Plasmonic Nanoparticle-Metal–Organic Framework (NP–MOF) Nanohybrid Platforms for Emerging Plasmonic Applications

Abstract

Because of the versatility of plasmonic nanoparticles, there have been major improvements in tailoring the plasmonic effects for a plethora of applications. However, a major bottleneck of plasmonic platforms is the poor performance for nonadsorbing molecules because the plasmon-induced properties are strongest only at the plasmonic surface. To address this fundamental challenge, porous metal−organic frameworks (MOFs) are increasingly incorporated with plasmonic nanoparticles (NP) platform to form plasmonic NP−MOF nanohybrid. Integrating porous MOFs with plasmonic NP enhances the applicability of the nanohybrid by allowing each material to complement each other and can give rise to additional functionalities. In this Perspective, we discuss the latest progress in the development of NP−MOF nanohybrid platforms. We focus on the strategies to fabricate different types of NP−MOF nanohybrids, and their corresponding properties and characteristics, which dictate their subsequent applications. We highlight how the combinative strengths of each material can achieve multiplicative and synergistic breakthrough in current and emerging plasmonic applications, including chemical sensing using LSPR, SERS, and SEIRA, driving and monitoring gas−liquid reactions, probing interactions at the NP−MOF interface, MOF-and plasmon-enhanced photocatalysis, and chemo-photothermal therapy. Finally, we conclude our discussion and present a critical outlook that explores the challenges and future opportunities in the design and applications of NP−MOF nanohybrids.

Recent Progress and Challenges in Plasmon‐Mediated Reduction of CO2 to Chemicals and Fuels

“…[142] Besides metal and semiconductor and some inorganic metal complexes as a functional component in plasmonic hybrid nanostructures, highly porous materials, such as, MOFs, zeolites have appeared as a promising alternative to the lacking catalytic activity of the pristine plasmonic metal nanostructures. [143] Along with the enhanced active surface area, these porous materials address the non-absorbing/low surface affinity of the plasmonic metals toward reactant species by incorporating the variety of analytes to the plasmonic interface through the pores. For example, materials such as zeolites provide a surface area typically within the range of 2000 m 2 g -1, whereas MOFs possess even higher specific surface areas of order >10 000 m 2 g -1 .…”

“…For example, materials such as zeolites provide a surface area typically within the range of 2000 m 2 g -1, whereas MOFs possess even higher specific surface areas of order >10 000 m 2 g -1 . [143,144] Additionally, MOFs impart tunability in their pore/cavity size, which can effectively change its chemical and physical properties and introduce selectivity to the chemical reactions performed using these plasmonic hybrids. In context to the present review, various MOFs have been introduced to Au or Ag nanoparticles (or vice versa) to form a plasmonic reticular photocatalyst and perform photoreduction of CO 2 .…”

Assembly of gold nanorods functionalized by zirconium-based metal–organic frameworks for surface enhanced Raman scattering

“…20,21 Core@shell nanostructures formed by encapsulating plasmonic nanocrystals within MOFs have been demonstrated as multi-functional platforms for SERS detection, catalysis and drug delivery. [22][23][24][25] The MOF shell can stabilize the plasmonic nanocrystals and enrich target molecules close to the metal surface, which are beneficial for improving the performance of the plasmonic nanocrystalbased SERS platform. 23 Necklace-like core@shell Ag@zeolitic imidazolate frameworks-8 (ZIF-8) heterostructured nanowires were reported for SERS detection of crystal violet molecules with an excellent reproducibility.…”

How Do Proteins Associate with Nanoscale Metal–Organic Framework Surfaces?

“…There is increasing interest in nanoscale materials that have controllable nanoscale pores; thus, synthetic methods that describe materials composed of both metal–organic frameworks (MOFs) and nanoparticles have appeared recently. − These materials have applications in drug delivery, sensing, and catalysis. − MOFs themselves have a wide variety of applications including gas storage, separations, and catalysis due to their very high surface areas. , Among nanoparticle types, plasmonic nanoparticles are particularly interesting because of their optical properties. Gold nanoparticles have garnered much attention due to their ability to scatter light, produce local electric fields, and produce heat upon resonant illumination at visible and near-infrared plasmon band maxima. , In particular, gold nanorods (AuNRs) are well known to produce tunable plasmons from ∼500 to 1200 nm. − These properties make gold nanoparticles suitable materials for applications such as sensing and diagnostics, surface-enhanced spectroscopies, and photothermal therapeutics. − …”