Tuning Electrical and Mechanical Properties of Metal–Organic Frameworks by Metal Substitution

Yan, Yabin; Wang, Chunyu; Cai, Zhengqing; Wang, Xiaoyuan; Xuan, Fuzhen

doi:10.1021/acsami.3c08470

Cited by 7 publications

(5 citation statements)

References 43 publications

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“…In addition, the ELF at the O site is spherically asymmetric, inferring the directional bonding between the Co and O atoms. 40 Meanwhile, the ELF of M-3375 at the Co site exhibits small values, which might be attributed to the Co–O ionic interactions. On the other hand, the ELF distribution between the C and O atoms shows large values, indicating the covalent bonds between these atoms.…”

Section: Resultsmentioning

confidence: 97%

Catalytic activities modulated by flexible bimetallic metal–organic frameworks

2023

CrystEngComm

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Section: Resultsmentioning

confidence: 97%

Catalytic activities modulated by flexible bimetallic metal–organic frameworks

2023

CrystEngComm

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“…Terahertz (THz, 1 THz = 10 12 Hz) waves, defined within the frequency range of 0.1-10 THz between microwave and infrared bands, have important applications in biochemical sensing, imaging, wireless communication, and radar [1][2][3][4][5]. With the development of THz technology, artificial microstructures have become a hot topic in recent research [6][7][8][9]. THz metasurfaces are electromagnetic structures with orderly arranged two-dimensional subwavelength unit elements.…”

Section: Introductionmentioning

confidence: 99%

Terahertz structured deep-subwavelength plasmonic grating metasurface for manipulating polarization-dependent coupling response

Wang,

Fan,

Zhao

et al. 2024

J. Phys. D: Appl. Phys.

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The complex electromagnetic anisotropy of terahertz (THz) metasurfaces with geometric symmetry breaking has attracted extensive attention. Typical effects arise from the coupling of polarization responses in orthogonal directions of various components of the metasurface structure, such as the electromagnetically induced transparency (EIT) effect. However, it is a challenge to precisely control or perfectly avoid the polarization-dependent coupling responses. In this work, deep-subwavelength plasmonic gratings (PGs) with a fine wire width of 1 μm at the order of deep subwavelengths of 1/100 THz wave are fabricated by electron beam lithography, and these wire gratings are graphically designed as a C-shaped metasurface pattern with a period of 100 μm in sub-wavelength scale. The complete anisotropic response in the single-oriented PG metasurface is demonstrated by both simulation and experiments, where the polarization-dependent coupling effect is eliminated. More interestingly, the hybrid-oriented PG metasurface exhibits narrowband and wideband EIT effects in the x and y polarization directions with the maximum polarization extinction ratio of 20 dB, respectively, indicating this mechanism can realize more flexible manipulation of polarization-dependent coupling. This patterned deep-subwavelength PG provides a new structure and mechanism for excitation, regulation, and restriction of polarization-dependent mode coupling, and has important applications in THz spectroscopic detection, polarization imaging, and wireless communication.

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“…25,26 Early DFT calculations using a semilocal exchange−correlation (XC) functional have classified MOF-5 as a semiconductor material, reporting an electronic band gap of around 3.6 eV. 12,27,28 Other ab initio calculations considering different XC hybrid functionals have reported band gaps between 4.6 and 5.0 eV. 26,29,30 Recently, many-body calculations have found that MOF-5 would be an insulator with an electronic band gap of around 8 eV and an optical band gap of 4.5 eV, exhibiting strong excitonic effects.…”

Section: ■ Introductionmentioning

confidence: 99%

“…33 The synthesis of stable MOF-5 doped with transition metals (V, Ti, Cr, Mn, and Fe) substituting Zn atoms has been previously reported. 28,34 In this context, it is demonstrated that metal doping induces redox reactivity, mediating reactions through electron transfer. In addition, Syzgantseva et al 15 have also considered metal doping and ligand functionalization as a strategy to modify MOF electronic structure, validated by experiments.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The MOF of composition Zn 4 O(BDC) 3 (BDC = benzene-1, 4-dicarboxylate), known as MOF-5 or IRMOF-1, was first synthesized by Li et al in 1999, , since then it has been the subject of intensive research in catalysis, − gas sensing, and optoelectronics. , Early DFT calculations using a semilocal exchange–correlation (XC) functional have classified MOF-5 as a semiconductor material, reporting an electronic band gap of around 3.6 eV. ,, Other ab initio calculations considering different XC hybrid functionals have reported band gaps between 4.6 and 5.0 eV. ,, Recently, many-body calculations have found that MOF-5 would be an insulator with an electronic band gap of around 8 eV and an optical band gap of 4.5 eV, exhibiting strong excitonic effects . On the other hand, experimental measurements of the optical band gap of MOF-5 are quite controversial.…”

Section: Introductionmentioning

confidence: 99%

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Metal Substitutions in the MOF-5 Metal–Organic Framework: A Hybrid Density Functional Theory Study

Orellana

2024

J. Phys. Chem. C

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Doping properties of the MOF-5 metal−organic framework [Zn 4 O(BDC) 3 , BDC = benzodicarboxylate] are explored using density functional theory calculations, with hybrid functional. Our investigation primarily focused on the stability, electronic structure, and formation energy of MOF-5 when doped with an M atom (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Al), occupying a single Zn site per unit cell. Our findings reveal that MOF-5 exhibits insulating characteristics with an electronic band gap of 4.8 eV. However, after metal doping, impurity levels are observed throughout the band gap. Sc and Al introduce semioccupied levels close to the conduction band minimum, which can impart donor-like characteristics to the material. Formation energy calculations indicate that Sc, Al, Ti, and V exhibit stability in the single-positive charge state for Fermi energy values lower than 3 eV, while Cr, Mn, Fe, Co, and Ni are stable in neutral charge states. It is noteworthy that dopants with unpaired electrons retain this property when inserted at Zn sites, inducing local magnetization in MOF-5. Consequently, our findings suggest that the electronic properties of MOF-5 undergo drastic modification after the incorporation of specific metal dopants, indicating the potential for the development of metal−organic frameworks as functional materials.

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Tuning Electrical and Mechanical Properties of Metal–Organic Frameworks by Metal Substitution

Cited by 7 publications

References 43 publications

Catalytic activities modulated by flexible bimetallic metal–organic frameworks

Catalytic activities modulated by flexible bimetallic metal–organic frameworks

Terahertz structured deep-subwavelength plasmonic grating metasurface for manipulating polarization-dependent coupling response

Metal Substitutions in the MOF-5 Metal–Organic Framework: A Hybrid Density Functional Theory Study

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