Ultimate Control over Hydrogen Bond Formation and Reaction Rates for Scalable Synthesis of Highly Crystalline vdW MOF Nanosheets with Large Aspect Ratio

Shen, Yuxia; Shan, Bohan; Cai, Hui; Qin, Ying; Agarwal, Ashutosh; Trivedi, Dipesh Kumar; Chen, Bin; Liu, Lei; Zhuang, Houlong; Mu, Bin; Tongay, Sefaattin

doi:10.1002/adma.201802497

Cited by 39 publications

(24 citation statements)

References 38 publications

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“…Our results show that the addition of pyridine agent in the upper phase (mixed with metal cations) is effective in producing highly lamellar MnBDC (Figure a,b). The termination effect of pyridine is consistent with our previous report …”

Section: Figuresupporting

confidence: 93%

“…Excited by incident laser with a wavelength of 488 nm, obtained lamellar MnBDC crystal shows four dominant Raman peaks (P 1 –P 4 ) in the range of 700 cm −1 to 1700 cm −1 , which are assigned as the vibrations of metal cluster breathing, benzene ring breathing, metal cluster contracting, and benzene ring breathing, respectively . These Raman features collected by attained lamellar MnBDC precisely match with previous results collected from other vdW 2D MOFs containing Zn or Cu metal atoms . Notably, we found that these four featured peaks in lamellar MnBDC uniformly show their full‐width at half‐maximum (FWHM) as narrow as 6.1–6.8 cm −1 .…”

Section: Figuresupporting

confidence: 87%

“…Previously, we reported the large‐scale synthesis of vdW layered mBDC (m=Cu or Zn) by engineering the capping agent, ligand, and other precursors types to stabilize the layered phase of 2D mBDC sheets . In these studies, it has been shown that the key factor in achieving layered mBDC layers relies on the use of carefully engineered ligands to terminate the out‐of‐plane sites on metal clusters thereby eliminating strong interlayer hydrogen bond formation.…”

Section: Figurementioning

confidence: 99%

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Achieving Morphological Control over Lamellar Manganese Metal‐Organic Framework through Modulated Bi‐Phase Growth

Shen

Shan

2020

Angewandte Chemie

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A modulated bi-phase synthesis towards large-scale manganese 1,4-benzenedicarboxylate (MnBDC) MOFs with a precise control over their morphology (bulk vs. layered) is presented. Metal precursors and organic ligands are separated to reduce the kinetic reaction rates for better control over the crystallization process. Based on scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), and Raman spectroscopy studies, the continuous ligand supply along with the presence of pyridine capping agent are highly effective in promoting the layer-bylayer growth and achieving large crystal sizes. Once layered MnBDC is stabilized, topotactic intercalation chemistry was used to demonstrate the feasibility of bromine intercalation on these layered materials. Bromine intercalation is possible between the MOFs layers for the first time. Bromine intercalation causes colossal reduction in layered MnBDC band gap while it has no observable effect on bulk MOFs.The structure and morphology of metal-organic frameworks (MOFs) play a key factor in determining their practical applications and functionalities ranging from gas separation to catalytic energy conversion and to sensing. Layered MOFs are a subcategory of MOFs in which metal clusters and organic ligands are connected through the coordination bonding which tiles up in two dimensions. In these layered MOFs, each individual layer couples with the adjacent layers through hydrogen or van der Waals (vdW) forces. [1] In comparison to traditional bulk MOFs, layered MOFs offer unique advantages in reaching much larger surface to volume ratios and high surface reactivity/sensitivity. [2] In particular, layered MOFs involving transition-metal cations are interesting owing to their partially filled orbitals with unique magnetic properties. [3] Liu et al. has demonstrated that a high capacity electrode based on Mn MOFs shows great potential application in supercapacitors. [4] Munn et al. investigated MIL-47 (Mn) containing both 1,4-benzenedicarboxylate (BDC) and pyridine-N-oxide (PNO) linkers exhibits anti-ferromagnetic behavior at low temperature. [5] Despite their potential, the studies to date have shown that it is hard to control the microstructure and crystallinity of Mn MOFs. One of the challenges encountered in the synthesis of Mn MOFs is the low electronegativity of Mn. Historically, the low electronegativity in titanium has hindered the fabrication of Ti-based MOFs with controllable crystallinity. The nature of ease of losing outer electrons in Ti leads to the intense electrostatic between TiÀO. The formed strong TiÀO bonds significantly impedes the ligand exchange process which is vital to control over MOF crystallinity. Although the modulation of Ti (or other Group 4 metals) MOFs synthesis via unidentate molecules (such as formic acid, pyridine, ethanol) is wellestablished, [6] there is no efficient way to gain control over the formation of Mn MOFs, let alone the precise manipulation in the reduced dimensionality (2D) landscape.Previou...

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Section: Figuresupporting

confidence: 93%

Section: Figuresupporting

confidence: 87%

Section: Figurementioning

confidence: 99%

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Achieving Morphological Control over Lamellar Manganese Metal‐Organic Framework through Modulated Bi‐Phase Growth

Shen

Shan

2020

Angewandte Chemie

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“…Furthermore, we applied Raman vibration to depict the unit cell structure of lamellar MnBDC (Figure d). Excited by incident laser with a wavelength of 488 nm, obtained lamellar MnBDC crystal shows four dominant Raman peaks (P 1 –P 4 ) in the range of 700 cm −1 to 1700 cm −1 , which are assigned as the vibrations of metal cluster breathing, benzene ring breathing, metal cluster contracting, and benzene ring breathing, respectively . These Raman features collected by attained lamellar MnBDC precisely match with previous results collected from other vdW 2D MOFs containing Zn or Cu metal atoms .…”

Section: Figuresupporting

confidence: 87%

Achieving Morphological Control over Lamellar Manganese Metal‐Organic Framework through Modulated Bi‐Phase Growth

Shen

Shan

et al. 2020

Angew Chem Int Ed

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A modulated bi‐phase synthesis towards large‐scale manganese 1,4‐benzenedicarboxylate (MnBDC) MOFs with a precise control over their morphology (bulk vs. layered) is presented. Metal precursors and organic ligands are separated to reduce the kinetic reaction rates for better control over the crystallization process. Based on scanning electron microscopy (SEM), X‐ray diffraction (XRD), energy‐dispersive X‐ray spectroscopy (EDS), and Raman spectroscopy studies, the continuous ligand supply along with the presence of pyridine capping agent are highly effective in promoting the layer‐by‐layer growth and achieving large crystal sizes. Once layered MnBDC is stabilized, topotactic intercalation chemistry was used to demonstrate the feasibility of bromine intercalation on these layered materials. Bromine intercalation is possible between the MOFs layers for the first time. Bromine intercalation causes colossal reduction in layered MnBDC band gap while it has no observable effect on bulk MOFs.

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“…As the starting point of all the subsequent steps, the acquisition of quality building blocks is imperative yet challenging. This is contingent on proper synthesis of bulk materials, and their exfoliation into dispersible, monolayered and defect‐free 2D nanosheets for membrane fabrication . On this basis, efficient surface modification methods should be available for the nanosheets so that desirable transporting characteristics can be obtained in resultant laminates .…”

Section: Discussionmentioning

confidence: 99%

2D Laminar Membranes for Selective Water and Ion Transport

Kang

Xia

Wang

et al. 2019

Adv Funct Materials

258

148

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energy storage and conversion devices, [26][27][28] as outlined in recent reviews (Figure 1, left). [29] Behind these applications lie a fundamental question: how water and ion transport are controlled in the laminar structure to obtain desired selectivity. A comprehensive summary of structure-transport relation is thereby imperative to understand and optimize membrane selective performance, but is so far lacking. In such context, our review aims to fill this gap by discussing: 1) how 2D materials with specific physicochemical features are assembled into laminar membranes; 2) most importantly, how membrane structure, and its response to external impacts, can tune mass transport (herein, water and ions); 3) how these transport mechanisms translate into selectivity in applications, and into future design of high-performance laminar membranes. Unsolved problems and emerging challenges around these topics are then concluded. We note that the knowledge summarized here can also, at least partly, assist the understanding of the selective gas, liquid, and micromolecule transport through laminar membranes, which are gaining considerable attention as well. [30][31][32] Transition Metal Carbides and/or Nitrides (MXene): MXene nanosheets are etched and delaminated from parent bulk MAX to M n+1 X n T x (e.g., Ti 3 C 2 T x ), and have thus several atom sublayers. [39] While M and X are early transition metal

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Ultimate Control over Hydrogen Bond Formation and Reaction Rates for Scalable Synthesis of Highly Crystalline vdW MOF Nanosheets with Large Aspect Ratio

Cited by 39 publications

References 38 publications

Achieving Morphological Control over Lamellar Manganese Metal‐Organic Framework through Modulated Bi‐Phase Growth

Achieving Morphological Control over Lamellar Manganese Metal‐Organic Framework through Modulated Bi‐Phase Growth

Achieving Morphological Control over Lamellar Manganese Metal‐Organic Framework through Modulated Bi‐Phase Growth

2D Laminar Membranes for Selective Water and Ion Transport

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