Aqueous Nanocoating Approach to Strong Natural Microfibers with

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Cite This: ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX

Aqueous Nanocoating Approach to Strong Natural Microfibers with Tunable Electrical Conductivity for Wearable Electronic Textiles Lan Xie,*,† Bo Shan,† Huan Xu,‡ Jinlai Li,‡ Zhong-Ming Li,§ and Qiang Zheng†,∥ †

Department of Polymer Materials and Engineering, College of Materials and Metallurgy, Guizhou University, Guiyang 550025, China ‡ ENN Graphene Technology Co., Ltd., ENN Group, Langfang 065001, China § College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, China ∥ College of Polymer Science and Engineering, Zhejiang University, Hangzhou 310000, China S Supporting Information *

ABSTRACT: Electronically conductive and mechanically strong natural fibers with desirable durability, flexibility, and environmental compatibility are in great need for manufacturing multifunctional textiles. Here we reveal a facile yet effective nanocoating approach to immobilization of few-layer graphene oxide (GO) nanosheets at ramie fiber by hydrogen-bond-driven self-assembly process under all-aqueous and additive-free condition. The surface morphology and chemistry of GOfunctionalized ramie fiber (GOFR) were significantly altered with the homogeneous decoration of trace amount of GO nanosheets, readying remarkable property improvements and functionality realization. The tensile strength of GOFR (553 MPa) witnessed an increase of over 25% compared to pristine ramie, as accompanied by moderate promotion of extensibility with the assistance of robust GO nanosheets. It is worth noting that exceptionally high electrical conductivity was achieved for thermally reduced GOFR (rGOFR), with values as high as 83.2 S/cm after reduction at 250 °C for only 30 min. By tuning the reduction time and temperature, the conductivity of rGOFR was well controlled in an extremely wide range of 0.1−83.2 S/cm. This effort provides useful insights into the fabrication of highly strong and conductive natural fibers in the promising field of smart fabrics integrating high strength, flexibility, intelligent functionality, and environmental compatibility. KEYWORDS: graphene oxide, natural fiber, smart fabric, mechanical properties, electronical conductivity

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conductive polymers onto fabrics.14−17 These dwarfs, in principle, lay down paramount bottlenecks for the realistic development of multifunctional textiles. The hybrid system integrating flexible textiles with multifunctional nanoparticles showcases several key features that can address emerging property needs such as adequate strength and flexibility and high electrical conductivity.18,19 This strategy is elaborated by the approach to manufacture yarns of lithium-ion battery materials and superconductors through biscrolling carbon nanotube sheets and various functional nanofillers.20

INTRODUCTION

Smart textiles have been among the first materials solution to revolution and implementation of intelligent technology, opening up new possibilities for diverse applications ranging from power storage to medical monitoring and wearable computing.1−5 Central to the unprecedented technological evolution is the development of flexible and durable textiles integrated with various transducers or electronics enabling ondemand functionality.6−10 The development of flexible and multifunctional textiles pursued by the scientific and industrial communities remains challenging.11 This is mainly associated with the insufficient flexibility of traditional metal wires to afford large bending or extension12,13 as well as the complex and specific technical demands required by depositing © XXXX American Chemical Society

Received: April 9, 2018 Accepted: May 4, 2018

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DOI: 10.1021/acsanm.8b00591 ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX

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ACS Applied Nano Materials

Figure 1. An aqueous nanocoating process to facile preparation of GOFR. (a) Digital photos and (b) schematic illustration showing the synthetic approach to produce GOFR fibers. Ultrasonication-assisted aqueous processing permits full exfoliation of GO nanosheets at very low concentration (0.02 mg/mL), essential for creation of strong interactions with hydrophilic ramie fiber. Uniform and close decoration of GO nanosheets leads to the color change from pure white to golden metallic luster.

Another example is the fabrication of energy storage textiles by integrating nanostructured MnO2 into cotton textiles,21 while a simple “dipping and drying” process enabled the preparation of conductive energy textiles displaying high areal capacitance and specific energy.22 Recent efforts moreover disclose tremendous promise of this novel class of hybrid textile materials for wound dressing,23 sensors of external strain and gas molecules,24 superhydrophobic aromatic cotton fabrics,25 thermoelectric generators,26 and antibacterial fabrics.27,28 Following the design principles of integrated hybrid textiles, it is imperative to customize the fiber host and nanoparticle guest. Among the available fiber candidates, natural fibers hold distinct advantages over synthetic fibers in terms of easy accessibility, low cost, high mechanical properties, and excellent weavability.29,30 This is further enhanced by the numerous oxygen-rich functional groups intrinsically carried by natural fibers, giving the possibility to create interaction with foreign nanoparticles.31−33 From the perspective of unique 2D dimensionality and surface chemistry, graphene oxide (GO) nanosheets fall into the category of versatile nanoparticles due to the superior mechanical properties and responsiveness to various external stimuli.34,35 Thermal or chemical reduction could trigger the conversion of GO to reduced GO (rGO),36 which may result in functionality expansion to superhydrophobicity,37 effective catalysis,38 and high electrical and thermal conductivity.39−42 The high specific surface area of GO nanosheets (with a BET-measured value as high as 600 m2 g−1) allows the creation of intensive interaction with the fiber host.43,44 Within this context, integrating GO nanosheets with natural fibers signifies a promising strategy to develop affordable and multifunctional textiles. Assuming that oxygen functional groups of high density are intrinsically carried by both GO and natural fibers, hydrogen bonding interactions provide a viable and facile approach to functionalization of ramie with GO. Following this conception, we propose an environment-respecting and technologically scalable route to create GO-functionalized ramie (GOFR) fibers under aqueous conditions (Figure 1). The key element is ultralow concentration of GO (0.02 mg/mL), essential for the full exfoliation and expansion of GO to few-layer nanosheets with a lateral size approaching 6 μm (Figure S1). It allows the creation of large sheet area with high surface energy for wellexfoliated GO nanosheets, readying strong anchoring interactions with ramie fibers through potential hydrogen bonding. After removal of water under vacuum drying at room temperature, GO nanosheets with the mass ratio of 0.02% are uniformly and closely adhered to ramie fibers, giving the

golden metallic luster. The anchoring of few-layer GO sheets at natural fibers probably afforded an exceptional combination of mechanical robustness and electrochemical functionality for the composite fibers, readying feasible fabrication of smart textiles. The distinct features of this approach are principally associated with (1) low-cost and effective functionalization method by hydrogen bonding during the aqueous processing, (2) sufficient coating of ramie fiber by extremely low concentration of GO sheets, (3) promotion of mechanical robustness for the GOFR and rGOFR fibers, and (4) facile reduction of GO sheets by simple thermal treatment to achieve high electrical conductivity. The proposed fiber functionalization strategy, offering the industrial feasibility and low production cost unattainable with common surface modification methods, may prompt materials scientists to pursue GO functionalization of textile precursor with multifunction yet lightweight.

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EXPERIMENTAL SECTION

Materials. Ramie fiber from outer culm of ramie plant was commercially purchased from Xinhe Textile Ltd., Nanjing, China. The diameter of the fiber mainly locates in the range of 8−30 μm, with an average value of approximately 15 μm. Starting from the commercial graphite powder (SP-1, Bay Carbon, USA), graphene oxide (GO) nanosheets were prepared via a modified Hummers method.44 Deionized water and ethanol were obtained from VWR, Germany. Sample Preparation. Following the schematic illustration in Figure 1, an aqueous route was applied to prepare GO-functionalized ramie (GOFR) fiber. With the assistance of ultrasonication (1 h), GO nanosheets were dispersed in water at an ultralow concentration (0.02 mg/mL), rendering complete exfoliation of GO nanosheets and uniform coating of ramie fibers with few-layer GO nanosheets. Ramie fiber was directly immersed in GO/water solution with gentle stirring for 0.5 h, allowing the immobilization of GO nanosheets at ramie fiber driven by hydrogen bonding. After vacuum drying at room temperature, GOFR was obtained. To prepare reduced GOFR (rGOFR), GOFR was thermally annealed in a heating furnace at 200 and 250 °C for up to 90 min, while a nitrogen atmosphere was applied to restrict thermal oxidation. SEM Observation. A field-emission SEM (Inspect F, FEI, Finland) operated at 5 kV was used to observe the surface morphology of GOFR and rGOFR, prior to which the fiber yarns were sputter-coated with gold. Polarized Optical Microscopy (POM) Observation. Individual fibers of GOFR and rGOFR were directly observed on an Optiphot 2 microscope equipped with a Leica digital camera. Fourier Transform Infrared Spectroscopy (FTIR). The FTIR spectra in the range of 4000−600 cm−1 for GO, GOFR, and rGOFR yarns were recorded on a PerkinElmer Spectrum 2000 spectrometer (PerkinElmer Instrument) with 16 scans at a resolution of 4 cm−1. B


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Figure 2. Morphological features of GOFR. (a, b) SEM images of individual GOFR fibers showing the tight attachment of extended few-layer GO nanosheets. (c) FTIR spectra of GO, ramie, and GOFR demonstrating the creation of strong interactions between GO and ramie in GOFR fibers. (d) Representative stress−strain curves of ramie and GOFR indicating the simultaneous promotion of strength and ductility for GOFR. Tensile Testing. Individual fibers of pristine ramie and GOFR were tested on an Instron universal test instrument (Model 3343, Instron Instruments, USA) with a load cell of 50 N at 23 °C and relative humidity of 50%. The crosshead speed was set at 1 mm/min, and the gauge length was 10 mm. At least five single fiber replicates were measured for each sample. Two-Dimensional Wide-Angle X-ray Diffraction (2D-WAXD) Measurements. The morphology of GO in GOFR was measured by 2D-WAXD measurements of GO and GOFR using a homemade laboratory instrument (Bruker NanoStar, Cu Kα radiation) in the Crystallography Lab, Department of Molecular Biology and Biotechnology, University of Sheffield. The X-ray beam with a wavelength of 0.154 nm was focused to a tiny area of 4 × 4 μm2, and the distance from sample to detector was fixed at 350 mm. The 2D diffraction patterns were collected by an X-ray CCD detector (Model Mar345, a resolution of 2300 × 2300 pixels, Rayonix Co. Ltd., USA). Raman Spectroscopy. The Raman spectra of GO, GOFR, and rGOFR yarns were recorded on a micro-Raman spectroscopy (DXRxi, Thermo Scientific Instrument, USA) with a laser wavelength of 532 nm. X-ray Photoelectron Spectroscopy (XPS). XPS measurements of GO, ramie, and GOFR were performed using a scanning ESCA microprobe (Quantum-2000, ULVAC-PHI, Japan) equipped with a hemispherical electron analyzer and a scanning monochromatic Al Kα X-ray source. Electrical Conductivity. The electrical conductivity of the rGOFR yarn was evaluated using the dc four-probe method by an impedance analyzer (model 1225B frequency response analyzer and model SI 1287 electrochemical interface, Solartron, UK). Five replicates were measured for rGOFR yarns reduced at various conditions. The specific electrical conductivity (σ) and specific electrical resistivity (ρ) was calculated using the following equations: σ = 1/ρ

(1)

ρ = R·S/L

(2)

direct TEM observation. Droplets of GO/water suspensions were deposited onto a lacey carbon film 400 mesh copper TEM grid (Ted Pella, Inc.) and allowed to dry under vacuum prior to TEM imaging (Hitachi, 80 keV). Dynamic Light Scattering (DLS). A rough measure of lateral size for graphene oxide nanosheets dispersed and exfoliated in water (0.02 mg/mL) was carried out using a Zetasizer Nano ZS from Malvern Instruments (Malvern, UK). Thermal Gravimetric Analysis (TGA). Thermal behavior of GO, ramie, and GOFR was evaluated by TGA, heating from 40 to 800 °C in nitrogen with a Mettler Toledo TGA/STDA 851e apparatus at a rate of 10 °C/min.

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RESULTS AND DISCUSSION It is hypothesized that our approach renders the immobilization of few-layer GO nanosheets at ramie fibers for GOFR, as examined by direct observation and measurements of interactive bonding (Figure 2 and Figure S2). Scanning electron microscopy (SEM) images show that GO nanosheets featuring ultralow thickness and large surface area were intimately anchored at the ramie fiber (Figure 2a,b). The nanosheets with sufficient extension gave rise to the generation of numerous wrinkles and ripples, giving the assumption of intense mechanical interlocking arising from the electrostatic attraction and geometrical displacement between GO and ramie.45−47 This is supported by the Fourier transform infrared spectroscopy (FTIR) spectra indicating the formation of hydrogen bonding in GOFR (Figure 2c). After the decoration of GO nanosheets, the prominent peaks in the −OH stretching region were red-shifted from 3337 and 3289 cm−1 for ramie to 3331 and 3271 cm−1 for GOFR, respectively, as accompanied by the red-shift from 2902 to 2898 cm−1 for the minor peak. Oxygen-rich functional groups such as hydroxyl and carboxyl are naturally carried by ramie fibers,48 giving the possibility for the creation of hydrogen bonds with the oxygen functional groups in GO nanosheets.49,50 The prominent peak of GO (3427 cm−1) was not traced in GOFR, again suggesting the immobilization of few-layer GO nanosheets at ramie.51 Of

where R is the electrical resistivity measured for the fiber yarn and S and L represent the sectional area and the length of the fiber yarn between the probes, respectively. Transmission Electron Microscopy (TEM) Observation. The morphology of GO dispersed in water (0.02 mg/mL) was examined by C


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Figure 3. Structural determination of GOFR. (a) 2D-WAXD images comparing the diffraction patterns for ramie and GOFR yarns. (b) 1D-WAXD intensity profiles of ramie and GOFR demonstrating the existence of few-layer GO nanosheets in GOFR. (c) Full-range Raman spectra of GO, ramie, and GOFR. (d) Raman spectra of GO and GOFR in the range of 1200−1800 cm−1.

Figure 4. Chemical composition of GOFR. (a) Full-range XPS spectra suggesting the C/O ratio of 2.29, 2.77, and 2.37 for GO, ramie, and GOFR, respectively. (b−d) Fitted XPS C 1s spectra resolving the compositions of carbons connected to hydrogen, carbon, and oxygen.

localize and redistribute the penetrating stress, so as to impart tremendous energy dissipation and promote resistance to yielding. The mechanical properties of pristine ramie and GOFR are located among those reported for the naturally occurring ramie fibers (Figure S3). The structural attributes of GO nanosheets were further explored by two-dimensional wide-angle X-ray diffraction (2DWAXD) measurements and Raman spectra (Figure 3). In addition to the diffraction dots arising from well-aligned cellulose crystals in ramie, the 2D-WAXD patterns of GOFR showed a diffraction ring located at 2θ = 9.8°, pointing to the lattice plane (001) of the randomly distributed GO nanosheets.53,54 It is in line with the characteristic stacking order of

particular interest is the significant improvement of mechanical property for GOFR with the assistance of immobilized nanosheets (Figure 2d). Specifically, the tensile strength and Young’s modulus witnessed increase of over 25% and approximately 17% from ramie (442 MPa and 24.4 GPa) to GOFR (553 MPa and 28.5 GPa), respectively. The elongation at break was slightly increased from 2.2% for ramie to 2.5% for GOFR, offering evidence for the promoted extensibility. The combination of elasticity and extensibility for GOFR was primarily a result of remarkable mechanical strength of GO nanosheets and strong interactive bonding between GO and ramie.52 In specific, the mechanically robust GO sheets and strong anchoring interphase are of significance to transfer, D


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Figure 5. Electrical properties of rGOFR yarns. (a) Digital photo showing the apparatus to test the electrical conductivity of rGOFR yarns. Silver paste was coated at the yarn ends to give good contact with the electrodes. (b−d) SEM images of rGOFR yarn showing the excellent flexibility of rGOFR fibers and tight adhesion of GO nanosheets to ramie fiber after thermal reduction at 250 °C for 90 min. (e) Electrical conductivity as a function of reduction time for rGOFR yarns reduced at 200 and 250 °C.

GO increased the proportion of oxygen bearing groups in GOFR such as O−CO (∼288.8 eV), CO (∼287.1 eV), and C−O/C−O−C (∼286.0 eV). The profound variations of the chemical composition at GOFR surfaces not only offer evidence for the tight decoration of GO nanosheets but also lay down the prerequisite for the functionalization of ramie fabrics. Electric conductivity represents one important criterion for the development of electronic textiles. Figure 5 demonstrates that thermal reduction of few-layer GO conferred GOFR highly conductive. To sustain the physical strength and flexibility of ramie fiber, the GOFR yarns were thermally reduced under a nitrogen atmosphere at 200 and 250 °C for up to 90 mina relatively low temperature level for reduction of GO.49,60,61 Figure 5a,b shows the desirable tenacity of reduced GOFR (rGOFR) that allowed the rGOFR to be highly twistable, permitting the design and fabrication of multifunctional threads and textile products using rGOFR yarns.62 Even after 90 min treatment at 250 °C, the reduced GO nanosheets were closely attached onto ramie surfaces (Figure 5c,d). Figures S5−S7 record the evolution of structural features for the thermally reduced GOFR (rGOFR) fibers. The nanosheets were characterized by large planar area and numerous wrinkles, displaying the similar morphological features with pristine GO nanosheets in GOFR (Figure 2a,b). It was important for electron transfer along or among the ramie fibers, essential to realization of high electrical conductivity for rGOFR yarns. Starting from nonconductive GOFR yarns (3.3 × 10−5 S/cm), Figure 5e suggests that thermal reduction at both 200 and 250 °C enabled drastic promotion in conductivity for rGOFR. As reduced at 200 °C, the conductivity of rGOFR substantially increased to 37.9 S/cm after 80 min, with slight decrease after 90 min treatment. The conductivity data measured for rGOFR treated at 250 °C was striking: over 2.5 × 106-fold increase of conductivity was obtained after 30 min (83.2 S/cm, I−V curves shown in Figure S8), followed by a gradual decline to around 40 S/cm with longer annealing treatment due presumably to thermal degradation of ramie fiber. It allows the assumption

few-layer GO, giving strong evidence for the complete exfoliation and full extension of GO nanosheets in GOFR. This assumption is supported by spectroscopic analysis by comparing the Raman spectra of GO, ramie, and GOFR (Figure 3c,d). In the range of 1200−1800 cm−1 (Figure 3d), GO displayed the characteristic Raman peaks for D-band (1346 cm−1) and G-band (1595 cm−1),36,38 originated essentially from the defect-induced double-resonant Raman feature and E2g of C−C bonds, respectively.55 It is of interest to note that the Dband and G-band substantially shifted to 1454 and 1517 cm−1 for GOFR, respectively. It resulted primarily from the suppressed distortion of the honeycomb lattice in the exfoliated and extended GO nanosheets as well as the formation of strong interfacial interactions with ramie.55,56 The existence of fewlayer GO nanosheets at ramie was evidenced by the largely decreased peak width at half-height (PWHF) for D-band and G-band, falling from 116 and 84 cm−1 for GO to 3 and 4 cm−1 for GOFR, respectively.57 In a recent study investigating the layer dependence on the PWHF for individual graphene sheets, Song et al. found that the folding within graphene sheets pushed up the PWHF values of G-band with increasing layers.58 In addition to the decreased crumps or ripples in the few-layer GO, intense interactions anchored at ramie were responsible for the unprecedentedly low PWHF for the D-band and Gband of GOFR. This explains the basically overlapped thermal gravimetric analysis curves of ramie and GOFR (Figure S4), again implying the existence of few-layer GO sheets. Albeit present at few-layer GO nanosheets, the chemical composition at the surfaces of GOFR was significantly altered, as examined by X-ray photoelectron spectroscopy (XPS) profiles (Figure 4). Figure 4a illustrates a C/O ratio of 2.29 for GO, in line with the widely reported scenarios.33,59 The C/ O ratio of GOFR (2.37) lay between those of ramie (2.77) and GO (2.29), suggesting the close attachment of GO nanosheets at ramie with high structural integrity. The XPS C 1s peaks were fitted to resolve the functional groups connected to carbons (Figure 4b−d). It is apparent that the introduction of E


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mechanical robustness for the GOFR and rGOFR fibers, and (4) facile reduction of GO sheets by simple thermal treatment to achieve high electrical conductivity. The profound morphological control over the nanosheets anchored at host fibers and the simplicity of nanocoating process together with the versatility and low cost of the composite fibers should make our strategy broadly applicable to functionalization for other fiber materials.

that the electrical conductivity of GOFR could be tuned by a combination of reduction time and temperature, which are closely associated with the surface chemistry and physical properties of textile products woven by rGOFR yarns. Using the layer-by-layer spray coating method, Tour et al. fabricated conductive Kevlar fibers coated by single-walled carbon nanotubes and graphene nanoribbons, showing a much lower conductivity of 20 and 65 S/cm, respectively.63 The remarkable conductivities of rGOFR fiber yarns were primarily ascribed to (1) superior electron transport along the well-extended rGO nanosheets, (2) good electrical contact between the rGO and host ramie due to intimate adhesion of rGO at host ramie, and (3) high conductivity of host ramie due to the simultaneous carbonization of host ramie at the elevated temperatures. More importantly, the rGOFR fibers were characterized by high elasticity and extensibility with weak relation to the reduction temperatures and time (Figure S9), primarily arising from the strong interfacial adhesion between rGO sheets and host fibers (Figure S10). It is apparent that our approach discloses a facile and straightforward route to highly conductive natural fiber yarns, readying large-scale fabrication of electronic textile products with industrial feasibility. A combination of high mechanical robustness and high electrical conductivity of the fiber candidates represents important criteria for the development of high-performance electronic textiles. To highlight the good balance between the mechanical and electrical properties achieved for rGOFR, we compared the conductivity−strength property space with other nanocoated fibers and nanocomposite fibers (Figure 6). The

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CONCLUSIONS Using a facile aqueous processing method, this work developed a reliable and efficient approach to immobilization of few-layer extended GO nanosheets at ramie fiber amenable to large-scale fabrication. The self-assembly process was primarily driven by hydrogen bonding, which was created between the oxygen-rich functional groups carried by both the GO nanosheets and ramie fiber. In addition to the significant modification of the surface chemistry, the immobilization of few-layer GO enabled large improvement of mechanical properties for GOFR, displaying an increase of over 25% in tensile strength compared to pristine ramie (442 MPa). Of particular interest was the exceptionally high electrical conductivity for rGOFR, achieving 37.9 S/cm after reduction at 200 °C for 80 min. This was coupled with high flexibility to control the conductivity of rGOFR by tuning the reduction time and temperature; e.g., the electric conductivity substantially increased to 83.2 S/cm when reduced at 250 °C for 30 min. This work paves a way to natural fibers functionalized by GO with well-controlled sheet morphology an ideal precursor for electronic textiles with high mechanical properties and tunable electrical conductivity. Our approach also enables easy yet effective control on the morphology of 2D nanosheets, which makes fabrication of multifunctional fabrics straightforward and scalable, and holds potential to suite other 2D fillers beyond GO.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsanm.8b00591. TEM image and DLS measurement of GO nanosheets dispersed in water, POM images of ramie and GOFR fibers, TGA curves of GO, ramie, and GOFR, XPS, FTIR and Raman spectra of rGOFR, I−V and stress−strain curves, and SEM images of rGOFR (PDF)

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Figure 6. Property space for electrical conductivity versus tensile strength for the rGOFR fibers, CNT-coated aramid,64 poly(styreneblock-butadiene−styrene) (SBS)/Ag-coated Kevlar,66 rGO/poly(vinyl alcohol) (PVA) composite fibers,67 CT/PDMS composite fibers,65 Ag nanowire (AgNW)/PU composite fibers,68 and rGO/CNT composite fibers.69

AUTHOR INFORMATION

Corresponding Author

*(L.X.) E-mail: [email protected] or [email protected]. cn. ORCID

Lan Xie: 0000-0003-0539-2077 Zhong-Ming Li: 0000-0001-7203-1453

poor conductivity−strength balance is usually observed when attempting to manufacture conductive fibers, as exemplified by extremely low conductivity of 5 × 10−6 S/cm for aramid fibers coated by carbon nanotubes (CNTs)64 and inferior strength of 1.2 MPa for carbon threads (CT) encapsulated with polydimethylsiloxane (PDMS) elastomer.65 The results presented here, therefore, indicate distinct features that are associated with this approach: (1) low-cost and effective functionalization method by hydrogen bonding during the aqueous processing, (2) sufficient coating of ramie fiber by extremely low concentration of GO sheets, (3) promotion of

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The National Natural Science Foundation of China (51763003 and 21604016), Scientific Research Project of Introduced Talents of Guizhou University (2016027), Outstanding Youth Program of Guizhou Province (20170430178) and Joint Research Program of Guizhou Province (20177251) are F


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ACS Applied Nano Materials acknowledged for the financial support. The authors are deeply indebted to Dr. Patrick Baker from the Department of Molecular Biology and Biotechnology, University of Sheffield, for his kind help during the X-ray measurements.

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