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

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

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Large-scale synthesis of van der Waals (vdW) metal–organic framework (MOF) nanosheets with controlled crystallinity and interlayer coupling strength is one of the bottlenecks in 2D materials that has limited its successful transition to large-scale applications. Here, scalable synthesis of mBDC (m = Zn and Cu) 2D MOFs at large scales through a biphase method is demonstrated. The results show replacing water molecules with pyridine eliminates hydrogen bond formation at metal cluster sites. This prohibits tight coupling across adjacent MOF layers and sustains controllable 2D vdW MOF growth. It is further shown that control over the growth speed, crystallinity, and thickness can be achieved by addition of a controlled amount of triethylamine and formic acid to achieve highly crystalline vdW MOF nanosheets with extraordinarily high aspect ratio. The described synthesis route can easily be scaled up for large-scale production either by deposition onto desired substrates or in crystalline layered powder form. Owing to its large lateral size, vdW nature, and high crystallinity, it is possible to perform atomic force microscopy, Kelvin probe force microscopy, and Raman measurements on the 2D MOFs. The results not only establish their vibrational properties and layer-dependent responses but also show striking differences from other 2D inorganic materials.

Original languageEnglish (US)
Article number1802497
JournalAdvanced Materials
DOIs
StateAccepted/In press - Jan 1 2018

Fingerprint

Nanosheets
Reaction rates
Aspect ratio
Hydrogen bonds
formic acid
Crystalline materials
Formic acid
Pyridine
Powders
Atomic force microscopy
Microscopic examination
Metals
Molecules
Water
Substrates

Keywords

  • crystallinity
  • hydrogen bonds
  • reaction rate
  • scalable synthesis
  • vdW 2D MOFs

ASJC Scopus subject areas

  • Materials Science(all)
  • Mechanics of Materials
  • Mechanical Engineering

Cite this

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 B.; Chen, Bin; Liu, Lei; Zhuang, Houlong; Mu, Bin; Tongay, Sefaattin.

In: Advanced Materials, 01.01.2018.

Research output: Contribution to journalArticle

@article{332b2877c40e4409866cc510519f11ee,
title = "Ultimate Control over Hydrogen Bond Formation and Reaction Rates for Scalable Synthesis of Highly Crystalline vdW MOF Nanosheets with Large Aspect Ratio",
abstract = "Large-scale synthesis of van der Waals (vdW) metal–organic framework (MOF) nanosheets with controlled crystallinity and interlayer coupling strength is one of the bottlenecks in 2D materials that has limited its successful transition to large-scale applications. Here, scalable synthesis of mBDC (m = Zn and Cu) 2D MOFs at large scales through a biphase method is demonstrated. The results show replacing water molecules with pyridine eliminates hydrogen bond formation at metal cluster sites. This prohibits tight coupling across adjacent MOF layers and sustains controllable 2D vdW MOF growth. It is further shown that control over the growth speed, crystallinity, and thickness can be achieved by addition of a controlled amount of triethylamine and formic acid to achieve highly crystalline vdW MOF nanosheets with extraordinarily high aspect ratio. The described synthesis route can easily be scaled up for large-scale production either by deposition onto desired substrates or in crystalline layered powder form. Owing to its large lateral size, vdW nature, and high crystallinity, it is possible to perform atomic force microscopy, Kelvin probe force microscopy, and Raman measurements on the 2D MOFs. The results not only establish their vibrational properties and layer-dependent responses but also show striking differences from other 2D inorganic materials.",
keywords = "crystallinity, hydrogen bonds, reaction rate, scalable synthesis, vdW 2D MOFs",
author = "Yuxia Shen and Bohan Shan and Hui Cai and Ying Qin and Ashutosh Agarwal and Trivedi, {Dipesh B.} and Bin Chen and Lei Liu and Houlong Zhuang and Bin Mu and Sefaattin Tongay",
year = "2018",
month = "1",
day = "1",
doi = "10.1002/adma.201802497",
language = "English (US)",
journal = "Advanced Materials",
issn = "0935-9648",
publisher = "Wiley-VCH Verlag",

}

TY - JOUR

T1 - Ultimate Control over Hydrogen Bond Formation and Reaction Rates for Scalable Synthesis of Highly Crystalline vdW MOF Nanosheets with Large Aspect Ratio

AU - Shen, Yuxia

AU - Shan, Bohan

AU - Cai, Hui

AU - Qin, Ying

AU - Agarwal, Ashutosh

AU - Trivedi, Dipesh B.

AU - Chen, Bin

AU - Liu, Lei

AU - Zhuang, Houlong

AU - Mu, Bin

AU - Tongay, Sefaattin

PY - 2018/1/1

Y1 - 2018/1/1

N2 - Large-scale synthesis of van der Waals (vdW) metal–organic framework (MOF) nanosheets with controlled crystallinity and interlayer coupling strength is one of the bottlenecks in 2D materials that has limited its successful transition to large-scale applications. Here, scalable synthesis of mBDC (m = Zn and Cu) 2D MOFs at large scales through a biphase method is demonstrated. The results show replacing water molecules with pyridine eliminates hydrogen bond formation at metal cluster sites. This prohibits tight coupling across adjacent MOF layers and sustains controllable 2D vdW MOF growth. It is further shown that control over the growth speed, crystallinity, and thickness can be achieved by addition of a controlled amount of triethylamine and formic acid to achieve highly crystalline vdW MOF nanosheets with extraordinarily high aspect ratio. The described synthesis route can easily be scaled up for large-scale production either by deposition onto desired substrates or in crystalline layered powder form. Owing to its large lateral size, vdW nature, and high crystallinity, it is possible to perform atomic force microscopy, Kelvin probe force microscopy, and Raman measurements on the 2D MOFs. The results not only establish their vibrational properties and layer-dependent responses but also show striking differences from other 2D inorganic materials.

AB - Large-scale synthesis of van der Waals (vdW) metal–organic framework (MOF) nanosheets with controlled crystallinity and interlayer coupling strength is one of the bottlenecks in 2D materials that has limited its successful transition to large-scale applications. Here, scalable synthesis of mBDC (m = Zn and Cu) 2D MOFs at large scales through a biphase method is demonstrated. The results show replacing water molecules with pyridine eliminates hydrogen bond formation at metal cluster sites. This prohibits tight coupling across adjacent MOF layers and sustains controllable 2D vdW MOF growth. It is further shown that control over the growth speed, crystallinity, and thickness can be achieved by addition of a controlled amount of triethylamine and formic acid to achieve highly crystalline vdW MOF nanosheets with extraordinarily high aspect ratio. The described synthesis route can easily be scaled up for large-scale production either by deposition onto desired substrates or in crystalline layered powder form. Owing to its large lateral size, vdW nature, and high crystallinity, it is possible to perform atomic force microscopy, Kelvin probe force microscopy, and Raman measurements on the 2D MOFs. The results not only establish their vibrational properties and layer-dependent responses but also show striking differences from other 2D inorganic materials.

KW - crystallinity

KW - hydrogen bonds

KW - reaction rate

KW - scalable synthesis

KW - vdW 2D MOFs

UR - http://www.scopus.com/inward/record.url?scp=85055926817&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85055926817&partnerID=8YFLogxK

U2 - 10.1002/adma.201802497

DO - 10.1002/adma.201802497

M3 - Article

JO - Advanced Materials

JF - Advanced Materials

SN - 0935-9648

M1 - 1802497

ER -