Three-dimensional (3D) porous metal and metal oxide nanostructures have received considerable interest because organization of inorganic materials into 3D nanomaterials holds extraordinary properties such as low density, high porosity, and high surface area. Supramolecular self-assembled peptide nanostructures were exploited as an organic template for catalytic 3D Pt-TiO2 nano-network fabrication. A 3D peptide nanofiber aerogel was conformally coated with TiO2 by atomic layer deposition (ALD) with angstrom-level thickness precision. The 3D peptide-TiO2 nano-network was further decorated with highly monodisperse Pt nanoparticles by using ozone-assisted ALD. The 3D TiO2 nano-network decorated with Pt nanoparticles shows superior catalytic activity in hydrolysis of ammonia-borane, generating three equivalents of H2 .
Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies.
Fabrication of supramolecular electroactive materials at the nanoscale with well-defined size, shape, composition, and organization in aqueous medium is a current challenge. Herein we report construction of supramolecular charge-transfer complex one-dimensional (1D) nanowires consisting of highly ordered mixed-stack π-electron donor-acceptor (D-A) domains. We synthesized n-type and p-type β-sheet forming short peptide-chromophore conjugates, which assemble separately into well-ordered nanofibers in aqueous media. These complementary p-type and n-type nanofibers coassemble via hydrogen bonding, charge-transfer complex, and electrostatic interactions to generate highly uniform supramolecular n/p-coassembled 1D nanowires. This molecular design ensures highly ordered arrangement of D-A stacks within n/p-coassembled supramolecular nanowires. The supramolecular n/p-coassembled nanowires were found to be formed by A-D-A unit cells having an association constant (K) of 5.18 × 10 M. In addition, electrical measurements revealed that supramolecular n/p-coassembled nanowires are approximately 2400 and 10 times more conductive than individual n-type and p-type nanofibers, respectively. This facile strategy allows fabrication of well-defined supramolecular electroactive nanomaterials in aqueous media, which can find a variety of applications in optoelectronics, photovoltaics, organic chromophore arrays, and bioelectronics.
A dynamic covalent crosslinking approach is used to crosslink supramolecular peptide gels. This novel approach facilitates tuning viscoelastic properties of the gel and enhances mechanical stability (storage modulus exceeding 10(5) Pa) of the peptide gels.
Portable and flexible energy devices demand lightweight and highly efficient catalytic materials for use in energy devices. An efficient water splitting electrocatalyst is considered an ideal future energy source. Well‐aligned high‐surface‐area electrospun polymers of intrinsic microporosity (PIM‐1)‐based nitrogen‐doped carbon nanofibers were prepared as a free‐standing flexible electrode. A non‐noble‐metal catalyst NiOOH/Ni(OH)2 was precisely deposited over flexible free‐standing carbon nanofibers by using atomic layer deposition (ALD). The morphology, high surface area, nitrogen doping, and Ni states synergistically showed a low onset potential (ηHER=−40 and ηOER=290 mV vs. reversible hydrogen electrode), small overpotential at η10 [oxygen evolution reaction (OER)=390.5 mV and hydrogen evolution reaction (HER)=−147 mV], excellent kinetics (Tafel slopes for OER=50 mV dec−1 and HER=41 mV dec−1), and high stability (>16 h) towards water splitting in an alkaline medium (0.1 m KOH). The performance was comparable with that of state‐of‐the‐art noble‐metal catalysts (e.g., Ir/C, Ru/C for OER, and Pt/C for HER). Post‐catalytic characterization with X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy further proved the durability of the electrode. This study provides insight into the design of 1D‐aligned N‐doped PIM‐1 electrospun carbon nanofibers as a flexible and free‐standing NiOOH/Ni(OH)2 decorated electrode as a highly stable nanocatalyst for water splitting in an alkaline medium.
We report the fabrication of a novel and highly active nanocatalyst system comprising electrospun carbon nanofiber (CNF)-supported ruthenium nanoparticles (NPs) (Ru@CNF), which can reproducibly be prepared by the ozone-assisted atomic layer deposition (ALD) of Ru NPs on electrospun CNFs. Polyacrylonitrile (PAN) was electropsun into bead-free one-dimensional (1D) nanofibers by electrospinning. The electrospun PAN nanofibers were converted into well-defined 1D CNFs by a two-step carbonization process. We took advantage of an ozone-assisted ALD technique to uniformly decorate the CNF support by highly monodisperse Ru NPs of 3.4 ± 0.4 nm size. The Ru@CNF nanocatalyst system catalyzes the hydrolytic dehydrogenation of methylamine borane (CHNHBH), which has been considered as one of the attractive materials for the efficient chemical hydrogen storage, with a record turnover frequency of 563 mol H/mol Ru × min and an excellent conversion (>99%) under air at room temperature with the activation energy ( E) of 30.1 kJ/mol. Moreover, Ru@CNF demonstrated remarkable reusability performance and conserved 72% of its inherent catalytic activity even at the fifth recycle.
A bioinspired peptide amphiphile nanofiber template for formation of one-dimensional Pd nanostructures is demonstrated. The Pd and peptide nanocatalyst system enabled efficient catalytic activity in Suzuki coupling reactions in water at room temperature. The nanocatalyst system can be easily separated and reused in successive reactions without significant loss in activity and structural integrity.
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