Microporous Porphyrin Networks Mimicking a Velvet Worm Surface

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Microporous Porphyrin Networks Mimicking Velvet Worm Surface and Their Enhanced Sensitivities towards Hydrogen Chloride and Ammonia Sang Hyun Ryu, Chang Wan Kang, Jaewon Choi, Yoon Myung, Yoon-Joo Ko, Sang Moon Lee, Hae Jin Kim, and Seung Uk Son ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b19119 • Publication Date (Web): 14 Feb 2018 Downloaded from http://pubs.acs.org on February 14, 2018

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ACS Applied Materials & Interfaces

Microporous Porphyrin Networks Mimicking Velvet Worm Surface and Their Enhanced Sensitivities towards Hydrogen Chloride and Ammonia Sang Hyun Ryu,†,‡ Chang Wan Kang,†,‡ Jaewon Choi,† Yoon Myung,∂ Yoon-Joo Ko,∞ Sang Moon Lee,§ Hae Jin Kim,§ and Seung Uk Son†,* †

Department of Chemistry, Sungkyunkwan University, Suwon 16419, Korea Department of Nanotechnology and Advanced Materials Engineering, Sejong University, Seoul 05006, Korea ∞ Laboratory of Nuclear Magnetic Resonance, The National Center for Inter-University Research Facilities (NCIRF), Seoul National University, Seoul 08826, Korea § Korea Basic Science Institute, Daejeon 34133, Korea ∂

Supporting Information

ABSTRACT: This work shows that the functions of microporous organic network materials can be enhanced through engineering of material structure. Mimicking the surface structure of velvet worms, we prepared the aligned 1D structure (rod) of microporous porphyrin networks by the Sonogashira coupling of tetra(4-ethynylphenyl)porphyrin with 1,4-diiodobenzene in an anodic aluminum oxide plate. The length of the 1D structure was controlled in the range of 1 ~ 5 m. The velvet worm surface-like microporous porphyrin networks (Velvet-MPNs) showed higher sensitivities to hydrogen chloride and ammonia gases by up to ~14 and 4.6 times, respectively, compared with a control MPN material without rods. Keywords: microporous organic polymer; Sonogashira; porphyrin; anodic aluminum oxide; sensing Sensing is a critical function of living organisms for their survival. Living organisms have adopted intriguing nano/microsized structures for efficient sensing. One of the most studied living organisms for their defensive performance is the velvet worm.1 The surface of velvet worms consists of villi that are sensitive to the change of chemical surroundings. (Figure 1a) When any sign of natural enemies touches the aligned bristles, the velvet worms recognize the situation to attack the enemies using chemical weapons. Mimicking the intriguing surface structure of velvet worms and understanding its sensing performance are valuable endeavors in the research and development of artificial2 systems such as robots. Our research group has studied the construction of nano/micro-sized molecular structures and their functions.3-5 For example, we have built octopus leg-like structures that show adhesive performance to the surface of solid supports.5 Recently, microporous organic networks (MONs) have been prepared by the coupling of various organic building blocks. 6-7 For example, the Sonogashira coupling of muti-ethynyl arenes with multi-halo arenes resulted in various MONs.8 In addition, MON films have been engineered on the surface.9-11 We have shown that the chemical performance of MONs is dependent on their morphological structure.4,12 In this work, we report the preparation of velvet worm surface-like aligned 1D structure of microporous poprhyrin networks (Velvet-MPNs) using anodic aluminum oxide (AAO) templates and their sensing behavior towards hydrogen chloride

and ammonia. As far as we are aware, MON-based porous sensing materials with an aligned 1D structure were not reported.13 Figure 1b shows a synthetic scheme for Velvet-MPNs. AAO plates with a pore diameter of 300 nm and pore depths of 1, 2, and 5 m were used as templates. When we used AAO plates with a pore diameter of 40 nm, building blocks could not be incorporated into pores during networking reaction. (Refer to corresponding SEM images in Figure S1 in the supporting information, SI) When we used AAO plates with a pore diameter of 160 nm, the obtained MPN rods were too thin to stand. (Refer to corresponding SEM images in Figure S1 in the SI) Thus, we used AAO plates with a pore diameter of 300 nm. The MPNs filled the pores and then, formed thin film outside of the AAO plate by the Sonogashira coupling of tetra(4-ethynylphenyl) porphyrin with 2 eq. 1,4-diiodobenzene using (PPh3)2PdCl2 and CuI catalysts. The etching of AAO plates with phosphoric acid resulted in aligned MPN rods on the MPN thin film (VelvetMPNs). The Velvet-MPNs could be transferred onto polyethylene teraphthalate (PET) film.

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Velvet-MPN-2

Velvet-MPN-1

(a) (a)

(d)

5 m

5 m

5 m

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(e)

(b)

Velvet worm

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(b) Sonogashira coupling 3 m

3 m N NH HN N

+

2I

AAO

I

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MPN-AAO Etching

H3PO4

N NH HN N

N NH HN N

3 m

(i)

Microporous Porphyrin network (MPN)

1 m

N NH HN N

Velvet-MPN Transfer

1 m

1 m

Figure 2. SEM images of (a-c) Velvet-MPN-1, (d-f) Velvet-MPN2, and (g-i) Velvet-MPN-5. (See Figures S2-4 in the SI for the enlarged SEM images, bottom view, and side view of Velvet-MPNs.)

PET

N NH HN N

Velvet-MPN-PET

Figure 1. (a) A photograph (under permission of Melvyn Yeo) and a cartoon of the velvet worm surface structure and (b) a synthetic scheme for Velvet-MPNs on polyethylene teraphthalate (PET) film based on the template synthesis using AAO plates.

The morphologies of Velvet-MPNs were investigated by scanning electron microscopy (SEM). (Figure 2) As shown in Figures 2 and S2 in the SI, the MPNs uniformly replicated AAO templates to reveal the homogeneous distribution of MPN rods on the MPN thin film. The bottom view of Velvet-MPNs showed a flat morphology without MPN rods. (Figure S3 in the SI) As the pore depth of AAO templates increased from 1 m to 2 and 5 m, the length of MPN rods in Velvet-MPPs increased from 1 m to 2 and 5 m, maintaining their diameters of ~300 nm. (Refer to the side views of Velvet-MPN materials in Figure S4 in the SI) The corresponding Velvet-MPNs were denoted as Velvet-MPN-1, Velvet-MPN-2, and Velvet-MPN-5, respectively in this work. The MPN rods in Velvet-MPN-1 and Velvet-MPN-2 overally stood well. (Figure 2a-f) In comparison, the Velvet-MPN-5 showed significant local aggregation of the end parts of MPN rods due to the relatively high aspect ratio of the rods. (Figure 2g-i)

To study the properties of Velvet-MPNs, we prepared a MPN thin film without rods (C-MPN) as a control material using the conventional thin layer chromatography plate (TLC). (Figure S5a in the SI) The MPN was formed on the surface of TLC plate by the Sonogashira coupling of tetra(4-ethynylphenyl) porphyrin with 2 eq. 1,4-diiodobenzene. The TLC plate in MPN/TLC could be removed easily by the treatment of HF solution. The thickness of C-MPN was controlled to match the Q absorption band intensity at 658 nm of Velvet-MPN-2 (vide infra) by screening the amount of building blocks and reaction times. As shown in Figure S5b in the SI, the C-MPN had an overall flat surface and ~1.5 m thickness. Porphyrin moieties in the materials can be characterized by the Q bands in the UV/vis absorption spectroscopy.14 Especially, Q band at 658 nm is a unique absorption peak of metal-free porphyrins and is sensitive to the change of chemical surroundings of porphyrin rings. As the length of MPN rods in Velvet-MPN1, Velvet-MPN-2, and Velvet-MPN-5 increased, the absorbance of Q band at 658 nm gradually increased from 0.44 to 0.88 and 1.26. (Figure 3a) In the case of Velvet-MPN-5, an additional absorption band appeared at 700 nm, which originates from the J-type aggregation of porphyrin materials.15 As described above, the Q band intensity of C-MPN is nearly the same as that of Velvet-MPN2. The chemical components of Velvet-MPNs and C-MPN were further characterized by solid state 13C nuclear magnetic resonance spectroscopy (NMR). As shown in Figure 3b, the 13C peaks of alkynes appeared at 75~90 ppm. The 13C peaks of phenyl rings ppm appeared at 119, 130, and 142 ppm, respectively. The 13C peaks of porphyrin rings appeared at 119, 138, and 153 ppm, matching well with those in the literature.4,16


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(a) Velvet-MPN-2 Velvet-MPN-5

* * * C-MPN

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Figure 3. (a) UV-vis absorption spectra and photographs, (b) solid state 13C NMR spectra, (c) N2 adsorption-desorption isotherm curves at 77K, and pore size distribution diagrams (based on the DFT method) of Velvet-MPNs and C-MPN.

Infrared absorption spectroscopy of Velvet-MPNs and CMPN showed N-H vibration peaks at 3300 (stretching) and 970 cm-1 (bending) and no significant peaks at 1000 ~ 1010 cm-1 (metal-N vibrations of metal porphyrins), which features match well with the IR absorption spectra of metal free porphyrins in the literature.16-17 (Figure S6 in the SI) These characterization

data indicate that the Velvet-MPNs and C-MPN have nearly the same chemical structure. According to the elemental analysis (N contents: 6.06, 6.01, 5.95, and 6.43wt%,), the amounts of porphyrins in Velvet-MPN-1, Velvet-MPN-2 Velvet-MPN-5, and C-MPN were calculated as 1.08, 1.07, 1.06, and 1.15 mmol/g, respectively. According to the analysis of N2 isotherm curves based on the Brunauer-Emmett-Teller (BET) theory, as the lengths of MPN rods in Velvet-MPNs increased, the surface areas increased from 249 m2/g (Velvet-MPN-1) to 326 (Velvet-MPN-2) and 528 m2/g (Velvet-MPN-5), respectively. (Figure 3c) Among the studied materials, the C-MPN showed the lowest surface area of 155 m2/g. These results indicate that the rod parts have higher porosity than the flat film, possibly due to more facile π-π stacking of porphyrin networks in the film. The micropore volumes (Vmic) also gradually increased from 0.05 cm3/g (CMPN) to 0.09 (Velvet-MPN-1), 0.11 (Velvet-MPN-2), and 0.16 cm3/g (Velvet-MPN-5), respectively. The pore size distribution diagrams obtained by the density functional theory (DFT) method revealed the microporosities of Velvet-MPNs and CMPN. While porphyrins are very versatile and functional molecules, they are subject to facile packing due to the intrinsic planar molecular geometry, resulting in the blocking of functional porphyrin sites. Thus, the networking-induced microporosities of Velvet-MPNs and C-MPN can enhance the functionalities of porphyrins. The powder X-ray diffraction studies (PXRD) showed amorphous characteristic of all MPN materials, which is the common property of MONs prepared by the Sonogashira coupling of organic building blocks. 8 (Figure S7 in the SI) Thermogravimetric analysis (TGA) showed that the Velvet-MPNs and C-MPN are thermally stable up to ~195oC. (Figure S8 in the SI) As living organisms have utilized porphyrins for various functions, artificial porphyrin systems have also been extensively synthesized and applied.18-19 Metal free porphyrin rings have reactivity towards acid due to the basic pyrrole rings.20-24 Also, the acidified metal free porphyrins can be neutralized by the reaction with bases such as ammonia.25-27 The porphyrin rings are sensitive to the change of chemical surroundings, followed by the change of optical properties.18-27 To understand any beneficial behavior of the velvet worm surface-like structure of Velvet-MPNs, we studied their sensing performance towards hydrogen chloride and ammonia gases. (Scheme S1 in the SI) Figure 4 and Table S1 in the SI summarize the results. Through the reaction of Velvet-MPNs with hydrogen chloride, a new absorption band appeared at 691 nm, which is attributed to the formation of the acidified pyrrolinium salts. (Figure 4a) Unfortunately, the sensing performance of Velvet-MPN-5 could not be studied due to the additional absorbance at 700 nm even before the reaction with hydrogen chloride.15 The Velvet-MPN2 with longer MPN rods was generally more sensitive than Velvet-MPN-1. (Figure 4b) While the Velvet-MPN-1 under 50 ppm HCl showed 56% of the A observed at 500 ppm HCl, the Velvet-MPN-2 under 21 ppm HCl showed 55% of the A observed at 500 ppm HCl. Velvet-MPN-1 and Velvet-MPN-2 showed initial (A)/C, (A change at 691 nm)/ (concentration change of HCl in ppm unit) values of 7.5 × 10-3 ppm-1 (R2: 0.99, standard deviation: 2.4 × 10-4) and 0.019 ppm-1 (R2: 0.99, standard deviation: 3.2 × 10-4) towards hydrogen chloride, respectively. The limits of detection (LODs)28 of Velvet-MPN-1 and VelvetMPN-2 for hydrogen chloride were calculated as 0.097 and



0.050 ppm, respectively. (Figure S9 in the SI) It is noteworthy that the recent porphyrin materials developed for the optical sensing of hydrogen chloride showed LODs in the range of 6.7 ~ 0.1 ppm.20-24 (Table S2 in the SI) (a)

HCl

NH3

(b)

0 ppm 1.5 ppm 5 ppm

10 ppm 20 ppm 50 ppm

100 ppm 200 ppm 500 ppm

0 ppm 0.75 ppm 1 ppm

2 ppm 5 ppm 10 ppm

20 ppm 50 ppm 100 ppm 200 ppm

(c) HCl

NH3

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C-MPN

Velvet-MPN-1

Velvet-MPN-1

Velvet-MPN-2 C-MPN

(e)

(d)

HCl

NH3

HCl

NH3

Figure 4. (a) The change of UV-vis absorption spectra of VelvetMPN-2 by reaction with hydrogen chloride and ammonia gases. The change of absorbance at 691 nm (the average values of three independent samples) of Velvet-MPN-1, Velvet-MPN-2, and CMPN by reaction with (b) hydrogen chloride and (c) ammonia gases. The repeatability (the retention of A at 691 nm in the repeated exposures to 50 ppm hydrogen chloride and 50 ppm ammonia) of the sensing performance of (d) Velvet-MPN-1 and (e) VelvetMPN-2.

The control C-MPN showed initial (A) (at 691 nm)/C (ppm) value of 3.5 × 10-3 ppm-1 (R2: 0.98, standard deviation: 8.0 × 10-4) and LOD of 0.69 ppm towards hydrogen chloride. These observations indicate that the 1D structure of VelvetMPNs (especially, Velvet-MPN-2 with longer rods) is much more sensitive in the sensing performance than C-MPN by up

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to ~14 times, possibly due to the enhanced surface area, the enhanced utilization of porphyrin sites, and the resulting more efficient contract of small molecules with sensing species in the Velvet-MPNs. Ammonia is a useful but toxic gas. It is known that humans can smell ammonia at concentrations higher than 50 ppm. 29 International environmental departments such as the US Occupational Safety and Health Administration (OSHA) set a permissible exposure limit of 50 ppm for ammonia and regulate the working time (8 h per day).29-30 Thus, the sensing of ammonia at concentrations lower than 50 ppm is important. The reaction of the salt forms of Velvet-MPNs with ammonia regenerated the original metal free porphyrin moieties. (Figure 4a) The sensitivities of Velvet-MPNs towards ammonia were much higher than those towards hydrogen chloride. (Figure 4c) The Velvet-MPN-1 and Velvet-MPN-2 were very sensitive towards ammonia and showed A values of 0.15 and 0.25, respectively even at 0.76 ppm NH3. These A values are 55 and 53% of the A values observed at 200 ppm NH3. Moreover, the Velvet-MPN-1 and Velvet-MPN-2 showed A values of 0.24 and 0.44 at 10 ppm NH3, respectively. These A values are 89 and 92% of the A values observed at 200 ppm NH3. VelvetMPN-1 and Velvet-MPN-2 showed initial (A) (at 691 nm)/C (ppm) of -0.086 ppm-1 (R2: 0.98, standard deviation: 4.0 × 10-3) and -0.21 ppm-1 (R2: 0.99, standard deviation: 4.7 × 10-3) towards ammonia, respectively. The limits of detection (LODs) of Velvet-MPN-1 and Velvet-MPN-2 for ammonia were calculated as 0.14 and 0.070 ppm, respectively. (Figure S9 in the SI) In comparison, the control C-MPN showed initial (A) (at 691 nm)/C (ppm) value of -0.018 ppm-1 (R2: 0.90, standard deviation: 1.9 × 10-3) and LOD of 0.32 ppm towards ammonia, indicating that the Velvet-MPNs are more sensitive towards ammonia than C-MPN by up to ~4.6 times. In the literature25-27, the LODs of recent porphyrins materials for the optical sensing of ammonia were reported in the range of 7 ~ 0.16 ppm. (Table S2 in the SI) The repeatability of the sensing performance was investigated. As shown in Figures 4d-e, the Velvet-MPN-1 and Velvet-MPN2 showed good repeatability in the five successive sensing of HCl (50 ppm) and ammonia (50 ppm). According to the SEM analysis of Velvet-MPNs recovered after five sensing cycles, the aligned 1D morphology was completely retained. (Figure S10 in the SI) In the literature (Refer to Table S2 in the SI), most porphyrinincorporated materials20,22,24-27 for the optical sensing of hydrogen chloride and ammonia were fabricated through the mixing or grafting of single molecular porphyrins with organic/inorganic polymer matrixes, resulting in nonporous materials. In these cases, it might be difficult to utilize the inner porphyrin moieties in the sensing. Recently, Wu et al21,23 reported the fabrication of nanostructured porphyrin polyimide materials, showing a LOD of 5 ppm for hydrogen chloride. In comparison, the enhanced sensitivities (LODs of 0.050 and 0.070 ppm for hydrogen chloride and ammonia, respectively) of Velvet-MPN-2 in this work are attributable to its 1D nanostructure and inner microporosity. In conclusion, this work shows that microporous organic network materials can be applied to the construction of nano/micro-sized molecular structure. By template synthesis, porphyrin network materials could be engineered to the aligned rods


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biomimicking the surface structure of velvet worms. The aspect ratios of MPN rods could be controlled by changing the AAO templates. The Velvet-MPNs showed much higher sensitivities than C-MPN to hydrogen chloride and ammonia by ~14 and ~4.6 times, respectively, due to the efficient contact of sensing species with gases. (Figure S11 in the SI) The Velvet-MPN-2 with longer MPN rods showed better sensitivity than the VelvetMPN-1. Especially, the Velvet-MPN-2 showed the A (at 691 nm) of 0.25 at 0.76 ppm NH3, initial (A)/C values of -0.21 ppm-1, and LOD of 0.070 ppm for ammonia. We believe that more various functional materials with an aligned 1D structure can be engineered by the synthetic strategy in this work.

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 ASSOCIATED CONTENT

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Supporting Information. Experimental procedures, SEM images of MPN materials prepared by various AAO templates, a scheme for control C-MPN, IR spectra, PXRD patterns, TGA curves of Velvet-MPNs and C-MPN, SEM images of Velvet-MPNs recovered after sensing cycles, and additional analysis of sensing performance. This material is available free of charge via the Internet at http://pubs.acs.org.

 AUTHOR INFORMATION Corresponding Author

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* E-mail: [email protected]

Author Contributions 15

‡These authors contributed equally Notes The authors declare no competing financial interests.

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 ACKNOWLEDGMENT This work was supported by Basic Science Research Program (2016R1E1A1A01941074) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning.

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Table of Contents

Enhanced Performance

N NH HN N

N NH HN N

HCl, NH3 Sensing

N NH HN N

N NH HN

3 m

N


Velvet-MPN-2

7

Microporous Porphyrin Networks Mimicking a Velvet Worm Surface

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