Monodispersed, Highly Interactive Facet (111)‐Oriented Pd Nanograins by ALD onto Free‐Standing and Flexible Electrospun Polymeric Nanofibrous Webs for Catalytic Application

Abstract

An atomic layer deposition (ALD) of monodispersed palladium (Pd) nanograins (≈2 nm) onto electrospun polymeric nanofibers (NF) is presented. By ALD, monodispersed Pd nanograins with (111) exposed facets are decorated on the surface of the free‐standing flexible nanofibrous webs (NW). The Pd nanograin‐decorated free‐standing NW exhibit catalytic reduction of 4‐nitrophenol to 4‐aminophenol. Even under low loading capacity (≈20 µg mg−1), Pd nanograins manifest effective catalytic performance which can be referred to direct exposure of Pd single crystalline highly interactive (111) plains with high surface area on the NW. The Pd nanograins and the interactive sites along with the high surface area NW yield effective catalytic reduction of 4‐nitrophenol to 4‐aminophenol with the catalytic reduction rate of 0.0531 min−1. Pd nanograins display thermally tunable effective catalytic reduction properties with activation energy (Ea) of 1.705 J mol−1 on varying the reaction temperature from 12 to 42 °C. Moreover, Pd nanograin‐decorated NW are exhibited the effective reusable behavior with stable structural integrity even after repeated catalytic reactions. The approach of this study opens up synthesis and surface decoration of metal nanostructures onto NF through ALD with controlled size and facet orientation for designing reusable and free‐standing flexible catalytic nanofibrous materials.

Atomic Layer Deposition of NiOOH/Ni(OH)2 on PIM‐1‐Based N‐Doped Carbon Nanofibers for Electrochemical Water Splitting in Alkaline Medium

“…[30] It has been reported as av ersatile techniquef or the functionalization of electrospun fibers with numerous metal oxides such as Pt, [31] Pd, [32] Zn, [33] and Ru. [24] In addition, controlling the facets [34] ando perating at al ower temperature than ac onventional chemical vapor deposition technique widensi ts application for numerous nanoparticles and thin-film deposition. Therefore, the ALD methodw as chosen to prepareauniform thin coating of Ni oxyhydroxy catalysts on PIM-CF.…”

Facile and green synthesis of palladium nanoparticles loaded into cyclodextrin nanofibers and their catalytic application in nitroarene hydrogenation

“…In this regard, numerous studies on Pd-NP functional nanofiber systems have been reported for different catalytic reactions, including the photocatalysis of methylene blue, 32 Heck coupling reactions between iodobenzene and acrylates, 33 and hydrogenation of aldehydes 34 and p-nitrophenol. 35 p-Nitrophenol is a nitroarene-type of molecule and can be found in wastewater, 36 and can damage the central nervous system, liver and kidneys. 37 It is thus considered as a pollutant by the U.S. Environmental Protection Agency (EPA).…”

Atomic layer deposition of palladium nanoparticles on a functional electrospun poly-cyclodextrin nanoweb as a flexible and reusable heterogeneous nanocatalyst for the reduction of nitroaromatic compounds

“…11 In addition to these approaches, atomic layer deposition (ALD) of metals or metal oxides onto electrospun nanowebs has emerged as a more advantageous technique since it promotes the growth of nanoparticles in an atomically controlled manner by chemical attachment to surface oxygen atoms and therefore, allows producing nanoparticles or ultrathin nanolayers on the supporting materials. [12][13][14][15][16][17][18] As the entire process follows a layer-bylayer growth, the deposition of atoms gives rise to nanostructures with atomically controlled interfaces. Furthermore, ALD as a chemical vapor deposition technique enables the chemical attachment of atoms and their subsequent growth into nanoparticles or nanolayers so that the materials can be reused many times without the loss or with a minimal loss of catalytic nanomaterials from the material's surface.…”

“…In this regard, our research group has made a signicant contribution in this area by exploiting different combinations of electrospun nanobrous materials as substrates and ALD of metal oxides and metals for catalytic purposes. [12][13][14][15][16]19 The ALD technique is based on self-terminating gas-solid reactions 20 and is mainly composed of repetitive cycles of the following reactions: (i) the reaction of a metal-ligand (ML) molecule and (ii) the reaction of water. 21 The rst step is likely to happen through ligand (L) swap with one or more surface OH groups, releasing a gaseous product, HL, while attaching the metal-ligand (ML) species to the surface.…”

“…31 Several approaches have been exploited for the chemical decoration of the ber surface with Pd-NPs and other nanoparticles to obtain handy, exible catalytic materials with the further advantage of reusability. 15,19,32 In this regard, the use of Pd-NPs with ALD enables the preparation of highly catalytic materials, and the deposition of Pd atoms takes place as a layer-by-layer process so that the layer growth can be achieved with ne control. 15 Such electrospun nanowebs can be exploited for the catalytic conversion of hazardous water pollutants to less harmful ones, such as nitroaromatics.…”