Abstract
Porous materials such as metal-organic frameworks (MOFs) with high theoretical volumetric gas uptake capacity are promising materials for gas storage and separation, but the structuring for practical applications is challenging. Herein, we report a general and feasible strategy to combine electrospinning with a phase conversion method to decorate polyacrylonitrile nanofibers (PAN NFs) with Cu-MOF (HKUST-1). The strategy is based on the combination of surface pretreatment of the NFs with Cu(OH)2 and a subsequent phase conversion into HKUST-1 crystals (PC-HKUST-1). A significant higher loading of HKUST-1 in the PAN NF matrix was achieved by the phase conversion method compared with direct electrospinning of MOF slurries or in-situ growth of MOF crystals on NFs. As a result, the hierarchical structured PC (phase conversion)-HKUST-1 NFs revealed the highest gravimetric storage capacity of 86 cm3 g−1 (STP) at 3500 kPa and 298 K for methane (CH4), which is higher than other HKUST 1 NFs reported previously. The improved CH4 uptake can be explained by the high loading of HKUST-1 due to the high availability of Cu-ions localized on the surface of the NFs during the phase conversion process, resulting in high surface area and excellent gas access of the phase converted HKUST-1. Thus, the developed strategy of structuring MOFs could be of interest for the fabrication of tailor-made MOF NF architectures for other energy and environmental applications.
摘要多
孔金属有机骨架材料MOFs在气体存储领域具有潜在应用 前景, 但是其面向实际应用的加工成型仍具有挑战. 本文报道了一 种基于静电纺丝技术和相转变结合的方法来构筑MOFs纤维, 有效 实现了Cu-MOF(HKUST-1)在PAN纳米纤维表面的高效负载. 该方 法首先将Cu(OH)2 生长在PAN纳米纤维表面, 进一步通过相转变 获得HKUST-1. 相比之前的文献报道, 该HKUST-1纳米纤维表现 出更优异的甲烷存储性能, 其在3500 kPa和298 K条件下的甲烷存 储量达到86 cm3 g−1. 研究表明该纤维使得负载在表面的MOF 高 度暴露, 具有高的比表面和负载量. 该工作为MOFs加工成型并用 于能源和环境领域提供了新的思路.
Article PDF
Similar content being viewed by others
References
Cherp A, Jewell J, Vinichenko V, et al. Global energy security under different climate policies, GDP growth rates and fossil resource availabilities. Climatic Change, 2016, 136: 83–94
Montoya JH, Seitz LC, Chakthranont P, et al. Materials for solar fuels and chemicals. Nat Mater, 2016, 16: 70–81
Li XB, Tung CH, Wu LZ. Semiconducting quantum dots for artificial photosynthesis. Nat Rev Chem, 2018, 2: 160–173
Makal TA, Li JR, Lu W, et al. Methane storage in advanced porous materials. Chem Soc Rev, 2012, 41: 7761–7779
Lee S, Kim B, Kim J. Predicting performance limits of methane gas storage in zeolites with an artificial neural network. J Mater Chem A, 2019, 7: 2709–2716
Lin RB, He Y, Li P, et al. Multifunctional porous hydrogen-bonded organic framework materials. Chem Soc Rev, 2019, 48: 1362–1389
Lozano-Castelló D, Alcañiz-Monge J, de la Casa-Lillo MA, et al. Advances in the study of methane storage in porous carbonaceous materials. Fuel, 2002, 81: 1777–1803
Santos JC, Lima JA, Gurgel JM, et al. Improvement of methane storage capacity in activated carbon bed with bidisperse packing. Braz J Chem Eng, 2016, 36: 831–843
Kang Z, Xue M, Fan L, et al. Highly selective sieving of small gas molecules by using an ultra-microporous metal-organic framework membrane. Energy Environ Sci, 2014, 7: 4053–4060
Eddaoudi M, Kim J, Rosi N, et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science, 2002, 295: 469–472
Bourrelly S, Llewellyn PL, Serre C, et al. Different adsorption behaviors of methane and carbon dioxide in the isotypic nanoporous metal terephthalates MIL-53 and MIL-47. J Am Chem Soc, 2005, 127: 13519–13521
Gedrich K, Senkovska I, Klein N, et al. A highly porous metal-organic framework with open nickel sites. Angew Chem Int Ed, 2010, 49: 8489–8492
Zhao XL, Sun D, Yuan S, et al. Comparison of the effect of functional groups on gas-uptake capacities by fixing the volumes of cages A and B and modifying the inner wall of cage C in rht-type MOFs. Inorg Chem, 2012, 51: 10350–10355
Tanaka S, Sakamoto K, Inada H, et al. Vapor-phase synthesis of ZIF-8 MOF thick film by conversion of ZnO nanorod array. Langmuir, 2018, 34: 7028–7033
Yang P, Mao F, Li Y, et al. Hierarchical porous Zr-based MOFs synthesized by a facile monocarboxylic acid etching strategy. Chem Eur J, 2018, 24: 2962–2970
Wang B, Zhao M, Li L, et al. Ultra-thin metal-organic framework nanoribbons. Natl Sci Rev, 2020, 7: 46–52
Shu Y, Hao JN, Niu D, et al. A smart luminescent metal-organic framework-based logic system for simultaneous analysis of copper ions and hydrogen sulfide. J Mater Chem C, 2020, 8: 8635–8642
Majano G, Pérez-Ramírez J. Scalable room-temperature conversion of copper(II) hydroxide into HKUST-1 (Cu3(btc)2). Adv Mater, 2013, 25: 1052–1057
Bazer-Bachi D, Assié L, Lecocq V, et al. Towards industrial use of metal-organic framework: Impact of shaping on the MOF properties. Powder Tech, 2014, 255: 52–59
Furukawa S, Reboul J, Diring S, et al. Structuring of metal-organic frameworks at the mesoscopic/macroscopic scale. Chem Soc Rev, 2014, 43: 5700–5734
Stassen I, Burtch N, Talin A, et al. An updated roadmap for the integration of metal-organic frameworks with electronic devices and chemical sensors. Chem Soc Rev, 2017, 46: 3185–3241
Li S, Huo F. Metal-organic framework composites: From fundamentals to applications. Nanoscale, 2015, 7: 7482–7501
Dou Y, Zhang W, Kaiser A. Electrospinning of metal-organic frameworks for energy and environmental applications. Adv Sci, 2020, 7: 1902590
Liang H, Jiao X, Li C, et al. Flexible self-supported metal-organic framework mats with exceptionally high porosity for enhanced separation and catalysis. J Mater Chem A, 2018, 6: 334–341
Talmoudi H, Khenoussi N, Adolphe D, et al. An in situ crystal growth of metal organic frameworks-5 on electrospun PVA nanofibers. Autex Res J, 2018, 18: 308–313
Lee G, Seo YD, Jang J. ZnO quantum dot-decorated carbon nanofibers derived from electrospun ZIF-8/PVA nanofibers for highperformance energy storage electrodes. Chem Commun, 2017, 53: 11441–11444
Laurila E, Thunberg J, Argent SP, et al. Enhanced synthesis of metal-organic frameworks on the surface of electrospun cellulose nanofibers. Adv Eng Mater, 2015, 17: 1282–1286
Zhao J, Lee DT, Yaga RW, et al. Ultra-fast degradation of chemical warfare agents using MOF-nanofiber kebabs. Angew Chem Int Ed, 2016, 55: 13224–13228
Liu C, Wu YN, Morlay C, et al. General deposition of metal-organic frameworks on highly adaptive organic-inorganic hybrid electrospun fibrous substrates. ACS Appl Mater Interfaces, 2016, 8: 2552–2561
Ji D, Peng S, Fan L, et al. Thin MoS2 nanosheets grafted MOFs-derived porous Co-N-C flakes grown on electrospun carbon nanofibers as self-supported bifunctional catalysts for overall water splitting. J Mater Chem A, 2017, 5: 23898–23908
Zhang Y, Yuan S, Feng X, et al. Preparation of nanofibrous metal-organic framework filters for efficient air pollution control. J Am Chem Soc, 2016, 138: 5785–5788
Su Z, Zhang M, Lu Z, et al. Functionalization of cellulose fiber by in situ growth of zeolitic imidazolate framework-8 (ZIF-8) nano-crystals for preparing a cellulose-based air filter with gas adsorption ability. Cellulose, 2018, 25: 1997–2008
Bian Y, Wang R, Wang S, et al. Metal-organic framework-based nanofiber filters for effective indoor air quality control. J Mater Chem A, 2018, 6: 15807–15814
Fan L, Xue M, Kang Z, et al. Electrospinning technology applied in zeolitic imidazolate framework membrane synthesis. J Mater Chem, 2012, 22: 25272–25276
Zhang R, Hu L, Bao S, et al. Surface polarization enhancement: High catalytic performance of Cu/CuOx/C nanocomposites derived from Cu-BTC for CO oxidation. J Mater Chem A, 2016, 4: 8412–8420
Weng Y, Guan S, Wang L, et al. Defective porous carbon polyhedra decorated with copper nanoparticles for enhanced NIR-driven photothermal cancer therapy. Small, 2020, 16: 1905184
Grande CA, Blom R, Möller A, et al. High-pressure separation of CH4/CO2 using activated carbon. Chem Eng Sci, 2013, 89: 10–20
Tian T, Zeng Z, Vulpe D, et al. A sol-gel monolithic metal-organic framework with enhanced methane uptake. Nat Mater, 2018, 17: 174–179
Wilmer CE, Farha OK, Yildirim T, et al. Gram-scale, high-yield synthesis of a robust metal-organic framework for storing methane and other gases. Energy Environ Sci, 2013, 6: 1158–1163
Gándara F, Furukawa H, Lee S, et al. High methane storage capacity in aluminum metal-organic frameworks. J Am Chem Soc, 2014, 136: 5271–5274
Jiang J, Furukawa H, Zhang YB, et al. High methane storage working capacity in metal-organic frameworks with acrylate links. J Am Chem Soc, 2016, 138: 10244–10251
Peng Y, Srinivas G, Wilmer CE, et al. Simultaneously high gravimetric and volumetric methane uptake characteristics of the metal-organic framework NU-111. Chem Commun, 2013, 49: 2992–2994
Li B, Wen HM, Wang H, et al. A porous metal-organic framework with dynamic pyrimidine groups exhibiting record high methane storage working capacity. J Am Chem Soc, 2014, 136: 6207–6210
Mason JA, Oktawiec J, Taylor MK, et al. Methane storage in flexible metal-organic frameworks with intrinsic thermal management. Nature, 2015, 527: 357–361
Alezi D, Belmabkhout Y, Suyetin M, et al. MOF crystal chemistry paving the way to gas storage needs: Aluminum-based soc-MOF for CH4, O2, and CO2 storage. J Am Chem Soc, 2015, 137: 13308–13318
Guo Z, Wu H, Srinivas G, et al. A metal-organic framework with optimized open metal sites and pore spaces for high methane storage at room temperature. Angew Chem Int Ed, 2011, 50: 3178–3181
Acknowledgements
This work was supported by the Grande Solution Project“HiGradeGas” (48279), and Innovation Fund Denmark, exploring NFs-based adsorbents for biogas upgrading and storage. We also thank the Danish Research Council to provide funding to support fundamental research on electrospinning (8022-00237B) and for investigating NFs structures for enzyme immobilization (6111-00232B).
Author information
Authors and Affiliations
Contributions
Dou Y, Zhang W, and Kaiser A conceived the idea and prepared the manuscript; Dou Y worked on the synthesis and characterization of MOF NFs; Grande C took part in the CH4 adsorption measurement. This article was discussed with contributions from all authors.
Corresponding authors
Additional information
Conflict of interest
The authors declare that they have no conflict of interest.
Supplementary information
Supporting data are available in the online version of the paper.
Yibo Dou obtained his BSc and PhD degrees from Beijing University of Chemical Technology in 2009 and 2015, under the supervision of Prof. Xue Duan. Currently, he is a Researcher at the Technical University of Denmark. His main research topic is electrospinning of porous material-based functional nanofibers for energy and environmental applications.
Andreas Kaiser received his PhD degree in chemistry/materials science in 1994 at the University of Würzburg/Fraunhofer Institute for Silicate Chemistry. He is currently an Associate Professor at the Technical University of Denmark. His research interests are on the development of advanced porous materials for energy and environmental applications, including membranes, gas adsorption devices, electrocatalysis and fuel cells/electrolyzers.
Wenjing Zhang received her Master and PhD degrees at the Hong Kong University of Science and Technology. She is currently an Associate Professor and group leader at the Technical University of Denmark, focusing on advanced material design for water treatment, catalysis, fuel cells, water splitting and CO2 reduction. She is also an Honorary Distinguished Professor at Qingdao University of Science and Technology in China.
Supplementary information
40843_2020_1575_MOESM1_ESM.pdf
Supporting information: Highly structured metal-organic frameworks nanofibers for methane storage (approximately 1.46 MB)
Rights and permissions
About this article
Cite this article
Dou, Y., Grande, C., Kaiser, A. et al. Highly structured metal-organic framework nanofibers for methane storage. Sci. China Mater. 64, 1742–1750 (2021). https://doi.org/10.1007/s40843-020-1575-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-020-1575-2