scholarly journals Rational incorporation of defects within metal-organic frameworks generates highly active electrocatalytic sites

2021 ◽  
Author(s):  
Nina Heidary ◽  
Daniel Chartrand ◽  
Amandine Guiet ◽  
Nikolay Kornienko
Keyword(s):  
Active Sites ◽  
A Priori ◽  
Metal Organic Frameworks ◽  
Highly Active ◽  
Catalytically Active ◽  
Metal Organic ◽  
Degree Of Control

The allure of metal-organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate...

scholarly journals Rational Incorporation of Missing Linker Defects Within Metal-Organic Frameworks Generates Highly Active Electrocatalytic Sites

2020 ◽  
Author(s):  
Nina Heidary ◽  
Daniel Chartrand ◽  
Nikolay Kornienko
Keyword(s):  
Active Sites ◽  
A Priori ◽  
Metal Organic Frameworks ◽  
Ex Situ ◽  
Redox Potentials ◽  
Faradaic Efficiency ◽  
Binding Motifs ◽  
Highly Active ◽  
Catalytically Active ◽  
Metal Organic

The allure of metal-organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal node. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni74D, is evaluated vs. the nominally defect-free Ni74 MOF with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni74D features a set of 4-coordinate Ni-O4 sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni74 MOF, being able to convert HMF to the desired 2,5- furandicarboxylic acid at 95% yield and 80% Faradaic efficiency. The strategy put forth to rationally design coordinatively-unsaturated electrocatalytic sites and the methodology put forth in investigating their behavior stand to bolster the understanding and growth of the field.

scholarly journals Rational Incorporation of Missing Linker Defects Within Metal-Organic Frameworks Generates Highly Active Electrocatalytic Sites

2020 ◽  
Author(s):  
Nina Heidary ◽  
Daniel Chartrand ◽  
Nikolay Kornienko
Keyword(s):  
Active Sites ◽  
A Priori ◽  
Metal Organic Frameworks ◽  
Ex Situ ◽  
Redox Potentials ◽  
Faradaic Efficiency ◽  
Binding Motifs ◽  
Highly Active ◽  
Catalytically Active ◽  
Metal Organic

The allure of metal-organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal node. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni74D, is evaluated vs. the nominally defect-free Ni74 MOF with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni74D features a set of 4-coordinate Ni-O4 sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni74 MOF, being able to convert HMF to the desired 2,5- furandicarboxylic acid at 95% yield and 80% Faradaic efficiency. The strategy put forth to rationally design coordinatively-unsaturated electrocatalytic sites and the methodology put forth in investigating their behavior stand to bolster the understanding and growth of the field.

scholarly journals Tuning Atomically Dispersed Fe Sites in Metal–Organic Frameworks Boosts Peroxidase-Like Activity for Sensitive Biosensing

2020 ◽  
Vol 12 (1) ◽  
Author(s):  
Weiqing Xu ◽  
Yikun Kang ◽  
Lei Jiao ◽  
Yu Wu ◽  
Hongye Yan ◽  
...  
Keyword(s):  
Active Sites ◽  
Rational Design ◽  
Limit Of Detection ◽  
Theoretical Calculations ◽  
Organophosphorus Pesticides ◽  
Metal Organic Frameworks ◽  
Atomic Scale ◽  
Electronic Effects ◽  
Highly Active ◽  
Metal Organic

AbstractAlthough nanozymes have been widely developed, accurate design of highly active sites at the atomic level to mimic the electronic and geometrical structure of enzymes and the exploration of underlying mechanisms still face significant challenges. Herein, two functional groups with opposite electron modulation abilities (nitro and amino) were introduced into the metal–organic frameworks (MIL-101(Fe)) to tune the atomically dispersed metal sites and thus regulate the enzyme-like activity. Notably, the functionalization of nitro can enhance the peroxidase (POD)-like activity of MIL-101(Fe), while the amino is poles apart. Theoretical calculations demonstrate that the introduction of nitro can not only regulate the geometry of adsorbed intermediates but also improve the electronic structure of metal active sites. Benefiting from both geometric and electronic effects, the nitro-functionalized MIL-101(Fe) with a low reaction energy barrier for the HO* formation exhibits a superior POD-like activity. As a concept of the application, a nitro-functionalized MIL-101(Fe)-based biosensor was elaborately applied for the sensitive detection of acetylcholinesterase activity in the range of 0.2–50 mU mL−1 with a limit of detection of 0.14 mU mL−1. Moreover, the detection of organophosphorus pesticides was also achieved. This work not only opens up new prospects for the rational design of highly active nanozymes at the atomic scale but also enhances the performance of nanozyme-based biosensors.

Metal-organic-framework derived hollow manganese nickel selenide spheres confined with nanosheets on nickel foam for hybrid supercapacitors

2021 ◽  
Author(s):  
Bahareh ameri ◽  
Akbar Mohammadi Zardkhoshoui ◽  
Saied Saeed Hosseiny Davarani
Keyword(s):  
Active Sites ◽  
Nickel Foam ◽  
Metal Organic Framework ◽  
High Surface ◽  
Metal Organic Frameworks ◽  
High Surface Area ◽  
Supercapacitive Performance ◽  
Hybrid Supercapacitors ◽  
Porous Networks ◽  
Metal Organic

Metal-organic frameworks (MOFs) derived nanoarchitectures have special features, such as high surface area (SA), abundant active sites, exclusive porous networks, and remarkable supercapacitive performance when compared to traditional nanoarchitectures. Herein,...

scholarly journals Effect of linker functionalisation on the catalytic properties of Cu nanoclusters embedded in MOFs in direct CO and CO2 reduction by H2

2021 ◽  
Author(s):  
Cornelia Elizabeth Pompe ◽  
Petra Agota Szilagyi
Keyword(s):  
Catalytic Properties ◽  
Metal Organic Frameworks ◽  
Co2 Reduction ◽  
Catalytically Active ◽  
Metal Organic ◽  
Cu Nanoclusters

Metal-organic frameworks are promising host supporting matrices for catalytically active guest. In particular, their crystallinity renders them desirable as their pores may act as atom-precise templates for the growth of...

A small molecular, a big scissoring effect: sodium dodecyl sulfate working on two-dimensional metal organic frameworks

CrystEngComm ◽  
2021 ◽  
Author(s):  
Qing Luo ◽  
Zhen Ding ◽  
Huamin Sun ◽  
Zhen Cheng ◽  
Naien SHI ◽  
...  
Keyword(s):  
Sodium Dodecyl Sulfate ◽  
Active Sites ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Sodium Dodecyl ◽  
Advanced Materials ◽  
Controlled Synthesis ◽  
Two Dimensional ◽  
Dodecyl Sulfate ◽  
Metal Organic

Ultrathin two-dimensional (2D) metal-organic framework (MOF) nanosheets are prosperous advanced materials due to their particularly thin thickness and exposed active sites. The difficulty in the controlled synthesis of 2D MOF...

From Ru nanoparticle-encapsulated metal–organic frameworks to highly catalytically active Cu/Ru nanoparticle-embedded porous carbon

2017 ◽  
Vol 5 (10) ◽  
pp. 4835-4841 ◽  
Author(s):  
Pradip Pachfule ◽  
Xinchun Yang ◽  
Qi-Long Zhu ◽  
Nobuko Tsumori ◽  
Takeyuki Uchida ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
High Temperature ◽  
Porous Carbon ◽  
Metal Organic Frameworks ◽  
Ammonia Borane ◽  
Carbon Composites ◽  
High Catalytic Activity ◽  
Catalytically Active ◽  
Metal Organic

High-temperature pyrolysis of Ru nanoparticle-encapsulated MOF (Ru@HKUST-1) afforded ultrafine Cu/Ru nanoparticle-embedded porous carbon composites (Cu/Ru@C), which show high catalytic activity for ammonia borane hydrolysis.

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