Band Alignment as the Method for Modifying Electronic Structure of Metal−Organic Frameworks

Syzgantseva, Maria A.; Stepanov, N. F.; Syzgantseva, Olga A.

doi:10.1021/acsami.0c02094

Cited by 49 publications

(51 citation statements)

References 70 publications

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“…[36] Syzgantseva et al studied and summarized the impact of the functional groups and scaffolds of ligands in MOFs. [37] The influence of F, Cl, Br, I, OH, SH, CN, NH 2 , NO 2 , SO 3 H, PO 3 H 2 , and NMe 2 in MIL-125 were studied systematically. Meanwhile, for UiO-66, F, Cl, Br, I, OH, SH, CN, NH 2 , and NO 2 were considered.…”

Section: Pristine Mofsmentioning

confidence: 99%

Designing MOF Nanoarchitectures for Electrochemical Water Splitting

et al. 2021

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carrier with an extremely high energy density (approximately 142 MJ kg −1 ) and zero-carbon content, has been regarded as a promising clean fuel. [1,2] In this context, electrochemical water splitting, which converts electricity into storable hydrogen, is a viable and efficient solution to mitigate severe energy shortages and greenhouse gas emissions. [3] Among these strategies, hydrogen and oxygen evolution reactions, which occur on the cathode and anode, respectively, in a water electrolyzer, are considered as two critical half-reactions of the water-splitting process. [4] Theoretically, water splitting requires a thermodynamic Gibbs free energy (ΔG) of approximately 237.2 kJ mol −1 , corresponding to a standard potential (ΔE) of 1.23 V versus a reversible hydrogen electrode (RHE), which allows the thermodynamically uphill reaction to occur in the electrolyzer. [5] However, the unfavorable thermodynamics and resulting large overpotential are the main barriers to the scalable implementation of water electrolysis for hydrogen generation. [6,7] Currently, noble metal-based electrocatalysts exhibit the most efficient activity for water splitting, particularly Pt-based hydrogen evolution reaction (HER) catalysts and Ir/Ru-based oxygen evolution reaction (OER) catalysts. [8,9] Nevertheless, the scarcity and high price of precious metals severely impede their widespread use in commercial water-splitting applications. Taking these limitations into Electrochemical water splitting has attracted significant attention as a key pathway for the development of renewable energy systems. Fabricating efficient electrocatalysts for these processes is intensely desired to reduce their overpotentials and facilitate practical applications. Recently, metal-organic framework (MOF) nanoarchitectures featuring ultrahigh surface areas, tunable nanostructures, and excellent porosities have emerged as promising materials for the development of highly active catalysts for electrochemical water splitting. Herein, the most pivotal advances in recent research on engineering MOF nanoarchitectures for efficient electrochemical water splitting are presented. First, the design of catalytic centers for MOF-based/derived electrocatalysts is summarized and compared from the aspects of chemical composition optimization and structural functionalization at the atomic and molecular levels. Subsequently, the fast-growing breakthroughs in catalytic activities, identification of highly active sites, and fundamental mechanisms are thoroughly discussed. Finally, a comprehensive commentary on the current primary challenges and future perspectives in water splitting and its commercialization for hydrogen production is provided. Hereby, new insights into the synthetic principles and electrocatalysis for designing MOF nanoarchitectures for the practical utilization of water splitting are offered, thus further promoting their future prosperity for a wide range of applications.

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Section: Pristine Mofsmentioning

confidence: 99%

Designing MOF Nanoarchitectures for Electrochemical Water Splitting

et al. 2021

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“…The actual band positions of MOCs differ with the metal centers and organic ligands systems. [ 67 ] The metal‐organic crystal (Cu‐MOC) based dielectric thin film may be articulated with molecular orbital or solid‐state energy band or metal nodes based periodic solids. [ 68 ] Combining the molecular functionalities and control of solid‐state systems, the Cu‐MOC materials may be modeled with a more localized highest occupied crystal orbital (HOCO) and lowest unoccupied crystal orbital (LUCO).…”

Section: Resultsmentioning

confidence: 99%

Integration of High‐Performance Cost‐Effective Copper‐Metal‐Organic‐Nanocluster‐based Gate Dielectric for Next‐Generation CMOS Applications

Gupta

Kumar

Sharma

2021

Adv Elect Materials

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The suitability of metal‐organic frameworks (MOFs) as functional materials for future electronic logic devices with desirable dielectric constant, bandgap, high‐quality interface, low leakage current, and better compatibility is still an open challenge. Owing to the synergistic complementary properties of MOFs systems, a low‐cost copper‐metal‐organic nanoclusters (Cu‐MOCs) has been synthesized comprising inorganic copper metal unit allied organic m‐toluic acid ligand by facile sol–gel strategy. It offers large‐area thin‐films uniformity, high dielectric constant (κ ≈ 5.49), improved interfacial properties, dynamic switching behavior with the stimuli field, and extends the realization of metal‐organic‐framework dielectric for scalable complementary‐metal‐oxide‐semiconductor (CMOS) logic applications over customary hybrid counterparts. Various techniques such as single crystal X‐ray diffraction, X‐ray photoelectron spectroscopy, thermogravimetric analysis, and energy dispersive X‐ray spectroscopy have been used to validate the Cu‐MOCs formulation. In particular, the fabricated Cu‐MOCs, metal–insulator–semiconductor structures exhibit promising dynamic switching behavior responsive to the applied field, hysteresis‐free capacitance–voltage characteristics, low interfacial trap density (≈1.4 × 1011 eV−1 cm−2), low effective oxide charges (≈1.1 × 1011 cm−2), and noteworthy small leakage current density (≈1.29 nA cm−2 @ 1 V) ever since in electrical analysis. Cost‐effective novel Cu‐MOCs successfully demonstrate high‐performance, reliable gate dielectrics for next‐generation CMOS logic devices.

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“…For example, our model recognises that the addition of an amino group leads to a redshi for UiO-66. Likewise, we can analyse the inuence of metal substitutions, e.g., the doping of UiO-66-NH 2 with Nb leading to a redshi as described by Syzgantseva et al 47…”

Section: Test On Experimental Compoundsmentioning

confidence: 99%

“…Likewise, we can analyse the influence of metal substitutions, e.g. , the doping of UiO-66-NH 2 with Nb leading to a redshift as described by Syzgantseva et al 47 …”

Section: Test On Experimental Compoundsmentioning

confidence: 99%