Atomically Conformal Metal Laminations on Plasmonic Nanocrystals for Efficient Catalysis

Abstract

Despite the enormous application potential, methods for conformal few-atomic-layer deposition on colloidal nanocrystals (NCs) are scarce. Similar to the process of lamination, we introduce a “confine and shine” strategy to homogeneously modify the different surface curvatures of plasmonic NCs with ultrathin conformal layers of diverse catalytic noble metals. This self-limited epitaxial skinlike metal growth harvests the localized surface plasmon resonance to induce reduction chemistry directly on the NC surface, confined inside hollow silica. This strategy avoids any kinetic anisotropic metal deposition. Unlike the conventional thick, anisotropic, and dendritic shells, which show severe nonradiative damping, the skinlike metal lamination preserves the key plasmonic properties of the core NCs. Consequently, the plasmonic–catalytic hybrid nanoreactors can carry out a variety of organic reactions with impressive rates.

Magnetic–Plasmonic Multimodular Hollow Nanoreactors for Compartmentalized Orthogonal Tandem Catalysis

“…This design challenge requires the integration of optimal molecular diffusion to and from active sites as well as switching the selected step “on” and “off” in situ by a benign and site-selective energy flow, tightly controlling different products while suppressing side reactions. − Such a compartmentalized energy supply can facilitate the arbitrary integration of steps from a diverse pool of catalytic reactions, facilitating a one-pot total synthesis irrespective of the thermodynamic compatibility. In addition, while they avoid the nonspecific heating of the bulk reaction, these systems would be adoptable for specific applications involving heat-sensitive media such as in locally synthesizing desired molecular probes or therapeutic molecules in a delicate bioenvironment, functioning on-demand with in-built stimuli-responsive plugins. − Unfortunately, commonly synthesized hybrid magnetic–plasmonic nanostructures such as core–shells, yolk shells, and heterodimers are unsuitable for these purpose-directed applications, in which the independent but synchronous operation of magnetic and plasmonic components is required. − In this study, we propose a suitable multimodular catalytic platform comprising nanocompartmentalized antennae-reactor components that can efficiently receive and supply hyperlocal energy to a specific reaction site without an interconflicting mechanism. To achieve this, we integrated “plasmonic–catalytic” and “magnetic–catalytic” components in an isolated but tethered configuration that independently recruits near-infrared light (NIR) and an alternating magnetic field (AMF), respectively, as selective excitation modules on the distinct energy spectrum.…”

“…17 nm thick), including numerous plasmonic nanogaps and -cavities (<1 nm) (designated as Pd/Fe 3 O 4 @AuShell) that extensively coupled localized surface plasmon resonance (LSPR) absorption expanding from the visible to NIR range (Figures S4 and S5). Furthermore, we selectively performed an LSPR-induced photochemical ultrathin metal Pt-layer growth (<1 nm thick) on the Au-shell part by employing NIR light (785 nm, 0.4 W/cm 2 ), resulting in an MPNR (TEM images in Figure C, D) . The LSPR band of Pd/Fe 3 O 4 @AuShell was minimally affected after ultrathin Pt modification and was broadened as a signature of the extensive plasmonic coupling and minimal plasmonic damping effects (Figure S5).…”

“…Next, we intended to confirm the operation of the PlasC and MagC segments in MPNR to catalyze two distinct reactions. First, we tested the MPNR for a [Pt]-catalyzed conversion of N -pentynoyl-protected rhodamine 110 (pro-Rh-110, 1a ) (5 mg/mL in H 2 O/DMSO) to green-fluorescent rhodamine 110 (Rh-110, 1b) via NIR laser irradiation (785 nm, 0.4 W/cm 2 ) while maintaining the bulk temperature (<40 °C) . The reaction produced free Rh-110 with >99% conversion (TOF = 0.41 min –1 ) within 2 h (Figure A and Figure S7).…”

Shell isolated nanoparticle enhanced Raman spectroscopy for mechanistic investigation of electrochemical reactions

“…Acharya et al . applied plasmon-induced photocatalytic ALD to deposit atomically thin catalytic-active metal on the Au nanorod surface [ 63 ]. Firstly, the gold nanorod was individually isolated with a hollow silica shell.…”

Critical Review on Synthetic Routes and Catalytic Applications of Hollow Nanomaterials

“…Layer by layer (LBL) adsorption technique and PMMA beads as templates used to obtain these nanostructures. [Tu et al] [71] Titania and graphene loading obtained by the successive modification with positively charged polyethylamine and negatively charged Ti 0.91 O 2 nanosheets. Which leads to second layer of polyethylamine (+ive charged) with graphene oxide (GO) suspension (-ive charged).…”