Plasmonic noble metal nanoparticles have emerged as a promising material in sensitizing wide-bandgap semiconductors for visible-light photocatalysis. Conventional methods in constructing such heterocatalysts suffer from either poor control over the size of the metal nanoparticles or inefficient charge transfer through the metal/semiconductor interface, which limit their photocatalytic activity. To solve this problem, in this work we construct Au/TiO2 photocatalysts by depositing presynthesized colloidal Au nanoparticles with well-controlled sizes to TiO2 nanocrystals and then removing capping ligands on the Au surface through a delicately designed ligand-exchange method, which leads to close Au/TiO2 Schottky contact after a mild annealing process. Benefiting from this unique synthesis strategy, the obtained photocatalysts show superior activity to conventionally prepared photocatalysts in dye decomposition and water-reduction hydrogen production under visible-light illumination. This study not only opens up new opportunities in designing photoactive materials with high stability and enhanced performance for solar energy conversion but also provides a potential solution for the well-recognized challenge in cleaning capping ligands from the surface of colloidal catalyst nanoparticles.
Ultrasmall gold nanoparticles (us-AuNPs, <3 nm) have been recently recognized as surprisingly active and extraordinarily effective green catalysts. Their stability against sintering during reactions, however, remains a serious issue for practical applications. Encapsulating such small nanoparticles in a layer of porous silica can dramatically enhance the stability, but it has been extremely difficult to achieve using conventional sol-gel coating methods due to the weak metal/oxide affinity. In this work, we address this challenge by developing an effective protocol for the synthesis of us-AuNP@SiO2 single-core/shell nanospheres. More specifically, we take an alternative route by starting with ultrasmall gold hydroxide nanoparticles, which have excellent affinity to silica, then carrying out controllable silica coating in reverse micelles, and finally converting gold hydroxide particles into well-protected us-AuNPs. With a single-core/shell configuration that prevents sintering of nearby us-AuNPs and amino group modification of the Au/SiO2 interface that provides additional coordinating interactions, the resulting us-AuNP@SiO2 nanospheres are highly stable at high temperatures and show high activity in catalytic CO oxidation reactions. A dramatic and continuous increase in the catalytic activity has been observed when the size of the us-AuNPs decreases from 2.3 to 1.5 nm, which reflects the intrinsic size effect of the Au nanoparticles on an inert support. The synthesis scheme described in this work is believed to be extendable to many other ultrasmall metal@oxide nanostructures for much broader catalytic applications.
Isolation
of specific rare cell subtypes from whole blood is critical
in cellular analysis and important in basic and clinical research.
Traditional immunomagnetic cell capture suffers from suboptimal sensitivity,
specificity, and time- and cost-effectiveness. Mimicking the features
of octopuses, a device termed a “NanoOctopus” was developed
for cancer cell isolation in whole blood. The device consists of long
multimerized aptamer DNA strands, or tentacle DNA, immobilized on
magnetic microparticle surfaces. Their ultrahigh sensitivity and specificity
are attributed to multivalent binding of the tentacle DNA to cell
receptors without steric hindrance. The simple, quick, and noninvasive
capture and release of the target cells allows for extensive downstream
cellular and molecular analysis, and the time- and cost-effectiveness
of fabrication and regeneration of the devices makes them attractive
for industrial manufacture.
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