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Sub-5 nm porous nanocrystals: interfacial site-directed growth on graphene for efficient biocatalysis.

ABSTRACT: The direct production of macromolecular scale (sub-5 nm) porous nanocrystals with high surface area has been a considerable challenge over the past two decades. Here we report an interfacial site-directed capping agent-free growth method to directly produce porous ultrasmall (sub-5 nm), fully crystalline, macromolecular scale nanocrystals. The porous sub-5 nm Prussian blue nanocrystals exhibit uniform sizes (?4 ± 1 nm), high surface area (?855 m2 g-1), fast electron transfer (rate constant of ?9.73 s-1), and outstanding sustained catalytic activity (more than 450 days). The nanocrystal-based biointerfaces enable unprecedented sub-nanomolar level recognition of hydrogen peroxide (?0.5 nM limit of detection). This method also paves the way towards the creation of ultrasmall porous nanocrystals for efficient biocatalysis.

SUBMITTER: Kong B

PROVIDER: S-EPMC5497271 | biostudies-other | 2015 Jul

REPOSITORIES: biostudies-other

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Sub-5 nm porous nanocrystals: interfacial site-directed growth on graphene for efficient biocatalysis.

Kong Biao B Sun Xiaotian X Selomulya Cordelia C Tang Jing J Zheng Gengfeng G Wang Yingqing Y Zhao Dongyuan D

Chemical science 20150414 7

The direct production of macromolecular scale (sub-5 nm) porous nanocrystals with high surface area has been a considerable challenge over the past two decades. Here we report an interfacial site-directed capping agent-free growth method to directly produce porous ultrasmall (sub-5 nm), fully crystalline, macromolecular scale nanocrystals. The porous sub-5 nm Prussian blue nanocrystals exhibit uniform sizes (∼4 ± 1 nm), high surface area (∼855 m<sup>2</sup> g<sup>-1</sup>), fast electron transfe ...[more]

PMID: 28717465

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Project description:Augmenting the oriented attachment (OA) crystal growth phenomena, herein, we demonstrate fabrication of ultrathin CuO nanowires from self-assembled one-dimensional (1D) nanowires of Cu(OH)2 nanocrystals. A facile environmentally benign sol-gel approach, which utilizes base-catalyzed hydrolysis followed by directed self-assembly and crystal growth of nanocrystals, is developed to prepare Cu(OH)2 nanowires. The sol of Cu(OH)2 nanocrystals shows aggregative self-assembly guided by the OA crystal growth process to form ultrathin Cu(OH)2 nanowires, with an average length of 675 ± 4 nm and diameter of 6 ± 2 nm. The time-dependent UV-visible spectral traces, along with real-time imaging of nanocrystals self-assembly and growth under the transmission electron microscope, are evidenced the concept of the OA crystal growth directed self-assembly, yielding 1D colloidal nanoarrays of Cu(OH)2. The powder XRD traces collected during the self-assembly and crystal growth process reveal the directional aggregative crystal growth along the facet of [001], confirming the OA directed crystal growth and fusion of nanocrystals to yield 1D nanostructures. The gradual blue-shift in optical absorption maxima from 770 nm in initial precursor solution, to 670 nm for Cu(OH)2 nanocrystals sol, and finally to 647 nm for self-assembled 1D Cu(OH)2 nanowires have further evidenced the formation of Cu(OH)2 nanowires. Upon subjecting self-assembled Cu(OH)2 nanowires for post-annealing treatment, ultrathin CuO nanowires with average length of 7 ± 0.50 μm and diameter of 27 ± 2 nm is obtained in high purity. The experimental powder XRD patterns of Cu(OH)2 and CuO nanowires match the simulated XRD patterns, indexing the crystal unit cell structures to orthorhombic and monoclinic, respectively. The tailored narrow optical band gaps for Cu(OH)2 and CuO nanowires are found to be 1.51 eV and 1.10 eV. The theoretical band gap predicted for Cu(OH)2 nanowires is 1.52 eV and is in good agreement with its optical band gap, whereas theoretical band computed for CuO nanowires is 0.13 eV lower than from its optical band gap.

Dataset Information

Sub-5 nm porous nanocrystals: interfacial site-directed growth on graphene for efficient biocatalysis.

Publications

Sub-5 nm porous nanocrystals: interfacial site-directed growth on graphene for efficient biocatalysis.

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