Chemistry:Conductive metal-organic frameworks

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Conductive metal−organic frameworks are a class of metal–organic frameworks with intrinsic ability of electronic conduction. Metal ions and organic linker self-assemble to form a framework which can be 1D/2D/3D[clarification needed] in connectivity. The first conductive MOF, Cu[Cu(2,3-pyrazinedithiol)2] was described in 2009 and exhibited electrical conductivity of 6 × 10−4 S cm−1 at 300 K.[1]

Fig.1 Typical multi-dentate ligands for synthesis of conductive MOFs. From left to right in top row are dihydroxy benzoquinone (DBHQ), hexahydroxybenzene (HHB), hexathiolbenzene (HTB), hexaaminobenzene (HAB), octahydroxy/amino metallophthalocyanine. In bottom row from left to right are hexahydroxytriphenylene (HHTP), hexathioltriphenylene (HTTP) and hexaaminotriphenylene (HITP).

Design and structure

The organic linkers for conductive MOFs are generally conjugated. 2D conductive MOFs have been explored well and several studies of 3D conductive MOFs have also been reported so far.[2][3][4][5][6][7][8][9][10] Single crystal structure of a 2D conductive MOF Co(HHTP) [hexahydroxytriphenylene] was reported in 2012.[5]

The conductivity of these materials are often tested by two probe method, i.e. a known potential is applied between two probes, the resulting current is measured, and resistance is calculated by using Ohm’s law. A four-probe method employs two wires on the extreme are used to supply a current and the inner two wires measure the drop in potential. This method eliminates the effect of contact resistance.[2]

Most MOFs have conductivity less than 10−10 S cm−1 and are considered as Insulator. Based on the literature reports so far, conductivity range in the MOFs can vary from 10−10 to 103 S cm−1.[11][12] Charge transfer in conductive MOFs have been attributed to three pathways: 1) Through-bond:- when d orbital of  transition metal ion overlaps with the p orbital of the organic linker, π electrons are delocalized across all the adjacent p orbitals. 2) Extended conjugation:- When transition metal ions are coupled with the a conjugated organic linker, the d-π conjugation allows delocalization of the charge carriers. 3) Through-space:- Organic linkers in one layer can interact with the one in the adjacent layer via π-π interaction. This will facilitate charge delocalization in the adjacent layers.[13]

Synthesis

Solvothermal synthesis

Fig. 2 Synthetic Scheme of phthalocyanine based conductive MOFs. Structure on the right side represents the connectivity in ab plane of phthalocyanine based MOFs

In 2017 Kimizuka reported a phthalocyanine based conductive MOF Cu-CuPc with an intrinsic conductivity in the range of 10−6 S cm−1. For the solvothermal synthesis of MOF, the organic linker Cu-octahydroxy phthalocyanine (CuPc) and metal ion is dissolved in a DMF/H2O mixture at heated at 130 °C for 48 hours.[14] Afterwards, Mirica and co-workers were able to enhance the conductivity to a range of 10−2 S cm−1 by synthesizing a bimetallic phthalocyanine based MOF NiPc-Cu.[15]

Hydrothermal synthesis

Examples include a series of isoretical catecholate-based MOFs employing hexahudroxytriphenylene (HHTP) as thee organic linker and Ni/Cu/Co as metal nodes. For the hydrothermal synthesis of these MOFs, both organic linker (hexahydroxytriphenylene) and metal ion is dissolved in H2O, aqueous ammonia is added and mixture is heated. Cu3(HHTP) also known as (Cu-CAT-1) showed a conductivity up to 2.1 × 10−1 S cm−1.[16] Another MOF based on hexaaminotriphenylene (HATP) organic linker and Ni metal ion showed an electronic conductivity of 40 S cm−1 when measured by using Van der Pauw method .[17]

Fig. 3 Synthetic Scheme of triphenylene-based conductive MOFs. General connectivity in ab plane of Triphenylene based MOFs (except NiHHTP, which has a ABAB packing)

Layering method

A Ni-BHT MOF nanosheet has been obtained using liquid-liquid interfacial synthesis. For the synthesis, organic linker is dissolved in dichloromethane upon which H2O is added and then metal salt (Ni(OAc)2) along with sodium bromide is added to the aqueous layer.[18]

Potential applications

Although no conductive MOF has been commercialized, potential applications have been identified.

Electrochemical sensors

Conductive MOF are of interest as a chemiresistive sensors. A 2D conductive MOF Cu3(HITP)2 and bulk  conductivity of this MOF was measured to be 0.2 S cm−1. It was employed for chemiresistive sensing of ammonia vapor and limit of detection of this material was 0.5 ppm.[19] Two isoreticular MOFs based on phthalocyanine and naphthalocyanine organic linkers have been tested for sensing of neurotransmitters. In this study authors were able to get a very low limit of detection, NH3 (0.31-0.33 ppm), H2S (19-32 ppb) and NO (1-1.1 ppb) at a driving voltage of (0.01- 1.0 V).[15] Later, same group also reported voltametric detection of neurochemical by isoreticular MOFs based on triphenylene organic linker. Ni3(HHTP)2 (2,3,6,7,10,11-hexahydroxytriphenylene) MOF showed nanomolar limit of detection of Dopamine (63±11 nM) and serotonin (40±17 nM).[20] A 2D conductive MOF based on 2,3,7,8,12,13‐hexahydroxyl truxene linker and copper metal has shown promising electrochemical detection of paraquat.[21]

Electrocatalysis

MOFs have been explored for electrolysis to enhance the rate and selectivity of reactions. Owing to their high surface area they can provide large number of interaction site for the reaction, conductivity of the material allows charge transfer during the electrocatalytic process. Two Cobalt based MOFs Co-BHT (Benzenehexathiol) and Co-HTTP (Hexathioltriphenylene) have been investigated for hydrogen evolution reaction (HER). In this report, overpotential values for Co-BHT and Co-HTTP are found to be 340 mV and 530 mV respectively at pH 1.3. The tafel slopes are between 149 and 189 mV dec−1 at pH 4.2.[2] Ultrathin sheets of Co-HAB MOF have been found to be catalytically active for oxygen evolution reaction (OER). Overpotential for this MOF was 310 mV at 10 mA cm−2 in 1M KOH. Authors claimed that the ultrathin sheets were better than nanoparticles/thick sheets/bulk Co-HAB MOF because of favourable electrode kinetics.[22] A 2-D conductive MOF has also been employed as an electrocatalyst for oxygen reduction reaction (ORR). Ni3(HITP)2 MOF film on glassy carbon electrode in their study showed a potential of 820 mV at 50 μA in 0.1 M potassium hydroxide (KOH).[4]

Energy storage

MOFs with high surface area, redox active organic linker/metal nodes, intrinsic conductivity have attracted attention as electrode materials for electrochemical energy storage. First Conductive MOF-based electrochemical double layer capacitor (EDLC) was reported by Dinca and co-workers in 2017. They used Ni3(HITP)2 MOF for the fabrication of the device without using conductive additives which are mixed to enhance the conductivity. The resulting electrodes showed a gravimetric capacitance of 111 F g−1 and areal capacitance of 18 μF cm−2 at a discharge rate of 0.05 A g−1. These electrodes also exhibited a capacity retention of 90% after 10000 cycles.[23] A conductive MOFs based on hexaaminobenzene (HAB) organic linker and Cu/Ni metal ions has been tested as electrode for supercapacitor. Ni-HAB and Cu-HAB exhibited gravimetric capacitance of 420 F g−1 and 215 F g−1 respectively. The pellet form of Ni-HAB electrode showed a gravimetric capacitance of 427 F g−1 and volumetric capacitance of 760 F g−1. These MOFs also exhibited a capacitance retention of 90% after 12000 cycles.[6] First conductive MOF based cathode material for Lithium-ion battery was reported by Nishihara and co-workers in 2018. In this study they employed Ni3(HITP)2 MOF, It exhibited a specific capacity of 155 mA h g−1, specific energy density of 434 Wh kg−1 at A current density of 10 mA g−1, and good stability over 300 cycles.[24] In another study, two MOFs based on 2,5‐dichloro‐3,6‐dihydroxybenzoquinone (Cl2dhbqn−) organic linker and Fe metal ions have been employed for Lithium ion battery. (H2NMe2)2Fe2(Cl2dhbq)3 (1) and (H2NMe2)4Fe3(Cl2dhbq)3(SO4)2 (2) showed electrical conductivity of 2.6×10−3 and 8.4×10−5 S cm−1 respectively. (2) exhibited discharge capacity of 165 mA h g−1 at a charging rate of 10 mA g−1) and (1) exhibited 195 mA h g−1 at 20 mA g−1 and a specific energy density of 533 Wh kg−1.[25]

See also

Metal−organic framework

Covalent−organic framework

Coordination polymer

Sensor

References

  1. ↑ Takaishi, Shinya; Hosoda, Miyuki; Kajiwara, Takashi; Miyasaka, Hitoshi; Yamashita, Masahiro; Nakanishi, Yasuyuki; Kitagawa, Yasutaka; Yamaguchi, Kizashi et al. (2009-10-05). "Electroconductive Porous Coordination Polymer Cu[Cu(pdt)2 Composed of Donor and Acceptor Building Units"]. Inorganic Chemistry 48 (19): 9048–9050. doi:10.1021/ic802117q. ISSN 0020-1669. PMID 19067544. https://doi.org/10.1021/ic802117q. 
  2. ↑ 2.0 2.1 2.2 Clough, Andrew J.; Yoo, Joseph W.; Mecklenburg, Matthew H.; Marinescu, Smaranda C. (2015-01-14). "Two-Dimensional Metal–Organic Surfaces for Efficient Hydrogen Evolution from Water". Journal of the American Chemical Society 137 (1): 118–121. doi:10.1021/ja5116937. ISSN 0002-7863. PMID 25525864. https://doi.org/10.1021/ja5116937. 
  3. ↑ Dong, Renhao; Zheng, Zhikun; Tranca, Diana C.; Zhang, Jian; Chandrasekhar, Naisa; Liu, Shaohua; Zhuang, Xiaodong; Seifert, Gotthard et al. (2017). "Immobilizing Molecular Metal Dithiolene–Diamine Complexes on 2D Metal–Organic Frameworks for Electrocatalytic H2 Production" (in en). Chemistry – A European Journal 23 (10): 2255–2260. doi:10.1002/chem.201605337. ISSN 1521-3765. PMID 27878872. https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.201605337. 
  4. ↑ 4.0 4.1 Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dincă, Mircea (2016-03-08). "Electrochemical oxygen reduction catalysed by Ni 3 (hexaiminotriphenylene) 2" (in en). Nature Communications 7 (1): 10942. doi:10.1038/ncomms10942. ISSN 2041-1723. PMID 26952523. Bibcode: 2016NatCo...710942M. 
  5. ↑ 5.0 5.1 Rubio‐Giménez, Víctor; Almora‐Barrios, Neyvis; Escorcia‐Ariza, Garin; Galbiati, Marta; Sessolo, Michele; Tatay, Sergio; Martí‐Gastaldo, Carlos (2018). "Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal–Organic Frameworks" (in en). Angewandte Chemie International Edition 57 (46): 15086–15090. doi:10.1002/anie.201808242. ISSN 1521-3773. PMID 30238608. https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201808242. 
  6. ↑ 6.0 6.1 Feng, Dawei; Lei, Ting; Lukatskaya, Maria R.; Park, Jihye; Huang, Zhehao; Lee, Minah; Shaw, Leo; Chen, Shucheng et al. (January 2018). "Robust and conductive two-dimensional metal−organic frameworks with exceptionally high volumetric and areal capacitance" (in en). Nature Energy 3 (1): 30–36. doi:10.1038/s41560-017-0044-5. ISSN 2058-7546. Bibcode: 2018NatEn...3...30F. https://www.nature.com/articles/s41560-017-0044-5. 
  7. ↑ Shinde, Sambhaji S.; Lee, Chi Ho; Jung, Jin-Young; Wagh, Nayantara K.; Kim, Sung-Hae; Kim, Dong-Hyung; Lin, Chao; Lee, Sang Uck et al. (2019). "Unveiling dual-linkage 3D hexaiminobenzene metal–organic frameworks towards long-lasting advanced reversible Zn–air batteries" (in en). Energy & Environmental Science 12 (2): 727–738. doi:10.1039/C8EE02679C. ISSN 1754-5692. http://xlink.rsc.org/?DOI=C8EE02679C. 
  8. ↑ Gándara, Felipe; Uribe‐Romo, Fernando J.; Britt, David K.; Furukawa, Hiroyasu; Lei, Liao; Cheng, Rui; Duan, Xiangfeng; O'Keeffe, Michael et al. (2012). "Porous, Conductive Metal-Triazolates and Their Structural Elucidation by the Charge-Flipping Method" (in en). Chemistry – A European Journal 18 (34): 10595–10601. doi:10.1002/chem.201103433. ISSN 1521-3765. PMID 22730149. https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.201103433. 
  9. ↑ Park, Jesse G.; Aubrey, Michael L.; Oktawiec, Julia; Chakarawet, Khetpakorn; Darago, Lucy E.; Grandjean, Fernande; Long, Gary J.; Long, Jeffrey R. (2018-07-11). "Charge Delocalization and Bulk Electronic Conductivity in the Mixed-Valence Metal–Organic Framework Fe(1,2,3-triazolate)2(BF4)x". Journal of the American Chemical Society 140 (27): 8526–8534. doi:10.1021/jacs.8b03696. ISSN 0002-7863. PMID 29893567. https://doi.org/10.1021/jacs.8b03696. 
  10. ↑ Xie, Lilia S.; Sun, Lei; Wan, Ruomeng; Park, Sarah S.; DeGayner, Jordan A.; Hendon, Christopher H.; Dincă, Mircea (2018-06-20). "Tunable Mixed-Valence Doping toward Record Electrical Conductivity in a Three-Dimensional Metal–Organic Framework". Journal of the American Chemical Society 140 (24): 7411–7414. doi:10.1021/jacs.8b03604. ISSN 0002-7863. PMID 29807428. https://doi.org/10.1021/jacs.8b03604. 
  11. ↑ Huang, Xing; Sheng, Peng; Tu, Zeyi; Zhang, Fengjiao; Wang, Junhua; Geng, Hua; Zou, Ye; Di, Chong-an et al. (2015-06-15). "A two-dimensional π–d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour" (in en). Nature Communications 6 (1): 7408. doi:10.1038/ncomms8408. ISSN 2041-1723. PMID 26074272. Bibcode: 2015NatCo...6.7408H. 
  12. ↑ Sun, Lei; Campbell, Michael G.; Dincă, Mircea (2016). "Electrically Conductive Porous Metal–Organic Frameworks" (in en). Angewandte Chemie International Edition 55 (11): 3566–3579. doi:10.1002/anie.201506219. ISSN 1521-3773. PMID 26749063. https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201506219. 
  13. ↑ Xie, Lilia S.; Skorupskii, Grigorii; Dincă, Mircea (2020-08-26). "Electrically Conductive Metal–Organic Frameworks". Chemical Reviews 120 (16): 8536–8580. doi:10.1021/acs.chemrev.9b00766. ISSN 0009-2665. PMID 32275412. 
  14. ↑ Nagatomi, Hisanori; Yanai, Nobuhiro; Yamada, Teppei; Shiraishi, Kanji; Kimizuka, Nobuo (2018). "Synthesis and Electric Properties of a Two-Dimensional Metal-Organic Framework Based on Phthalocyanine" (in en). Chemistry – A European Journal 24 (8): 1806–1810. doi:10.1002/chem.201705530. ISSN 1521-3765. PMID 29291261. https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.201705530. 
  15. ↑ 15.0 15.1 Meng, Zheng; Aykanat, Aylin; Mirica, Katherine A. (2019-02-06). "Welding Metallophthalocyanines into Bimetallic Molecular Meshes for Ultrasensitive, Low-Power Chemiresistive Detection of Gases". Journal of the American Chemical Society 141 (5): 2046–2053. doi:10.1021/jacs.8b11257. ISSN 0002-7863. PMID 30596491. https://doi.org/10.1021/jacs.8b11257. 
  16. ↑ Hmadeh, Mohamad; Lu, Zheng; Liu, Zheng; Gándara, Felipe; Furukawa, Hiroyasu; Wan, Shun; Augustyn, Veronica; Chang, Rui et al. (September 2012). "New Porous Crystals of Extended Metal-Catecholates". Chemistry of Materials 24 (18): 3511–3513. doi:10.1021/cm301194a. ISSN 0897-4756. https://doi.org/10.1021/cm301194a. 
  17. ↑ Sheberla, Dennis; Sun, Lei; Blood-Forsythe, Martin A.; Er, Süleyman; Wade, Casey R.; Brozek, Carl K.; Aspuru-Guzik, Alán; Dincă, Mircea (2014-06-25). "High Electrical Conductivity in Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2, a Semiconducting Metal–Organic Graphene Analogue". Journal of the American Chemical Society 136 (25): 8859–8862. doi:10.1021/ja502765n. ISSN 0002-7863. PMID 24750124. https://doi.org/10.1021/ja502765n. 
  18. ↑ Kambe, Tetsuya; Sakamoto, Ryota; Hoshiko, Ken; Takada, Kenji; Miyachi, Mariko; Ryu, Ji-Heun; Sasaki, Sono; Kim, Jungeun et al. (2013-02-20). "π-Conjugated Nickel Bis(dithiolene) Complex Nanosheet". Journal of the American Chemical Society 135 (7): 2462–2465. doi:10.1021/ja312380b. ISSN 0002-7863. PMID 23360513. https://doi.org/10.1021/ja312380b. 
  19. ↑ Campbell, Michael G.; Sheberla, Dennis; Liu, Sophie F.; Swager, Timothy M.; Dincă, Mircea (2015). "Cu3(hexaiminotriphenylene)2: An Electrically Conductive 2D Metal–Organic Framework for Chemiresistive Sensing" (in en). Angewandte Chemie International Edition 54 (14): 4349–4352. doi:10.1002/anie.201411854. ISSN 1521-3773. PMID 25678397. https://www.onlinelibrary.wiley.com/doi/abs/10.1002/anie.201411854. 
  20. ↑ Ko, Michael; Mendecki, Lukasz; Eagleton, Aileen M.; Durbin, Claudia G.; Stolz, Robert M.; Meng, Zheng; Mirica, Katherine A. (2020-07-08). "Employing Conductive Metal–Organic Frameworks for Voltammetric Detection of Neurochemicals". Journal of the American Chemical Society 142 (27): 11717–11733. doi:10.1021/jacs.9b13402. ISSN 0002-7863. PMID 32155057. https://doi.org/10.1021/jacs.9b13402. 
  21. ↑ Zhao, Qian; Li, Sheng-Hua; Chai, Rui-Lin; Ren, Xv; Zhang, Chun (2020-02-12). "Two-Dimensional Conductive Metal–Organic Frameworks Based on Truxene". ACS Applied Materials & Interfaces 12 (6): 7504–7509. doi:10.1021/acsami.9b23416. ISSN 1944-8244. PMID 31965783. https://doi.org/10.1021/acsami.9b23416. 
  22. ↑ Li, Chun; Shi, Lingling; Zhang, Lili; Chen, Peng; Zhu, Junwu; Wang, Xin; Fu, Yongsheng (2020). "Ultrathin two-dimensional π–d conjugated coordination polymer Co 3 (hexaaminobenzene) 2 nanosheets for highly efficient oxygen evolution" (in en). Journal of Materials Chemistry A 8 (1): 369–379. doi:10.1039/C9TA10644H. ISSN 2050-7488. http://xlink.rsc.org/?DOI=C9TA10644H. 
  23. ↑ Sheberla, Dennis; Bachman, John C.; Elias, Joseph S.; Sun, Cheng-Jun; Shao-Horn, Yang; Dincă, Mircea (February 2017). "Conductive MOF electrodes for stable supercapacitors with high areal capacitance" (in en). Nature Materials 16 (2): 220–224. doi:10.1038/nmat4766. ISSN 1476-4660. PMID 27723738. Bibcode: 2017NatMa..16..220S. https://www.nature.com/articles/nmat4766. 
  24. ↑ Wada, Keisuke; Sakaushi, Ken; Sasaki, Sono; Nishihara, Hiroshi (2018). "Multielectron-Transfer-based Rechargeable Energy Storage of Two-Dimensional Coordination Frameworks with Non-Innocent Ligands" (in en). Angewandte Chemie International Edition 57 (29): 8886–8890. doi:10.1002/anie.201802521. ISSN 1521-3773. PMID 29675949. 
  25. ↑ Ziebel, Michael E.; Gaggioli, Carlo Alberto; Turkiewicz, Ari B.; Ryu, Won; Gagliardi, Laura; Long, Jeffrey R. (2020-02-05). "Effects of Covalency on Anionic Redox Chemistry in Semiquinoid-Based Metal–Organic Frameworks". Journal of the American Chemical Society 142 (5): 2653–2664. doi:10.1021/jacs.9b13050. ISSN 0002-7863. PMID 31940192. https://doi.org/10.1021/jacs.9b13050. 




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