Ultrathin 2D Cu-porphyrin MOF nanosheets as a heterogeneous catalyst for styrene oxidation

Xiao, Yawen; Guo, Wenxiao; Chen, Huanhuan; Li, Hongfeng; Xu, Xiujie; Wu, Peng; Shen, Yu; Zheng, Bing; Huo, Fengwei; Wei, Wei David

doi:10.1039/c9qm00201d

Cited by 49 publications

(28 citation statements)

References 55 publications

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“…As known, MOFs are widely used in heterogeneous catalysis because of their high surface area, porosity, and chemical tunability. More importantly, like other 2D materials, the MOF nanosheets possess many highly accessible active sites on their surface, which can act as diffusion-free heterogeneous catalysts and should be significant for the catalytic applications Huang et al, 2017;Wang Y. et al, 2019;Xiao et al, 2019). As a proof-of-concept application, the molecular oxygen epoxidation of olefins, which is a highly important oxidation reaction in industrial processes (Punniyamurthy et al, 2005), was chosen as a probe reaction.…”

Section: Resultsmentioning

confidence: 99%

General Approach to Metal-Organic Framework Nanosheets With Controllable Thickness by Using Metal Hydroxides as Precursors

et al. 2020

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Metal-organic frameworks (MOFs) nanosheets have attracted great attention in recent years due to their unprecedented properties. However, the synthesis of MOF nanosheets with controllable thickness still remains a challenge. In this work, a series of MOF nanosheets, such as CuBDC (BDC = 1, 4-benzenedicarboxylate), CoNDC (NDC = naphthalene-2, 6-dicarboxylate), CoBPDC (BPDC = biphenyl-4,4'dicarboxylate), NiBDC and ZnTCPP (TCPP = tetrakis(4-carboxyphenyl)porphyrin) were successfully synthesized by using a metal hydroxide precursor approach. Importantly, the thicknesses of the obtained MOF nanosheets can be well-regulated by controlling the conversion rate of the metal hydroxides. As a proof-of-concept application, the obtained CuBDC nanosheets were used as the catalyst for olefin epoxidation, which showed much higher catalytic activity compared to the bulk crystals. This work provides an alternative method for the synthesis of various MOF nanosheets, holding great potential for various promising applications.

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Section: Resultsmentioning

confidence: 99%

General Approach to Metal-Organic Framework Nanosheets With Controllable Thickness by Using Metal Hydroxides as Precursors

et al. 2020

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“…Polyvinylpyrrolidone (PVP) mediated CuTCPP (TCPP = Tetrakis(4-carboxyphenyl)porphyrin) synthesis yielded ultrathin MONs exhibiting higher efficiency and selectivity in styrene oxidation than bulk CuTCPP synthesized without PVP (Figure 2b). [50] Mesoporous CuBDC MONs obtained by cetyltrimethylammonium bromide (CTAB) assisted synthesis showed higher conversion in C-S coupling of bulk substituents than the microporous MOF. [51] More recently MONs based on the more robust and Lewis acidic Zr and Hf clusters have been reported.…”

Section: Metal Sitesmentioning

confidence: 99%

Metal–Organic Framework Nanosheets: Programmable 2D Materials for Catalysis, Sensing, Electronics, and Separation Applications

Nicks¹,

Sasitharan²,

Prasad³

et al. 2021

Adv Funct Materials

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offers advantages over simple inorganic nanosheets in that a diverse range of physical and chemical properties can be programmed into their crystalline structure (Figure 1). This distinct combination of properties makes MONs ideal for a wide range of catalysis, sensing, electronics, and separation applications which will be the focus of this review.Much of the early literature in this field focused on the development of novel MON architectures and new routes towards their synthesis. A diverse range of different metal ions and organic linkers have been used to construct MONs. [4] However the field has rapidly converged on a handful of popular secondary building units (SBUs) which dominate much of the literature thanks to their reliable formation of high aspect ratio nanosheets. Popular classes of MONs that have been widely applied by different groups in applications include those based on the metal paddlewheel (PW) motif, [5][6][7] axially capped Zr and Hf clusters, [8][9][10][11] 2D zeolitic imidazolate frameworks (ZIFs), [12][13][14] and square planar Ni, Co, and Cu SBUs. [15][16][17][18] The modular structure of MONs, ease of functionalization and diverse range of materials they can be combined with means that MONs can be readily "programmed" to provide the desired topology and properties required for a given application.A wide variety of methods have been explored to synthesize MONs, either "top-down" by the exfoliation of layered metalorganic frameworks (MOFs) or "bottom-up" by assembly of molecular building blocks directly into nanosheets. The majority of top-down approaches utilize mechanical energy to overcome inter-layer interactions, such as liquid-assisted ultrasonication, [19] shear-mixing, [20] and grinding/ball-milling, [13] or the less common freeze-thaw [21] and "scotch-tape" methods. [22,23] Other methods involving photochemical, [24] electrochemical, [25] and chemical intercalation, [26] have also been developed but are less widely used. Bottom-up methodologies typically utilize surfactants or modulators to inhibit crystal growth in one dimension, [12,27,28] or layering/interfacial methods to promote anisotropic growth. [15,29,30] The use of sacrificial 2D templates has also recently emerged a promising route. [31,32] Each approach has advantages and disadvantages in terms of the thickness, lateral dimensions, size distribution, quantity and quality of the MONs produced, and the best approach therefore varies depending on the application.

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“…Their enhanced catalytic activity is associated with the ultra-thin thickness and more accessible active sites, which decrease the diffusion resistance and increase the host-guest interactions, rendering these materials much better than the corresponding bulk MOFs [ 188 ]. For example, 2D MOFs based on tetrakis(4-carboxyphenyl)-porphyrin display unique photochemistry and high efficiency in light-harvesting applications and showed catalytic activity in photooxidation reactions ( Figure 6 ) [ 189 , 190 , 191 ]. Incorporation of nanoparticles or enzymes as well as post-synthetic modification provided new materials with enhanced catalytic activities [ 192 ].…”

Section: Applications Of Mofsmentioning

confidence: 99%

Metal-Organic Frameworks: Synthetic Methods and Potential Applications

Raptopoulou

2021

Materials

176

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Metal-organic frameworks represent a porous class of materials that are build up from metal ions or oligonuclear metallic complexes and organic ligands. They can be considered as sub-class of coordination polymers and can be extended into one-dimension, two-dimensions, and three-dimensions. Depending on the size of the pores, MOFs are divided into nanoporous, mesoporous, and macroporous items. The latter two are usually amorphous. MOFs display high porosity, a large specific surface area, and high thermal stability due to the presence of coordination bonds. The pores can incorporate neutral molecules, such as solvent molecules, anions, and cations, depending on the overall charge of the MOF, gas molecules, and biomolecules. The structural diversity of the framework and the multifunctionality of the pores render this class of materials as candidates for a plethora of environmental and biomedical applications and also as catalysts, sensors, piezo/ferroelectric, thermoelectric, and magnetic materials. In the present review, the synthetic methods reported in the literature for preparing MOFs and their derived materials, and their potential applications in environment, energy, and biomedicine are discussed.

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Ultrathin 2D Cu-porphyrin MOF nanosheets as a heterogeneous catalyst for styrene oxidation

Abstract: Cu-TCPP nanosheets exhibit a high density of active sites and low diffusion barriers for styrene epoxidation.

Cited by 49 publications

References 55 publications

General Approach to Metal-Organic Framework Nanosheets With Controllable Thickness by Using Metal Hydroxides as Precursors

General Approach to Metal-Organic Framework Nanosheets With Controllable Thickness by Using Metal Hydroxides as Precursors

Metal–Organic Framework Nanosheets: Programmable 2D Materials for Catalysis, Sensing, Electronics, and Separation Applications

Metal-Organic Frameworks: Synthetic Methods and Potential Applications

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