtain the simulated wall paintings with the degraded binder gelatine. Next, the calcined samples were brushed with a certain amount of acetone solution containing an ionic liquid ([BMIm]PF6) to obtain the corresponding repaired samples. Based on the results from various characterization methods (UV–vis, FTIR, XRD, XPS, SEM, TG), the following conclusions were drawn. The degradation of the binder caused by calcination increases the surface roughness of the painting layer, resulting in enhanced scattering. In this case, because scattering decrease the light absorption by the pigments, even if unchanged pigment exists in the painting layer, its colour can become blurred. The filling of the ionic liquid into the pores caused by gelatine decay in the painting layer can decrease the scattering, and the blurred colour can be restored to some extent. As typical examples, this principle was successfully applied to restore the blurred colour of an ancient Chinese wall painting (Tang Dynasty) and a pottery (Eastern Han Dynasty).