Facet-dependent catalytic activity of ZIF-8 nanocubes and rhombic dodecahedra based on tracing substrate diffusion in pores by SERS: a case study for surface catalysis of MOFs

Chen, Li‐Yong; Duan, Binhua; Luo, Qian; Gu, Zhizhi; Liu, Jing; Duan, Chunying

doi:10.1039/c5cy01882j

Cited by 43 publications

(34 citation statements)

References 21 publications

(12 reference statements)

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“…Therefore, in most cases, the majority of a gaseous analyte is swept away by the prevailing flow, leaving a low proportion of molecules adsorbed to the SERS substrate. In this manuscript, we demonstrate a reliable SERS strategy for detecting gaseous aldehydes by employing a specific core–shell 3D structure ( Scheme ), wherein ordered gold superparticles (GSPs) act as SERS hotspots and metal organic framework (MOF) depress the attenuation of the electromagnetic field around the GSP surface. This approach effectively slowed the gas flow rate to allow adequate time for the adsorption of analytes onto the SERS substrate.…”

Section: Methodsmentioning

confidence: 99%

Selective Surface Enhanced Raman Scattering for Quantitative Detection of Lung Cancer Biomarkers in Superparticle@MOF Structure

et al. 2017

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Surface enhanced Raman scattering (SERS) is a trace detection technique that extends even to single molecule detection. Its potential application to the noninvasive recognition of lung malignancies by detecting volatile organic compounds (VOCs) that serve as biomarkers would be a breakthrough in early cancer diagnostics. This application, however, is currently limited by two main factors: (1) most VOC biomarkers exhibit only weak Raman scattering; and (2) the high mobility of gaseous molecules results in a low adsorptivity on solid substrates. To enhance the adsorption of gaseous molecules, a ZIF-8 layer is coated onto a self-assembly of gold superparticles (GSPs) in order to slow the flow rate of gaseous biomarkers and depress the exponential decay of the electromagnetic field around the GSP surfaces. Gaseous aldehydes that are released as a result of tumor-specific tissue composition and metabolism, thereby acting as indicators of lung cancer, are guided onto SERS-active GSPs substrates through a ZIF-8 channel. Through a Schiff base reaction with 4-aminothiophenol pregrafted onto gold GSPs, gaseous aldehydes are captured with a 10 ppb limit of detection, demonstrating tremendous prospects for in vitro diagnoses of early stage lung cancer.

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Section: Methodsmentioning

confidence: 99%

Selective Surface Enhanced Raman Scattering for Quantitative Detection of Lung Cancer Biomarkers in Superparticle@MOF Structure

et al. 2017

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“…The ZIF‐8 crystals obtained by spray‐drying (SP) are cubic with dimensions of 5–10 µm, whereas the crystals synthesized by the solvothermal method (SV) are much larger (60–100 µm) with a truncated rhombic dodecahedral shape. A reasonable explanation would be, in the case of the SP method, that the time for crystal growth is very short, which results in small cubic‐shaped materials, whereas a longer time for crystallization in the SV procedure allows crystal evolution and consequently larger‐sized crystals with a truncated rhombic dodecahedral shape were obtained , . Recently, time‐resolved in situ energy‐dispersive X‐ray diffraction (EDXRD) and ex situ SEM were applied to study the solvothermal synthesis of ZIF‐8 at different concentrations and temperatures .…”

Section: Resultsmentioning

confidence: 99%

One‐Step Synthesis of 2,5‐Bis(chloromethyl)‐1,4‐dioxane from Epichlorohydrin Using ZIF‐8, Taking Advantage of Structural Defects

et al. 2017

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We demonstrate herein the ZIF‐8‐only‐mediated catalysis of the cyclodimerization of epichlorohydrin to 2,5‐bis(chloromethyl)‐1,4‐dioxane in the absence of co‐catalyst and solvent. The easy handling and economic aspects of ZIF‐8, in addition to the one‐step reaction to produce the cyclodimer, make this catalyst attractive even for industry. It has been clearly illustrated that the nature of the method used to synthesize ZIF‐8 affected the yields of the cyclodimers. Specifically, the method employed to produce ZIF‐8 directly influences the amount of crystal structural defects, which in turn impacts their performance as catalysts. To emphasize the role of defects, other physical properties, such as surface area and particle size, were controlled during the synthesis of the ZIF‐8 catalysts. Remarkably, the amount of structural defects was quantified by temperature program desorption analysis.

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“…The shape dependence of ZIF-8 rhombic dodecahedra and nanocubes was systematically studied for the Knoevenagel condensation. [468] The higher catalytic activity of the nanocubes compared to rhombic dodecahedra of similar surface area could be attributed to the intrinsically higher density of coordinatively unsaturated metal sites on {100} facets. In another study, ZIF-8 nanoparticles were used for the Knoevenagel synthesis of α,βunsaturated cyanoesters and 3-cyanocoumarins with excellent yields ranging from 89% to 95%, and the particles could be reused up to five times.…”

Section: Heterogeneous Catalysismentioning

confidence: 98%

The Chemistry of Reticular Framework Nanoparticles: MOF, ZIF, and COF Materials

Ploetz

Engelke

Lächelt

et al. 2020

Adv Funct Materials

214

145

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Nanoparticles have become a vital part of a vast number of established processes and products; they are used as catalysts, in cosmetics, and even by the pharmaceutical industry. Despite this, however, the reliable and reproducible production of functional nanoparticles for specific applications remains a great challenge. In this respect, reticular chemistry provides methods for connecting molecular building blocks to nanoparticles whose chemical composition, structure, porosity, and functionality can be controlled and tuned with atomic precision. Thus, reticular chemistry allows for the translation of the green chemistry principle of atom economy to functional nanomaterials, giving rise to the multifunctional efficiency concept. This principle encourages the design of highly active nanomaterials by maximizing the number of integrated functional units while minimizing the number of inactive components. State-ofthe-art research on reticular nanoparticles-metal-organic frameworks, zeolitic imidazolate frameworks, and covalent organic frameworks-is critically assessed and the beneficial features and particular challenges that set reticular chemistry apart from other nanoparticle material classes are highlighted. Reviewing the power of reticular chemistry, it is suggested that the unique possibility to efficiently and straightforwardly synthesize multifunctional nanoparticles should guide the synthesis of customized nanoparticles in the future.

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Facet-dependent catalytic activity of ZIF-8 nanocubes and rhombic dodecahedra based on tracing substrate diffusion in pores by SERS: a case study for surface catalysis of MOFs

Abstract: We employed ZIF-8 rhombic dodecahedra and nanocubes as catalysts to obtain insights into the surface catalysis of MOFs based on facet-dependent catalytic activity for Knoevenagel condensation.

Cited by 43 publications

References 21 publications

Selective Surface Enhanced Raman Scattering for Quantitative Detection of Lung Cancer Biomarkers in Superparticle@MOF Structure

Selective Surface Enhanced Raman Scattering for Quantitative Detection of Lung Cancer Biomarkers in Superparticle@MOF Structure

One‐Step Synthesis of 2,5‐Bis(chloromethyl)‐1,4‐dioxane from Epichlorohydrin Using ZIF‐8, Taking Advantage of Structural Defects

The Chemistry of Reticular Framework Nanoparticles: MOF, ZIF, and COF Materials

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