Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites

Heidary, Nina; Chartrand, Daniel; Guiet, Amandine; Kornienko, Nikolay

doi:10.1039/d1sc00573a

Cited by 62 publications

(43 citation statements)

References 74 publications

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“…The Raman spectra recorded with the presence of HMF exhibit a similar result. Based on the above results and previous achievements made by Wang's and Kornienko's groups, [35, 44] we propose that the HMFOR over Ru 1 ‐NiO is dominated by the OH*‐participated oxidation pathway, instead of the E−C mechanism.…”

Section: Resultssupporting

confidence: 68%

Selective Electrooxidation of Biomass‐Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel‐Oxide‐Supported Ruthenium Single‐Atom Catalyst

Wang

et al. 2022

Angewandte Chemie

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The biomass‐derived alcohol oxidation reaction (BDAOR) holds great promise for sustainable production of chemicals. However, selective electrooxidation of alcohols to value‐added aldehyde compounds is still challenging. Herein, we report the electrocatalytic BDAORs to selectively produce aldehydes using single‐atom ruthenium on nickel oxide (Ru1‐NiO) as a catalyst in the neutral medium. For electrooxidation of 5‐hydroxymethylfurfural (HMF), Ru1‐NiO exhibits a low potential of 1.283 V at 10 mA cm−2, and an optimal 2,5‐diformylfuran (DFF) selectivity of 90 %. Experimental studies reveal that the neutral electrolyte plays a critical role in achieving a high aldehyde selectivity, and the single‐atom Ru boosts HMF oxidation in the neutral medium by promoting water dissociation to afford OH*. Furthermore, Ru1‐NiO can be extended to selective electrooxidation of a series of biomass‐derived alcohols to corresponding aldehydes, which are conventionally difficult to obtain in the alkaline medium.

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Section: Resultssupporting

confidence: 68%

Selective Electrooxidation of Biomass‐Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel‐Oxide‐Supported Ruthenium Single‐Atom Catalyst

Wang

et al. 2022

Angewandte Chemie

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“…[ 36 ] For example, Kornienko's group synthesized a defective metal–organic framework (MOF) by incorporating a fraction of 2‐hydroxyterephthalic acid to replace original 2,5‐dihydroxyterephthalic acid in Ni‐MOF‐74. [ 37 ] The defective MOF (named Ni‐MOF‐74D) features 4‐coordinate NiO 4 sites in comparison with the NiO 5 sites in Ni‐MOF‐74, as shown in the Figure 3h,i. Compared with the original Ni‐MOF‐74, the defective Ni‐MOF‐74D presents increased performance for the HMF oxidation with 95% yield and 80% FE to FDCA via the DFF pathway in the presence of 10 m m HMF at pH = 12.…”

Section: Oxidative Refining Of Biomassmentioning

confidence: 99%

Earth‐Abundant Metal‐Based Electrocatalysts Promoted Anodic Reaction in Hybrid Water Electrolysis for Efficient Hydrogen Production: Recent Progress and Perspectives

Deng

Toe

Xuan

et al. 2022

Advanced Energy Materials

126

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Figure 14. a) Schematic diagram of the ammonia-assisted HWE electrolyzer. b) LSVs curves of LNCO55-Ar and Pt/C. c) Electrolysis current density at 1.23 V, and d) the concentration profile of ammonia and removal efficiency of LNCO55-Ar. Reproduced with permission. [219] Copyright 2021, Wiley-VCH. e) Schematic illustration of the AmOR over ternary NiCuFe oxyhydroxide. f) Energy barrier profiles of different reaction steps in NiCuFe oxyhydroxide and NiCu oxyhydroxide via pathway II. Charge difference g) in NiCu oxyhydroxide system, and h) NiCuFe oxyhydroxide. Reproduced with permission. [221] Copyright 2021, Wiley-VCH. i) Performance comparison of sulfide oxidation and OER catalyzed by CoNi@NGs. j) Photo of the H 2 S electrolysis device driven by a 1.2 V commercial battery directly. k) FE and H 2 evolution rates in a galvanostatic test at 100 mA cm −2 . l) Comparison of the projected density of states of S(3p) and its bonded C(2p) when S is adsorbed on the surface of pristine graphene, CoNi@Gs and CoNi@NGs. m) Free energy profiles of the formation of polysulfides (S x *) in the aqueous solution on N-Graphene's surface and CoNi@NGs' surface. Reproduced with permission. [222]

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“…[252] Similar enhancement was also observed in Ni 2 (OH) 2 (BDC), [Co 3 (C 4 O 4 ) 2 (OH) 2 ]•3H 2 O, and Ni-MOF-74 with vacancies. [253][254][255] Li, Liu, and co-workers demonstrated that by introducing carboxyferrocene to linker vacancies in CoBDC, its OER activity is facilitated. [256]…”

Section: Chemical Conversion At the Vacancy Sitesmentioning

confidence: 99%

Vacancies in Metal−Organic Frameworks: Formation, Arrangement, and Functions

Pang

Yang

2022

Small Structures

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Vacancies in crystalline materials are missing single atoms and missing clusters of atoms in the ordered lattice. In reticular structures such as metal−organic frameworks (MOFs), vacancy can exist in the form of organic linker vacancy, inorganic cluster vacancy, and macroscopic vacancy. In last decade, extensive researches have been developed in exploring the formation, arrangement, and functions of vacancies in MOFs. In this review, an overview of progress in introducing structural vacancies into MOFs either by de novo synthesis or by postsynthetic modification is provided. Different spatial arrangements of vacancies (random, site‐selective, and correlated/ordered) are also highlighted, with an emphasis on new synthetic strategies and mechanisms, and advanced characterization methods needed to control vacancies in a sophisticated manner. Furthermore, enhanced gas adsorption, precise framework grafting, and efficient molecular conversion empowered by vacancies in MOFs are summarized. Future opportunities in this field are envisioned by considering vacancies as a new kind of constituents to reshape the MOF backbone and pores for higher structural complexities and tailored functions.

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Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites

Abstract: 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...

Cited by 62 publications

References 74 publications

Selective Electrooxidation of Biomass‐Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel‐Oxide‐Supported Ruthenium Single‐Atom Catalyst

Selective Electrooxidation of Biomass‐Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel‐Oxide‐Supported Ruthenium Single‐Atom Catalyst

Earth‐Abundant Metal‐Based Electrocatalysts Promoted Anodic Reaction in Hybrid Water Electrolysis for Efficient Hydrogen Production: Recent Progress and Perspectives

Vacancies in Metal−Organic Frameworks: Formation, Arrangement, and Functions

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