Tetrazole-functionalized benzoquinoline-linked covalent organic frameworks with efficient performance for electrocatalytic H<sub>2</sub>O<sub>2</sub>production and Li–S batteries

Wu, Zhuangzhuang; Luo, Junming; Liang, Ying; Yu, Xinxin; Zhao, Yue; Li, Yongpeng; Wang, Wenxin; Sui, Zhuyin; Tian, Xinlong; Chen, Qi

doi:10.1039/d2qm01301k

Cited by 20 publications

(12 citation statements)

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“…In the tetrazolinyl ring, the chemical environments of the four nitrogen atoms are very similar, thus, within the experimental resolution, we expect a single asymmetric line, as it is the actual case both for powders and assemblies. This is consistent with previously published results on the diamagnetic tetrazole-based systems. − The main line at around 400 eV shows a pronounced shoulder. This suggests a stronger delocalization/screening of the core hole created upon photoemission in one of the nitrogen atoms.…”

Section: Resultsmentioning

confidence: 99%

Thermally Ultrarobust S = 1/2 Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface

et al. 2023

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Open-shell organic molecules, including S = 1/2 radicals, may provide enhanced properties for several emerging technologies; however, relatively few synthesized to date possess robust thermal stability and processability. We report the synthesis of S = 1/2 biphenylene-fused tetrazolinyl radicals 1 and 2. Both radicals possess near-perfect planar structures based on their X-ray structures and density-functional theory (DFT) computations. Radical 1 possesses outstanding thermal stability as indicated by the onset of decomposition at 269 °C, based on thermogravimetric analysis (TGA) data. Both radicals possess very low oxidation potentials <0 V (vs. SCE) and their electrochemical energy gaps, E cell ≈ 0.9 eV, are rather low. Magnetic properties of polycrystalline 1 are characterized by superconducting quantum interference device (SQUID) magnetometry revealing a one-dimensional S = 1/2 antiferromagnetic Heisenberg chain with exchange coupling constant J′/k ≈ −22.0 K. Radical 1 in toluene glass possesses a long electron spin coherence time, T m ≈ 7 μs in the 40–80 K temperature range, a property advantageous for potential applications as a molecular spin qubit. Radical 1 is evaporated under ultrahigh vacuum (UHV) forming assemblies of intact radicals on a silicon substrate, as confirmed by high-resolution X-ray photoelectron spectroscopy (XPS). Scanning electron microscope (SEM) images indicate that the radical molecules form nanoneedles on the substrate. The nanoneedles are stable for at least 64 hours under air as monitored by using X-ray photoelectron spectroscopy. Electron paramagnetic resonance (EPR) studies of the thicker assemblies, prepared by UHV evaporation, indicate radical decay according to first-order kinetics with a long half-life of 50 ± 4 days at ambient conditions.

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Section: Resultsmentioning

confidence: 99%

Thermally Ultrarobust S = 1/2 Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface

et al. 2023

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“…This is consistent with previously published results on the diamagnetic tetrazolebased systems. [84][85][86][87][88] The main line at around 400 eV shows a pronounced shoulder. This suggests a stronger delocalization/screening of the core hole created upon photoemission in one of the nitrogen atoms.…”

Section: S21 Si) the Resultant Value Ofmentioning

confidence: 99%

Thermally Ultra-Robust S = ½ Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface.

Yang

Pink

Nowik-Boltyk

et al. 2023

Preprint

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Open-shell organic molecules, including S = ½ radicals, may provide enhanced properties for several emerging technologies, however, relatively few synthesized to date possess robust thermal stability and processability. We report synthesis of S = ½ biphenylene-fused tetrazolinyl radicals 1 and 2. Both radicals possess near-perfect planar structures based on their X-ray structures and DFT computations. Radical 1 possesses an outstanding thermal stability as indicated by the onset of decomposition at 269 °C, based on thermogravimetric analysis (TGA) data. Both radicals possess very low oxidation potentials < 0 V (vs. SCE) and their electrochemical energy gaps, Ecell 0.9 eV, are rather low. Magnetic properties of polycrystalline 1 are characterized by SQUID magnetometry revealing a one-dimensional S = ½ antiferromagnetic Heisenberg chain with exchange coupling constant J’/k –22.0 K. Radical 1 in toluene glass possesses a long electron spin coherence time, Tm ≈ 7 μs in the 40 – 80 K temperature range, a property advantageous for potential applications as a molecular spin qubit. Radical 1 is evaporated under ultrahigh vacuum (UHV) forming assemblies of intact radicals on a silicon substrate, as confirmed by high-resolution X-ray photoelectron spectroscopy (XPS). Scanning electron microscope (SEM) images indicate that the radical molecules form nanoneedles on the substrate. The nanoneedles are stable for at least 64 hours under air as monitored by using X-ray photoelectron spectroscopy. EPR studies of the thicker assemblies, prepared by UHV evaporation, indicate radical decay according to first-order kinetics with a long half-life of 50 +/-4 days at ambient conditions.

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“…45 The existence of C−O (531.8 eV) and C�O (533.2 eV) bonds is also confirmed by the XPS spectra of the O 1s (Figure 4g). Also, the presence of N�N and C�N (that is, N−N�N and N−N�C in tetrazole moiety, respectively) bonds is depicted by the existence of their corresponding peaks at 399.3 and 401.2 eV, respectively, 46,47 (Figure 4h). Furthermore, the S 2p XPS spectra (Figure 4i) was deconvoluted into two peaks positioned at 162.5 and 163.8 eV, and given to C−S 2p 3/2 and C−S 2p 1/2 , respectively.…”

Section: Structural Description and Characterization Ofmentioning

confidence: 99%

Zn-MOF as a Single Catalyst with Dual Lewis Acidic and Basic Reaction Sites for CO₂ Fixation

Eskemech,

Chand,

Karmakar

et al. 2024

Inorg. Chem.

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Continuous increase in carbon dioxide (CO 2 ) emissions are causing imbalances in the environment, which impact biodiversity and human health. The conversion of CO 2 to cyclic carbonates by means of metal−organic frameworks (MOFs) as a heterogeneous catalyst is a prominent strategy for rectifying this imbalance. Herein, we have developed nitrogen-rich Zn (II) based metal−organic framework, [Zn(CPMT)(bipy)] n (CPMT = 1-(4-carboxyphenyl)-5-mercapto-1Htetrazole; bipy = 4,4′-bipyridine), synthesized via a mixed ligand strategy. This Zn-MOF showed high chemical stability in both acidic and basic conditions, and in organic solvents for a long time. On account of the concurrent presence of acid− base active sites and strong chemical stability under abrasive conditions, this Zn-MOF was employed as an effective catalyst for the coupling of CO 2 and epoxides, under atmospheric pressure, mild temperature, and neat conditions. This Zn-MOF shows remarkable activity by producing high yields of epichlorohydrin carbonate (98%) and styrene carbonate (82%) at atmospheric CO 2 pressure, 70 °C temperature, and 24 h reaction time, with turnover numbers (TON) of 217 and 181, respectively. The Zn-MOF could be reused for up to seven cycles with structural and framework integrity. Overall, this work demonstrates the synthesis of a novel and highly efficient MOF for CO 2 conversion.

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Tetrazole-functionalized benzoquinoline-linked covalent organic frameworks with efficient performance for electrocatalytic H₂O₂production and Li–S batteries

Abstract: It is of pressing necessity in clean energy conversion and storage to develop electrochemical materials with high activity and stability toward electrocatalytic hydrogen peroxide (H2O2) production and lithium-sulfur (Li-S) batteries....

Cited by 20 publications

References 61 publications

Thermally Ultrarobust S = 1/2 Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface

Thermally Ultrarobust S = 1/2 Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface

Thermally Ultra-Robust S = ½ Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface.

Zn-MOF as a Single Catalyst with Dual Lewis Acidic and Basic Reaction Sites for CO₂ Fixation

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Tetrazole-functionalized benzoquinoline-linked covalent organic frameworks with efficient performance for electrocatalytic H2O2production and Li–S batteries

Abstract: It is of pressing necessity in clean energy conversion and storage to develop electrochemical materials with high activity and stability toward electrocatalytic hydrogen peroxide (H2O2) production and lithium-sulfur (Li-S) batteries....

Cited by 20 publications

References 61 publications

Thermally Ultrarobust S = 1/2 Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface

Thermally Ultrarobust S = 1/2 Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface

Thermally Ultra-Robust S = ½ Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface.

Zn-MOF as a Single Catalyst with Dual Lewis Acidic and Basic Reaction Sites for CO2 Fixation

Contact Info

Product

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Tetrazole-functionalized benzoquinoline-linked covalent organic frameworks with efficient performance for electrocatalytic H₂O₂production and Li–S batteries

Zn-MOF as a Single Catalyst with Dual Lewis Acidic and Basic Reaction Sites for CO₂ Fixation