Water Molecule-Triggered Anisotropic Deformation of Carbon Nitride Nanoribbons Enabling Contactless Respiratory Inspection

Open AccessCCS ChemistryRESEARCH ARTICLE1 Jun 2021Water Molecule-Triggered Anisotropic Deformation of Carbon Nitride Nanoribbons Enabling Contactless Respiratory Inspection Yuye Zhang†, Yongxiu Song†, Yanfei Shen, Kaiyang Chen, Qing Zhou, Yanqin Lv, Hong Yang, Ensheng Xu, Songqin Liu, Lei Liu and Yuanjian Zhang Zhang† Jiangsu Engineering Laboratory Smart Carbon-Rich Materials Device, Provincial Hi-Tech Key for Biomedical Research, School Chemistry Chemical Engineering, Medical School, Southeast University, Nanjing 211189 †Y. Y. Song contributed equally to this work.Google Scholar More articles by author , Song† Institute Advanced Materials, Material Science Technology, Zhenjiang 212013 Shen Google Chen Zhou Lv Yang Xu *Corresponding authors: E-mail Address: [email protected] https://doi.org/10.31635/ccschem.020.202000361 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd favoritesTrack Citations ShareFacebookTwitterLinked InEmail The exploitation the interaction between nanostructured matter small molecules, such as H2O at interfaces via dynamic hydrogen bonding, is essentially key smart, responsive nanodevices but remains challenging. Herein, authors report that carbon nitride nanoribbons (CNNRs) with an anisotropic intraplanar interplanar molecular arrangement underwent a deformation triggering. Both experiments bulk samples single disclosed reversible formation hydrogen-bonded adsorption layer was source CNNRs deformation, reminiscent hydration-triggered twist natural bean pods in seeding. Nonetheless, had more balanced affinity, enabling superior response recovery time. By coupling nanotubes, also converted into straightforward electrical readouts record-fast Further applied capture fluctuations humidity real-time respiration, higher detection sensitivity obtained contactless mode, which compared favorably clinical breath-testing station. Given family various C/N ratios, surface properties, topography, finding are outstanding transducer would significantly pave way H2O-triggered smart devices broad prospective applications. Download figure PowerPoint Introduction exploration low-dimensional materials exceptional electronic, optical, mechanical properties has increasingly attracted interest many fields.1,2 For instance, external stimuli heat, light, electricity, pH, solvents perturb microscopic shape graphene, nanotubes (CNTs), Mxene, molybdenum disulfide feature high surface-to-volue abundant interfacial active sites, and/or unique crumpled topography.3–6 As often strongly associated their magnetic, chemical exploiting change these matters envisioned open up new applications, example, nanodevices.7,8 such, comprehensive understanding surfaces present subject great interest, elusive. one few semiconducting two-dimensional (2D) matters, polymeric (p-CN, denoted g-C3N4) unusual optoelectronic thus already gaining success artificial photosynthesis.9–13 Along mainstream use p-CN photocatalyst, nonetheless, much less explored its stacked structures made repetitive triangular heptazine units hydrophilic edge groups. When tailored nanoribbons,14 arrangements along directions very similar (a biopolymer gradient structure).15 Bean well known seeding due inner-stress generated after losing water molecules (Figures 1a 1b). These intriguing facts inspire us hypothesize holds potential biomimetic scarcely been investigated.16 Figure 1. | (a) Scheme photographs pod structure upon dehydration. (b) Proposed hydrophilic/hydrophobic domains. (c) TEM image dry state [see larger version simulated (d)]. AFM height images (e) 40% RH (f) 70% RH. Insets: scheme coiled partially recovered CNNR. Line profiles CNNR indicated arrows 1 (g), 2 (h), 3 (i) (f). Here, we reported first discovery triggered interacting forming layer. Moreover, CNTs π–π interaction, delicate could be simply efficiently easy-to-measure resistance change. result, CNNRs-based exhibited ultrafast ca. 50 ms, reproducibility, selectivity linearity almost full range, outperforming pulmonary function testing station demonstration respiratory monitoring. This study initiate conceptually application form low-cost molecule diverse range emerging fields performances. Experimental Methods Chemicals Dicyandiamide (DCDA, 99%) purchased from Sigma-Aldrich (St. Louis, USA). Sodium hydroxide (NaOH, 96+%) Sinopharm Reagent Co., Ltd. (Shanghai, China). Multiwalled (product no. S-MWNT-1020) were Shenzhen Nanotech Port (Shenzhen, interdigitated Au Pt electrodes nos. ED-IDE3-Au ED-IDE3-Pt) Micrux Technologies (Asturias, Spain). Ultrapure (18.2 MΩ cm), Smart2Pure purification system (Thermo, Waltham, USA), used all experiments. Preparation CNNRs–CNTs prepared according our previous report. Briefly, initially thermal condensation DCDA 550 °C ground fine powders agate mortar before use. Then, powder (500 mg) added NaOH solution (3 M, 20 mL), mixture stirred 60 12 h treated under ultrasonication every 4 h. After that, removing excessive dialysis membrane weight cutoff 3500 Da (D306-50; Biodesign Inc., Shanghai, China) against until neutral. synthesized adding (1 0.5 mL dispersion (8.9 mg/mL), then volume adjusted same mL) using water. mixtures ultrasonicated 15 min obtain homogeneous dispersion. Characterization Scanning electron microscopy (SEM) collected on Zeiss Ultra Plus SEM (Potsdam, Germany). Transmission (TEM) JEM-2100 microscope (JEOL, Tokyo, Japan). circular dichroism experiment measured Chirascan spectrometer (Applied Photophysics, Leatherhead, United Kingdom) quartz. Raman spectra DXR™-laser micro spectrophotometer (Ex = 532 nm; Thermo). Elemental analysis (EA) carried out Vario EL Cube analyzer (Elementar, Langenselbold, X-ray diffraction (XRD) patterns recorded SmartLab Ultima IV diffractometers (Rigaku, Japan) sealed capillaries. Brunauer–Emmett–Teller (BET) area calculated 77 K N2 adsorption–desorption isotherms acquired Nova 1000e instrument (Quantachrome, Boynton Beach, FL). All measurements potentiostat (Gamry Reference Gamry 600, Philadelphia, Atomic force (10 μL) deposited onto freshly cleaved mica air-dried 10 min. Then residues removed, sample dried measurement. performed ambient conditions (Multimode SPM Nanoscope V controller; Veeco Instruments, Bruker, Billerica, cantilever (ultrasharp silicon probe, OMCL-AC160TS-R3; Olympus, spring constant 26 N m−1. nanoscale material property mapping, calibrated ramp tuning beforehand. We imaged 8 quantitative nanomechanical mapping mode atomic (AFM) conditions, named PeakForce (PF-QNM, USA) precise control. Tapping® oscillates, far below resonant frequency, vertical motion (main) Z piezo element relies peak feedback. Peak each individual tap. tapping or Tapping scan frequency Hz optimized feedback parameters 512 × 512-pixel resolution. air hygroscopic test controlled Parkoo dehumidifier (no. YDA-870EB; Parkoo, Guangzhou, down eight random places three confirm consistency height. average calculating subtracting substrate data analyzed NanoScope Analysis software (version 1.7, Gwyddion 2.51, Czech Metrology Institute, Brno, Republic) processing. Fabrication sensor- humidity-sensing 5 μL (CNNRs: 0.89 mg/mL, CNTs: 0.2 mg/mL) clean electrode drop casting drying sensor. static sensing measurement homemade container (25 cm×18 cm×15 cm). To simulate environment different humidity, 200 dropped cm cellulose paper container. An electric fan convection accelerate volatilization moist atmosphere. High purity (99.999%, 79% 21% O2) replace part humidity. atmosphere detected commercial humidometer (Benetech, current–voltage (I–V) plots potentiostat. response-/recovery-time measurement, sensor placed silicone pipeline 8-mm diameter, airflow passing through (0.1 MPa). humid pulse, 100% relative (RH) injected up-pipeline (ca. cm) syringe. responded signal monitoring, front mouths noses 5–7 away) volunteers noncontact manner ( Supporting Information Movie S1). breathing, Results Discussion tailoring pristine alkaline hydrolysis condition.14 shown (Figure 1c), uniform width tens nanometers length several micrometers, distinct mostly consisted particles micrometers size morphology further confirmed S2a), thickness 3.26 ± 0.30 nm profile S2b), corresponded layers. interestingly, twisted observation 1d), differed traditional planar structure. A phenomenon clearly observed image, periodic CNNRs, axial periodicity S2a depicted S2c. Besides, spectrum stronger absorption intensity than S3), indicating chirality CNNRs. explored. S4 demonstrated Fourier transform infrared (FT-IR) enhanced vibration nearby 3200 cm−1, ascribed −OH/NHx It groups decorated basic skeleton p-CN, consistent combustion EA. line, hydrophilicity alter comparison studied contact angle In general, existing –NHx –OH terminals/defects hydrophilic. Nevertheless, slight increase initial observed, explained wetted owing nanorough S5a). complete droplet <4 s, faster (at least >30 s), absorbability substantially improved. remarkably wrinkled absorbing providing evidence strong presence S5b). worth noting because aforementioned low Owing dedicated terminal groups, remitted combining environment. demonstrate desorption Figures 1e–1g 1g show decreased 3.4 1.5 nm, increased 62.0 101.8 when environmental 70%. According loss fluctuation 1h 1i), significant swelling uncoiling effect molecules,17,18 structural transformation wet conditions. understand interactions FT-IR exposed set 2a revealed peaks 3080 3460 cm−1 rising 6% 86% RH, can attributed absorbance restored strength 7% reversibility adsorption/desorption From enlarged 1200 1700 S6), influence heterocycles stretching proved reversible. proven capillary XRD 2b 2c). interlayer (002) found slightly shift smaller angle, indicative expanded distance, latter evident suggested tailoring, strengthened led massive swelling, presumably ascribable density edges 2. humidification. dashed lines peaks. (not scale) molecules. adhesion map (d) Representative curve (up panel) line (bottom arrow (d, e) verify it highly desired characterize fundamental quantity, tip measured. 2d 2e) 2f, upper panel), maximum approximately 20.30 nN while position only 8.53 statistical bottom general trend. supposed probe identical relatively good hydrophilicity, Van der Waals absorbed control, excellent maintained 20.80 nN) both Exploring Young’s modulus provided softening water.19,20 S7, 1578 48 MPa Note variation compatible some polymers, macromolecular nature.21 Therefore, reversibly interacted internal concentration polymer, release residual stress bonding Different photocatalysis study, should noted nature rarely so far,17,18 applications devices, discussed following context. readout slow inconvenient practical molecules-transducing signals widely systems they quickly processed integrated circuits most electronic devices. Since conductivity derivatives inadequate S8), reinforcement agent sensed poorly alone, boost readout, improve mass transfer, optimize interface conductivity, nanostructure (approximately diameter length; S9a S9b), (144.3 m2/g; S10a). nanoribbon slit-type porosity (194.7 m2/g) (8.6 helpful efficient transport sites (–NHx terminals) throughout whole network reaching equilibrium, vice versa processes. similarity conjugated framework, ready coupled effective noncovalent S9c, S9d, a10b). shown, dispersed cooperation simple one-step ultrasonic agitation process S11). Because difficult disperse aqueous solution, environmentally friendly solvent, successful synthesis expected device fabrication maximization sensing. deformed interconnection as-prepared influenced, subsequently altered 3a). Based principle, investigate performance, interdigital two-electrode (see details Information). I–V curves 3b) atmospheres. linear passed coordinate origin, Ohm’s law typical conductor behavior CNNRs–CNTs. With gradual decrease slope I-V observed. occurred, covered conductive among decrease, increasing composite showed wide 3c), shows attractive possibility realistic eliminate substrate, Compared those electrode, similarly over entire originated exclusively rather metal electrodes. 3. absorption/desorption Relative ranging 5% 97%. Response time pulsed flow air. Time-resolved tests changing 55% reproducibility test. normalized current (inset: I–T curves) gases solvent vapors showing selectivity. development fast critical monitoring rapidly fluctuating defined output reach 90% final amplitude.22 proposed ms current, 3d inset) Such superfast competitive state-of-the-art Table S1).23–34 exact value here does not fully represent real performances, evaluation methods studies reports. end, context, Notably, 3d) reached longer time, pulse took specific details). times factors: (1) rapid structure, (2) affinity