Nanocatalosomes as Plasmonic Bilayer Shells with Interlayer Catalytic Nanospaces for Solar‐Light‐Induced Reactions

Abstract

Interest and challenges remain in designing and synthesizing catalysts with nature-like complexity at few-nm scale to harness unprecedented functionalities by using sustainable solar light. We introduce "nanocatalosomes"-a bioinspired bilayer-vesicular design of nanoreactor with metallic bilayer shell-in-shell structure,h aving numerous controllable confined cavities within few-nm interlayer space,customizable with different noble metals.T he intershell-confined plasmonically coupled hot-nanospaces within the few-nm cavities play apivotal role in harnessing catalytic effects for various organic transformations,a sd emonstrated by "acceptorless dehydrogenation", "Suzuki-Miyaura cross-coupling" and "alkynyl annulation" affording clean conversions and turnover frequencies (TOFs) at least one order of magnitude higher than state-of-the-art Au-nanorod-based plasmonic catalysts.T his work paves the wayt owardsn ext-generation nanoreactors for chemical transformations with solar energy.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Plasmonic Coupling Architectures for Enhanced Photocatalysis

“…[ 78 ] Besides, polymer‐assisted and template‐supported synthetic methods were also employed to prepare coupled nanostructures, such as Au@SiO 2 dual shell NPs, [ 76 ] Au core–Ag satellite nanostructures, [ 107 ] Au core–satellite nanostructures, [ 108 ] Au‐nanobridged NPs, [ 109 ] porous triple‐shell Au nanostructures, [ 110 ] and hollow bilayer shell Au‐Au/Pd/Pt nanocatalosomes (Figure 8b,c). [ 102 ] Novel plasmonic coupling properties and excellent catalytic activities were obtained by using these unique coupled nanostructures.…”

“…[ 53 ] As such, these hot spots allow for higher exciton generation rates at the interfaces between the coupled metal nanostructures and the semiconductor photocatalysts, which are beneficial to plasmonic photocatalytic reactions. [ 102 ] In addition, a larger amount of hot electrons may exist at the hot spots, and could be injected into the molecular orbital of the adsorbed reactants to activate surface redox reactions. [ 62 ] There might be also strong interactions between the dipole moments of the adsorbed reactants and the confined EM field in the hot spots region, that can modify the chemical reaction pathways.…”

“…[ 37 ] Varying the composition of core–shell nanostructures can alter the catalytic performance for different reactions. [ 102 ] The nanocatalosome with Au−Au bilayer shells was found effective for alkynyl annulation, while Au−Pt and Au−Pd nanocatalosomes were competent for dehydrogenation and CC coupling reactions, respectively. In these bilayer nanocatalosomes, plasmonic hot spots were formed in the narrow interparticle gaps and cavities, which could concentrate strong EM field, promote charge generation and separation, and increase local temperature.…”

Confined space design by nanoparticle self-assembly

“…Kumar et al have recently reported plasmonic-catalytic nanoreactors named "nanocatalosomes (NCat)", characterized by a metal-bilayer hollow shell-in-shell structure composed of arrays of closely spaced NPs (Figure 9). 98 The interlayer space of NCat presents a large number of plasmonic nanocavities intimately interfaced with the chosen catalytic metal (Au/Pt/Pd). NCat were obtained starting from hollow porous silica nanoshells modified with Au seeds and coated with a 3 nm film of tannic (TA) and iron coordination polymer (TA-Fe).…”

“…9 ). 98 The interlayer space of NCat presents a large number of plasmonic nanocavities intimately interfaced with the chosen catalytic metal (Au/Pt/Pd). NCat were obtained starting from hollow porous silica nanoshells modified with Au seeds and coated with a 3 nm film of tannic (TA) and iron coordination polymer (TA–Fe).…”