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Article
Bio-inspired general synthesis of superplastic metal-organic framework aerogels and their applications
sheng chen
Nanjing University of Science and Technology
Corresponding Author
ORCiD: https://orcid.org/0000-0002-6224-2051
License:
This work is licensed under a CC BY 4.0 License. Read Full License
Many proposed utilizations for metal-organic frameworks (MOFs) demand their assembly into three-dimensional (3D) monolithic architectures. The capability of sustaining structural integrity during considerable deformations is important to allow a monolithic material that works reliably. Nevertheless, it remains a significant challenge to realize high superplasticity in 3D macroscopic MOF networks. Here we report the ice-template-driven assembly of MOF nanobelts to form superelastic MOF-based cellular aerogels. Inspired by the hierarchical architecture of natural cork, the resulting materials can fully and rapidly recover its initial architecture after 50% strain compression and unloading for 2000 cycles. The characteristic hierarchical structure can be extended to single (Ni-, Mn-, and Co-), binary (NiMn-, NiCo-, and CoMn-), and ternary (NiCoMn-) MOF aerogels with exceptionally structural and chemical properties. Potential application has been further demonstrated for NiMn-MOF aerogels in flexible energy conversion, which can effectively electrocatalysize hydrogen evolution in natural seawater even in the presence of considerable electrode deformations. The successful fabrication of such a class of fascinating architectures opens up enormous opportunities for exploring new application of MOFs in a free-standing, structurally adaptive, and macroscopic form
Keywords
Metal-organic frameworks, superplasticity, aerogels, electrocatalysis, hydrogen evolution
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This is a list of supplementary files associated with this preprint. Click to download.
- SI.pdf
Supporting information for publication
- FigS1.png
Additional morphology characterizations of reaction intermediates for the formation of NiFe-MOF nanobelts at different reaction durations (scale bars for a, c, e, g, i, k and m are 10 μm, b, d, f, h, j, l and n are 1 μm).
- FigS2.png
SEM elemental mappings of reaction intermediates for NiFe-MOF nanobelts at different reaction durations (scale bars, 1 μm).
- FigS3.png
Optical photographs of Co-MOF hydrogels after solvothermal reaction.
- FigS4.png
The zeta potential of NiMn-MOF nanobelt aqueous solution.
- FigS5.png
Optical photographs of NiMn-MOF nanobelts aqueous solutions after standing still for different time durations.
- FigS6.png
Morphological characterizations of bulk NiMn-MOF obtained by directly drying nanobelts at 60oC in air. (a-d) SEM images (scale bars for a, b, c and d are 20, 10, 10, and 2 μm); inset of (a) is an optical image; (e-i) SEM elemental mappings of Ni, Mn, S, O, C (scale bars: 2 μm); (j) EDS elemental mapping images.
- FigS7.png
Morphological characterizations of NiMn-MOF aerogels obtained by rapid liquid nitrogen freezing (freezing rate: 50oC min-1). (a, b) the morphology before and after compression, without superplasticity; (c, d) SEM image (scale bars are 30 μm).
- FigS8.png
Morphology characterizations of Ni-MOF aerogels. (a-e) SEM images (scale bars for a, b, c, d and e are 40 μm, 20 μm, 10 μm, 200 nm and 200 nm); inset of (a) is an optical image; (f-i) SEM elemental mappings of Ni, S, O, C (scale bars: 200 nm); (j) EDS elemental mapping images.
- FigS9.png
Morphology characterizations of Co-MOF aerogels. (a-e) SEM images (scale bars for a, b, c, d, and e are 100 μm, 40 μm, 30 μm, 200 nm and 200 nm); inset of (a) is an optical image; (f-i) SEM elemental mappings of Co, S, O, C (scale bars: 200 nm); (j) EDS elemental mapping images.
- FigS10.png
Morphology characterizations of Mn-MOF aerogels. (a-e) SEM images (scale bars for a, b, c, d and e are 40 μm, 20 μm, 10 μm, 1 μm and 200 nm); inset of (a) is an optical image; (f-i) SEM elemental mappings of Mn, S, O, C (scale bars: 200 nm); (j) EDS elemental mapping images.
- FigS11.png
Morphology characterizations of NiCo-MOF aerogels. (a-d) SEM images (scale bars for a, b, c and d are 20 μm, 10 μm, 200 nm and 100 nm); inset of (a) is an optical image; (e-i) SEM elemental mappings of Ni, Co, S, O, C (scale bars: 200 nm); (j) EDS elemental mapping images.
- FigS12.png
Morphology characterizations of CoMn-MOF aerogels. (a-d) SEM images (scale bars for a, b, c and d are 40 μm, 20 μm, 10 μm and 200 nm); inset of (a) is an optical image; (e-i) SEM elemental mappings of Co, Mn, S, O, C (scale bars: 200 nm); (j) EDS elemental mapping images.
- FigS13.png
Morphology characterizations of NiCoMn-MOF aerogels. (a-c) SEM images (scale bars for a, b and c are 40 μm, 20 μm and 200 nm); inset of (a) is an optical image; (d-i) SEM elemental mappings of Ni, Co, Mn, S, O, C (scale bars: 200 nm); (j) EDS elemental mapping images.
- FigS14.png
EDS elemental mapping images of NiMn-MOF.
- FigS15.png
(a) XPS survey spectrum of NiMn-MOF; (b) S 2p, C-S-C and (c) O 1s regions of NiMn-MOF.
- FigS16.png
(a) XRD pattern of NiMn-MOF (25% of Mn), NiMn-MOF (80% of Mn) and NiMn-MOF (powder); (b) NiMn-MOF (treated at 600°C) as comparison with standard cards, showing the production of Ni3S2, MnO, and nickel foam (NF) components.
- FigS17.png
XRD pattern of (a) Co-MOF, (b) NiCo-MOF, (c) CoMn-MOF and (d) NiCoMn-MOF.
- FigS18.png
FT-IR spectra of Mn-MOF, Ni-MOF, NiMn-MOF (powder), NiMn-MOF (80% of Mn) and NiMn-MOF (25% of Mn).
- FigS19.png
FT-IR spectra of (a) Co-MOF, (b) NiCo-MOF, (c) CoMn-MOF and (d) NiCoMn-MOF.
- FigS20.png
Density of states (DOS) of NiMn-MOF calculated by density fucntion theory (DFT) method.
- FigS21.png
(a, b) LSV curves of NiMn-MOF and other comparison electrodes for HER at 5 mV s-1 with 85% iR-compensation in 3 wt% NaCl electrolyte.
- FigS22.png
Overpotentials of NiMn-MOF and other comparison electrode at different current densities in 3 wt% NaCl electrolyte.
- FigS23.png
(a, b) Tafel plots of NiMn-MOF and other electrode during HER process in 3 wt% NaCl electrolyte.
- FigS24.png
(a, b) EIS plots of NiMn-MOF and other comparison electrode in 3 wt% NaCl electrolyte. According to Supplementary Figs. 23,24 and Table 4, the catalyst electrodes show excellent reaction kinetics, as verified by the similar Tafel slopes and charge-transfer resistance (Rct) from EIS analysis compared with other comparative samples.
- FigS25.png
Stability of NiMn-MOF in 3 wt% NaCl electrolyte. (a) Stability test for 12 hrs; (b) EIS plots of NiMn-MOF before and after stability; (c) LSVs before and after stability test. Remarkably, NiMn-MOF electrode shows excellent electrochemical durability as confirmed by chronoamperometry (10 mA cm-2 for 12 hrs, panel a), EIS (panel b), and LSVs (panel c) before and after testing.
- FigS26.png
a) LSVs and (b) EIS plots of NiMn-MOF electrode in NaCl electrolyte of different concentrations.
- FigS27.png
Morphology characterizations of NiMn-MOF before electrochemical cycling. (a-d) SEM images (scale bars for a, b, c and d are 200 μm, 100 μm, 50 μm and 20 μm); inset of (d) is SEM image (scale bars: 300 nm); (e-i) SEM elemental mappings of Ni, Mn, S, O, C (scale bars: 50 μm).
- FigS28.png
Morphology characterizations of NiMn-MOF after electrochemical cycling. (a-d) SEM images (scale bars for a, b, c and d are 200 μm, 100 μm, 50 μm and 20 μm); inset of (d) is SEM image (scale bars: 300 nm); (e-i) SEM elemental mappings of Ni, Mn, S, O, C (scale bars: 50 μm).
- FigS29.png
Structure characterizations of NiMn-MOF before and after electrochemical cycling. (a) XRD patterns; (b) FT-IR spectra.
- FigS30.png
Optimized lattice structure for NiMn-MOF absorbed hydrogen atoms at different active sites. Color code: gray, nickel; green, manganese; red, oxygen; yellow, sulfur; white, hydrogen; black, carbon.
- FigS31.png
Optimized lattice structure for Ni-MOF and Mn-MOF absorbed hydrogen atoms. Color code: gray, nickel; green, manganese; red, oxygen; yellow, sulfur; white, hydrogen; black, carbon.
- FigS32.png
(a) N2 adsorption-desorption isotherms of the NiMn-MOF and NiMn-MOF (powder); (b) shows the BJH pore size distributions.
- FigS33.png
Cyclic voltammetry curve and corresponding capacitive plots for (a, b) NiMn-MOF, (c, d) Ni-MOF, (e, f) Mn-MOF and (g, h) Pt/C at different scan rates (10-20 mV s-1) in a 3 wt% NaCl solution.
- FigS34.png
Cyclic voltammetry curve and corresponding capacitive plots for (a, b) NiMn-MOF (powder), (c, d) NiMn-MOF (treated at 600°C) and (e, f) NF at different scan rates (10-20 mV s-1) in 3 wt% NaCl solution.
- TableS1.png
Electrical conductivity of NiMn-MOF and other comparison samples. Each sample was measured by repeatitieve nine times.
- TableS2.png
Average mass loadings of NiMn-MOF catalysts on nickel foam substrates.
- TableS3.png
Brunauer-Emmett-Teller (BET) surface area of NiMn-MOF and its powder counterpart.
- TableS4.png
Comparison of the HER activity for NiMn-MOF with other electrocatalysts in 3 wt% NaCl solution.
- TableS5.png
Comparison of the HER activity for NiMn-MOF in different concentrations of NaCl electrolyte.
- TableS6.png
Comparison of the HER activity for NiMn-MOF with different folding times in natural seawater.
- TableS7.png
Comparison of the HER activity for NiMn-MOF with recently reported electrocatalysts in neutral electrolytes.
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Article
Bio-inspired general synthesis of superplastic metal-organic framework aerogels and their applications
sheng chen
Nanjing University of Science and Technology
Corresponding Author
ORCiD: https://orcid.org/0000-0002-6224-2051
Badges
Prescreen
This manuscript passed our Prescreen assessment
Complete author information
Appropriate declaration statements
Potential risks to human health
Prescreen
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CURRENT STATUS: Posted
Version 1
Posted 14 Aug, 2020
No community comments so far
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License:
This work is licensed under a CC BY 4.0 License. Read Full License
Many proposed utilizations for metal-organic frameworks (MOFs) demand their assembly into three-dimensional (3D) monolithic architectures. The capability of sustaining structural integrity during considerable deformations is important to allow a monolithic material that works reliably. Nevertheless, it remains a significant challenge to realize high superplasticity in 3D macroscopic MOF networks. Here we report the ice-template-driven assembly of MOF nanobelts to form superelastic MOF-based cellular aerogels. Inspired by the hierarchical architecture of natural cork, the resulting materials can fully and rapidly recover its initial architecture after 50% strain compression and unloading for 2000 cycles. The characteristic hierarchical structure can be extended to single (Ni-, Mn-, and Co-), binary (NiMn-, NiCo-, and CoMn-), and ternary (NiCoMn-) MOF aerogels with exceptionally structural and chemical properties. Potential application has been further demonstrated for NiMn-MOF aerogels in flexible energy conversion, which can effectively electrocatalysize hydrogen evolution in natural seawater even in the presence of considerable electrode deformations. The successful fabrication of such a class of fascinating architectures opens up enormous opportunities for exploring new application of MOFs in a free-standing, structurally adaptive, and macroscopic form
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