Forum Article www.acsami.org
Cite This: ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Ultrafastly Interweaving Graphdiyne Nanochain on Arbitrary Substrates and Its Performance as a Supercapacitor Electrode Fan Wang,†,‡ Zicheng Zuo,*,† Hong Shang,† Yingjie Zhao,§ and Yuliang Li*,†,‡ †
Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Research/Education Center for Excellence in Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China ‡ University of Chinese Academy of Sciences, Beijing 100049, P. R. China § Key Laboratory of Biobased Polymer Materials, Shandong Provincial Education Department, School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, P. R. China S Supporting Information *
ABSTRACT: A moderate method is first developed here for superfast (in seconds) growth of an ultrafine graphdiyne (GDY) nanochain on arbitrary substrates in the atmosphere. This is an environmentally friendly and metal-catalyst-free method, efficiently eliminating extraneous contaminations for the carbon materials. The seamless GDY coating on any substrates demonstrates that an all-carbon GDY possesses outstanding controllability and processability, perfectly compensating for the drawbacks of prevailing all-carbon materials. After the decoration of 3D GDY nanostructures, the substrates become superhydrophobic with contact angles high up to of 148° and can be used as outstanding frameworks for storing organic pollution. Because of the reasonable porous and 3D continuous features, the as-prepared samples can be applied as high-performance binder-free supercapacitor electrodes with high area capacitance of up to 53.66 mF cm −2, prominent power performance, and robust long-term retention (99% after 1300 cycles). KEYWORDS: graphdiyne, all-carbon material, 2D material, supercapacitor, electrode
■
INTRODUCTION All-carbon materials, such as graphene, carbon nanotube, carbon black, carbon fiber, and graphite,1−4 have begun to affect human daily life by making devices much lighter, more efficient, stouter, and safer. However, there is a bottleneck for more effective utilization of these all-carbon materials because of their fabrication conditions, such as high temperature, inert atmosphere, and so on. Graphene, carbon nanotube, and fullerene are showing intensive reliance on the substrates, temperature, and metal catalysts,5−7 leading to low efficiency, high cost, and extraneous contamination. It is evident that these limitations hinder applications of all-carbon materials in many imperative areas. For example, in electrochemical fields, the surface protection of highenergy-density cathodes and anodes by all-carbon materials has strived for a long time to alleviate primary and secondary structure changes and relieve safety problems against the organic electrolyte, but this cannot be reached because of carbothermic reduction and low efficiency under the above conditions;8−10 the uniform carbon coating for electrochemical anticorrosion is also heavily hindered because the growth of the carbon protection layer shows high substrate reliance;11−13 for the catalysts, the in situ growth methods for all-carbon materials, which can efficiently control the metal nanoparticle size and fasten the © XXXX American Chemical Society
nanoparticles onto substrates, are mightily required to operate under low temperature.14,15 Until now, no efficient method for producing all-carbon materials has been developed to satisfy these aforementioned demands. Graphdiyne (GDY), since its first preparation under mild conditions in 2010,16 has shown impressive promise in green energy fields,17−26 such as in lithium-ion batteries, photocatalysis, electrocatalysis, solar cells, and so forth,27 making these devices more efficient. Considering the ever-increasing practical requirements, these experimental cases were just the beginning of the development and application of this moderate all-carbon material. From our recent progress, we find that GDY is the first all-carbon material that can be prepared the easiest and most efficiently under a striking mild condition (120 °C).28,29 The preparation of GDY under such a condition is a significant breakthrough for the development of moderate all-carbon materials in many fields, offering all-carbon materials Special Issue: Graphdiyne Materials: Preparation, Structure, and Function Received: January 24, 2018 Accepted: March 2, 2018
A
DOI: 10.1021/acsami.8b01383 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Forum Article
ACS Applied Materials & Interfaces
Then, the large-scale GDY on the nickel foam is systematically investigated by scanning electron microscopy (SEM) as the representative (Figures S4 and S5). Figure 1a demonstrates that the large-scale GDY nanostructure can be seamlessly coated onto the 3D nickel foam, further inferring that this approach is highly efficient for decorating the all-carbon nanostructure on the substrates. According to the magnified images of Figure 1b,c, it can be noticed that GDY has a nanochain-like structure with a width of 20 nm (very close to that of carbon nanotube), which is densely interweaved together like cotton on the backbone of the framework. Except for weaving of the GDY nanochains on the backbones, the large voids of the foam are also interweaved by the well-oriented ultrafine nanochains (Figure1d), which are more than 100 μm in length (Figure S6). Such ultrafine and long nanochains can greatly increase the surface area for storage of active matters and form excellent conductive networks during the electrochemical applications, efficiently enhancing the electrochemical response. As for the hydrophobic property, the ultrafine GDY nanochains might help to change the static water/oil contact angle and capture the organic solvent. For evidently investigating the continuousness in large scale, the sample was first blown with high-pressure nitrogen gas to remove the GDY nanochain in the voids; then the backbone of nickel foam was dissolved by overnight immersion of samples into a hydrochloric acid and ferric chloride aqueous solution. After the removal process, it could be observed that the GDY nanostructures possess a good 3D continuousness, and removal of the backbones leaves 3D perforative channels conforming the nickel foam, similar to the graphene growth on the nickel foam under high temperature.30 To reveal how the GDY nanochain grows on the nickel foam, the SEM image (Figure 1g) close to the backbone side is enlarged, indicating that the GDY nanochains are firmly implanted on an ultrathin GDY nanofilm (20 nm). Thus, such a kind of morphology confirms that the GDY hierarchical nanostructures can be steady and intimately adhered onto the substrates, reducing the interfacial impedance in the following electrochemical applications. The bottom side of the nanofilm (Figure 1h,i) is smooth, transparent, and folded, representing the ultrathin and flexible properties of this nanofilm. The 3D GDY nanostructure was further characterized by TEM measurement for investigating the relationship between the nanochain and nanofilm. Figure 2a clearly reveals that the GDY hierarchical morphology containing the nanofilm and nanochain is coincident with the SEM results. Furthermore, the nanofilm well conforms the backbone feature of the nickel foam. Highresolution TEM (HRTEM) in Figure 2b reveals that the GDY nanochains are stringed together with onion-like nanospheres with well-defined lamellas in large scale. The anfractuous lamellas mean the formation of a strong chemical bonding between the onion-like nanospheres, confirming the consecutive conductive channels in the GDY nanochain. Interestingly, the temperature (120 °C) for this onion-like all-carbon material here shows many preponderances compared with the reported results, which were carried out under high temperature from 400 to 1700 °C.31,32 In addition, Figure 2b demonstrates that the interweaved GDY nanochain maintains the all-carbon backbones for electronic conductivity and the nanopores for ionic migration, which is preferred for the electrochemical electrodes. Further amplifying the margin of the nanofilm, the protuberance with well-defined lamellas on the nanofilm is indicative that the nanochains are strongly implanted on the nanofilm. The HRTEM image of Figure 2d demonstrates that the onion-like nanostructure has an interlayer distance ranging from 3.6 to 3.8 Å, well consistent
more editability and processability for realizing some special properties. In this paper, the incomparable controllability and processability of all-carbon GDY are presented. The GDY nanostructures can be in situ superfleetly grown on the foam and planar substrates without using any metal catalyst and toxic solvents in air, thoroughly avoiding extraneous contamination. Furthermore, such an approach is the first case for the mild (120 °C) modification of all-carbon nanostructures on arbitrary substrates in air, showing great promise in some special circumtances, which need low-temperature all-carbon materials in air. Via our investigations, it was found that the as-prepared GDY on these substrates present as ultrafine nanochains, with high surface area and 3D interconnectivity, firmly planting on the all-carbon film. These substrates all show superhydrophobic properties with high static contact angle up to 148° and can be used as excellent absorbents for organic pollutants. Furthermore, the seamless coating of GDY on 3D foams makes GDY a promising supercapacitor electrode, having high area capacitance, powerful performance, and long-term retention.
■
RESULTS AND DISCUSSION Scheme 1 illustrates the preparation processes of the GDY nanostructures on an arbitrary substrate (Figures S1 and S2). First, the precursor hexaethynylbenzene (HEB) was drip-drying on the substrates under the protection of argon with an area loading of about 0.4 mg cm −2. During the period, the HEB monomer was uniformly coated onto the substrates. Then the as-coated substrates were immediately placed on a preheated (120 °C) panel in air, and the reaction was completed in no more than 3 s because of the intensive reaction rate, causing the phenomenon of slight combustion. As shown in Scheme 1b−e, it can be found that, after the reaction, the substrates were uniformly covered with dark-black GDY materials. The uniformity of GDY on the foamlike (nickel and copper foams) and planar (copper foil and silicon wafer) substrates indicates that this preparation strategy of GDY has no relationship with the nature of substrates. Thus, this is the first case for the ultramild and highly efficient growth of all-carbon materials on these substrates in air without any metal catalyst and toxic solution, which might efficiently diminish extraneous contamination to all-carbon decorations. Therefore, it has great potential compared to the prevailing technologies of all-carbon preparation because graphene and carbon nanotube are both prepared under extremely harsh conditions. X-ray photoelectron (XPS) and Raman spectroscopies were performed for identifying the quality of the as-prepared allcarbon GDY, as shown in Scheme 1f,g. The XPS measurement demonstrates that GDY formed on these substrates only contains carbon and oxygen elements, in which the carbon content is from 90% to 94%, showing the all-carbon property of the as-prepared GDY. The high-resolution XPS spectral C 1s peaks are coincident with those of the GDY structure (Figure S3). Negligible signal from the substrates and no signal ascribed to other elements mean that GDY can be densely interweaved on the substrates without any extraneous contamination. The Raman spectra of Scheme 1g exhibit the typical characteristic peaks of GDY attributed to the G (1588 cm −1), D (1360 cm −1), and acetylenic (2170 cm −1) bands.25,33 Because the all-carbon GDY can easily grow on many substrates without any contaminative additives in air and apparently shows no relationship with the nature of substrates, it should be revealed which morphologies of the all-carbon GDY can be constructed on these substrates for the following applications. B
DOI: 10.1021/acsami.8b01383 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Forum Article
ACS Applied Materials & Interfaces
Scheme 1. Preparation and Composition of a GDY Nanostructure on Different Substrates: (a) Scheme Illustrating the Typical Weaving Processes of a GDY Nanostructure on 3D Foamlike Substrates, Photographs of GDY-Modified Substrates of (b) Copper Foam, (c) Nickel Foam, (d) Silicon Wafer, and (e) Copper Foil, (f) XPS Spectra of As-Prepared Samples (Silicon Wafer, Nickel Foam, and Copper Foam), and (g) Raman Spectra of GDY on Different Substrates
with the previously reported results33 and larger than that of graphene (3.4 Å).
As shown in the above-mentioned photographs and SEM images, it can be found that the all-carbon nanostructure can be C
DOI: 10.1021/acsami.8b01383 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Forum Article
ACS Applied Materials & Interfaces
Figure 1. Typical SEM images of the GDY nanochains on the nickel foam: (a) large-scale GDY nanostructure weaving on the nickel foam; (b and c) magnified images of the GDY nanochain weaved on the framework of the foam; (d and e) magnified images of the oriented GDY nanochain interweaving in the voids of the foam; (f) 3D continuousness of the GDY framework grown on the foam after removal of the backbone; (g−i) magnified areas close to the bottom side of GDY.
Figure 2. TEM image of the GDY nanostructure after removal of the nickel foam backbone: (a) large-scale image showing the GDY nanochains uniformly grown on the GDY nanofilm; (b) well-defined lamellar structure of the GDY nanochains, with good continuousness; (c and d) typical structures of the GDY nanochains sprouting from the GDY nanofilm.
angles in Figure 3, it can be found that the GDY-nanochainmodified substrates all exhibit obviously superhydrophobic characteristics, the contact angles are no less than 134.8° (silicon wafer), and the highest contact angle is up to 148° (nickel foam). Such contact angles by the easiest method are remarkably higher than others decorated by hydrophobic polymers.34,35 The hydrophobicities of the as-prepared samples are better than those reported for the GDY nanowall using a solution synthesis method.36 This achievement indicates that many substrates can be mild and
easily and uniformly modified on the metal (copper foam, nickel foam, and copper foil) and nonmetal (silicon wafer) substrates without the introduction of a metal catalyst. The growth of GDY on these substrates can remarkably change their surface properties, which may be meaningful for carbon-coating strategies in some special applications for protecting the substrates against some severe surroundings. Here, the roughness caused by these mildly grown GDY nanostructures on different substrates was tested for its superhydrophobicity. According to the contact D
DOI: 10.1021/acsami.8b01383 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Forum Article
ACS Applied Materials & Interfaces
Figure 3. Static contact angles on different substrates modified by the all-carbon GDY: (a) nickel foam; (b) copper foam; (c) copper foil; (d) silicon wafer. Bottom: Corresponding SEM images of GDY on the substrates. (e) Series of photographs presenting the absorption ability of the GDY foam. (f) Absorption capacity of the GDY foam against diverse organic solvents.
easily modified with a superhydrophobic surface, economically avoiding the fabrication harmfulness of high temperature to the substrates. Because of the superhydrophobic property, the 3D GDY foam can be used as high-performance separator for water/oil separation (Figure S7). The GDY nanostructure in situ grown on 3D metal foams has interpenetrating macropores with a superhydrophobic backbone and a large pore volume, which is ideal for capturing organic pollutants. To directly survey the absorption ability of the porous samples, one piece of 3D GDY on copper foam was used for removal of the contaminated toluene by a perylene derivative in Figure 3e. The procedure photographs showcase the strong capability of 3D GDY to remove the dyed toluene, which can be completed in a few seconds. Moreover, during the absorption process, the 3D GDY foam was floating on the water like a water strider leg because of its superhydrophobic property.37
Additionally, this porous framework was applied in testing its capability in absorbing the harmful organic solvent. As shown in Figure 3f, it can be found that, after removal of the metal framework, the absorption ability of such a structure was high, up to 175.4 (methanol) and 322 (nitrobenzene) times its initial weight, because of the ultralow-area mass loading of GDY on the 3D foam (0.4 mg cm −2). Besides, the sample without removal of the metal backbones also has excellent absorption capability of up to 147 g g −1 (Figure S8). Impressively, the absorption capability of our 3D GDY is higher than those of many other porous carbonaceous materials, such as graphene foam, sponge, and carbon nanofiber aerogels38−40 because the large voids and interweaved ultrafine GDY nanochains are very reasonably combined together for retention of the solvents. Because the above-mentioned carbonaceous sponges are all prepared from time-consuming approaches, the excellent performance of our materials demonstrates E
DOI: 10.1021/acsami.8b01383 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Forum Article
ACS Applied Materials & Interfaces
Figure 4. Supercapacitor performance based on 3D GDY on the nickel foam using a 7 M KOH aqueous electrolyte: (a) CV curves obtained at different scanning rates; (b) galvanostatic charge/discharge profiles under different current densities; (c) specific capacitance retention via the current density; (d) Nyquist plot. Inset: Magnified portion over the high-frequency range. (e) Long-term CV at a scanning rate of 200 mV s −1 for investigating the cell stability.
extrapolating the straight line to intersect the real axis, indicating that the 3D nanostructure has very strong contact with the framework of the nickel foam. Such a low electron spin resonance is helpful for enhancing electron transfer through the ultratiny all-carbon nanochain and guaranteeing the excellent rate performance of the supercapacitor. The long-term retention of the twoelectrode supercapacitor by CV indicates that GDY has excellent stability even after 1300 cycles because there is only a feeble decrease in the CV profiles. Because the energy storage is proportional to the square of the voltage, for a high-energy supercapacitor, the 3D GDY on the nickel foam was also measured as an electrode in the organic electrolyte system [1 M tetraethylammonium tetrafluoroborate (TEABF4) in propylene carbonate (PC)] in a wide electrochemical window from 0 to 2.7 V (Figure 5). Because of the accessibility of organic solvents, the CV profiles are nearly rectangular shape even at 3000 mV s −1, a significant indication of the efficient electrochemical double-layer capacitance and charge transfer in the hierarchical porous nanostructure. According to the CV curves, the specific capacitance can be obtained, which is gradually decreased from 50.2 mF cm −2 (100 mV s −1) to 30.7 mF cm −2 (3 V s −1). In the Nyquist plot, its intersection with the real axis over the high frequency range is only 2.6 Ω, which is slightly higher than that in the aqueous electrolyte, mainly because of the lower systematic conductivity in the organic electrolyte. Such a value suggests that the electrodes have small resistance as well as good ion response. In the diffusion range, the almost 45° angle between the impedance curves and the real axis shows the typical feature of a porous electrode saturated by an electrolyte.45 Meanwhile, over the lowfrequency area in the Nyquist plot is a near-perpendicular line to the real axis, meaning a good capacitor behavior, as mentioned above. Additionally, the cell in the organic electrolyte was operated in long-term CV testing, as shown in Figure 5d, delivering a very robust capacitance retention even after 800 cycles.
that this is one of the most efficient methods for constructing 3D all-carbon materials for promising applications in sorbent because of the superfast growth characteristic. The supercapacitor is thought to be an important compensation of the lithium-ion batteries for achieving much higher power delivery and uptake in seconds, in which the high-surfacearea all-carbon materials are widely utilized as reliable electrodes.41−43 Because of the seamless 3D coating of GDY on foams and the outstanding reserving capability for electrolytes, the GDY nanostructure on the nickel foam was used as a typical binder-free electrode for supercapacitor testing. First, the supercapacitor with a two-symmetric electrode configuration was assembled with a 7 M KOH aqueous electrolyte (Figure 4). The cyclic voltammetry (CV) profiles under different scan rates are all rectangular in shape, even at a high sweeping rate of up to 1000 mV s −1, meaning a near-ideal capacitance characteristic. The symmetric profiles and linear slopes in the galvanostatic charge/discharge curves further demonstrate that the electrical double layer is efficiently formed in the 3D framework. The insignificant voltage drop at the top of the symmetric triangle is indicative of low equivalent series resistance. Via calculation from the discharge curves in Figure 4b, the specific area capacitance of the samples is 53.66 mF cm −2 at a discharge current density of 0.2 mA cm −2, higher than that of many state-of-the-art methods (Figure S9).44 Moreover, the supercapacitor cell shows an impressive rate performance even at 4 mA cm −2, maintaining 49.42 mF cm −2. Upon conversion of the area capacitance into the mass capacitance, the samples have a high capacitance of up to 134.2 F g −1 in a two-electrode configuration. The Nyquist plot is shown in Figure 4d, which obviously exhibits a near-ideal capacitive behavior according to the approximately vertical plot to the real axis in the low-frequency range. In the magnified high-frequency area, the plot intersects with the real axis at 1.5 Ω; furthermore, the equivalent series resistance is 2.3 Ω by F
DOI: 10.1021/acsami.8b01383 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Forum Article
ACS Applied Materials & Interfaces
Figure 5. Electrochemical performance of the 3D GDY on the nickel foam in a TEABF4/PC electrolyte: (a) CV curves obtained at different scanning rates; (b) specific capacitance retention via the current density; (c) Nyquist plot. Inset: Magnified portion over the high-frequency range. (d) Long-term stability under a scanning rate of 800 mV s −1.
■
the sample was immersed in an aqueous solution of HCl (2%) and FeCl 3 (2%) for about 24 h. Then the sample was washed five times with a deionized water/ethanol solution (1:1, v/v) and dried in a vacuum oven. Characterization of GDY. The as-prepared samples were characterized by field-emission scanning electron microscopy (SEM; Hitachi S-4800) and transmission electron microscopy (TEM; JEM2100F) for their morphology information without further treatment. Raman spectra was obtained using an NT-MDT NTEGRA spectral system with excitation from an argon laser at 473 nm. X-ray photoelectron spectroscopy (XPS) was recorded on a ESCALab250Xi spectrometer for analysis of the elementary information. The contact angles were measured using a SL200 KB apparatus at room temperature. Electrochemical Tests. The supercapacitors based on the 3D GDY on the nickel foam were assembled in a symmetry two-electrode configuration in the coin cell. Two identical GDYs on the nickel foam (0.5 cm × 0.5 cm) were used as the electrodes. For the 7 M KOH aqueous electrolyte, filter paper was used as the separator, and for a 1 M TEABF4/PC electrolyte, a glass fiber was used as the separator. The supercapacitors were assembled in the atmosphere for the aqueous electrolyte and in the argon-protected glovebox for the organic electrolyte. Electrochemical impedance spectroscopy (EIS) spectra, cyclic voltammograms, and galvanostatic charge/discharge curves were all taken using a CHI 660D electrochemical station, and EIS was tested in the frequency range of 0.1 Hz to 100 kHz with a 5 mV alternating-current amplitude. The gravimetric specific capacitances for the two-electrode systems were calculated from the galvanostatic discharge curves using the following equation:
CONCLUSION In conclusion, our results demonstrate that GDY could be ultrafastly grown on several arbitrary substrates under low temperature in air; without using any metal catalyst and toxic solvent, with no substrate dependence, this successfully avoids the extraneous contamination. Such a simple and convenient pathway to grow an all-carbon material is very attractive and beyond example. After all-carbon modification, the substrates show outstanding superhydrophobicity (148°) and 3D continuousness, which is preferred in many imperative applications. Because of the seamless 3D coating of GDY on foams and the outstanding reserving capability for electrolytes, the high-surface-area samples show great potential as binder-free electrochemical supercapacitor electrodes for accommodating active ions and transferring electrons. Besides, this moderate stratagy for the preparation of GDY paves the way for much wider applications in the evergrowing electrochemical fields.
■
EXPERIMENTAL METHODS
Material Preparation. The preparation of hexaethynylbenzene (HEB) monomer was following the state-of-the-art method reported in 2010 from our group.16 After the preparation of HEB, it was dissolved in tetrahydrofuran for a 1 mg mL −1 solution and stored in the refrigerator for succeeding applications. Various substrates for the in situ growth of the GDY nanochain were alternately washed three times in an ultrasonic cleaner by deionized water and ethanol. Then the predesigned HEB solution was drop-coated onto the pretreated substrates; for example, the HEB solution was drop-coated onto the nickel foam with an area loading of 0.4 mg cm −2 under the protection of argon flow. The coating process only costs about 5−10 min. Then, the as-coated substrates were transferred to the preheated platform (120 °C) in the air. It can be viewed that an ultrafast reaction took place and caused a slight explosion in seconds. After the color immediately changed from yellow to deep dark, the reaction was finished and the 3D GDY was obtained for the following characterizations. For removal of the nickel framework,
Csp =
4I Δt mΔE
where Δt (s) is the discharge time, I (A) is the discharge current, m (g) is the total mass of the two electrodes, ΔE (V) is the voltage difference of the discharge portion, and ΔE/Δt (V s −1) is the slope of the discharge curve after the ohmic drop. G
DOI: 10.1021/acsami.8b01383 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Forum Article
ACS Applied Materials & Interfaces
■
(9) Son, I. H.; Hwan Park, J.; Kwon, S.; Park, S.; Rummeli, M. H.; Bachmatiuk, A.; Song, H. J.; Ku, J.; Choi, J. W.; Choi, J. M.; Doo, S. G.; Chang, H. Silicon Carbide-Free Graphene Growth on Silicon for Lithium-Ion Battery with High Volumetric Energy Density. Nat. Commun. 2015, 6, 7393. (10) Lin, F.; Markus, I. M.; Nordlund, D.; Weng, T. C.; Asta, M. D.; Xin, H. L.; Doeff, M. M. Surface Reconstruction and Chemical Evolution of Stoichiometric Layered Cathode Materials for Lithium-Ion Batteries. Nat. Commun. 2014, 5, 3529. (11) Fan, F.; Zhou, C.; Wang, X.; Szpunar, J. Layer-by-Layer Assembly of a Self-Healing Anticorrosion Coating on Magnesium Alloys. ACS Appl. Mater. Interfaces 2015, 7, 27271−27278. (12) Zhu, M.; Du, Z.; Yin, Z.; Zhou, W.; Liu, Z.; Tsang, S. H.; Teo, E. H. T. Low-Temperature in Situ Growth of Graphene on Metallic Substrates and Its Application in Anticorrosion. ACS Appl. Mater. Interfaces 2016, 8, 502−510. (13) Khan, M. H.; Jamali, S. S.; Lyalin, A.; Molino, P. J.; Jiang, L.; Liu, H. K.; Taketsugu, T.; Huang, Z. Atomically Thin Hexagonal Boron Nitride Nanofilm for Cu Protection: The Importance of Film Perfection. Adv. Mater. 2017, 29, 1603937. (14) Wu, Z.-S.; Chen, L.; Liu, J.; Parvez, K.; Liang, H.; Shu, J.; Sachdev, H.; Graf, R.; Feng, X.; Müllen, K. High-Performance Electrocatalysts for Oxygen Reduction Derived from Cobalt Porphyrin-Based Conjugated Mesoporous Polymers. Adv. Mater. 2014, 26, 1450−1455. (15) Wang, J.; Cui, W.; Liu, Q.; Xing, Z.; Asiri, A. M.; Sun, X. Recent Progress in Cobalt-Based Heterogeneous Catalysts for Electrochemical Water Splitting. Adv. Mater. 2016, 28, 215−230. (16) Li, G.; Li, Y.; Liu, H.; Guo, Y.; Li, Y.; Zhu, D. Architecture of Graphdiyne Nanoscale Films. Chem. Commun. 2010, 46, 3256−3258. (17) Chen, Y.; Liu, H.; Li, Y. Progress and Prospect of Two Dimensional Carbon Graphdiyne. Chin. Sci. Bull. 2016, 61, 2901−2912. (18) Li, Y.; Li, Y. Two Dimensional Polymers-Progress of Full Carbon Graphyne. Acta Polym. Sin. 2015, 2, 147−165. (19) Huang, C.; Li, Y. Structure of 2D Graphdiyne and Its Application in Energy Fields. Acta Phys. Chim. Sin. 2016, 32, 1314−1329. (20) Kuang, C.; Tang, G.; Jiu, T.; Yang, H.; Liu, H.; Li, B.; Luo, W.; Li, X.; Zhang, W.; Lu, F.; Fang, J.; Li, Y. Highly Efficient Electron Transport Obtained by Doping PCBM with Graphdiyne in Planar-Heterojunction Perovskite Solar Cells. Nano Lett. 2015, 15, 2756−2762. (21) Qi, H.; Yu, P.; Wang, Y.; Han, G.; Liu, H.; Yi, Y.; Li, Y.; Mao, L. Graphdiyne Oxides as Excellent Substrate for Electroless Deposition of Pd Clusters with High Catalytic Activity. J. Am. Chem. Soc. 2015, 137, 5260−5263. (22) Li, Y.; Xu, L.; Liu, H.; Li, Y. Graphdiyne and Graphyne: from Theoretical Predictions to Practical Construction. Chem. Soc. Rev. 2014, 43, 2572−2586. (23) Jia, Z.; Li, Y.; Zuo, Z.; Liu, H.; Huang, C.; Li, Y. Synthesis and Properties of 2D Carbon-Graphdiyne. Acc. Chem. Res. 2017, 50, 2470− 2478. (24) Li, Y. Design and Self-assembly of Advanced Functional Molecular Materials-from Low Dmension to Multi-dimension. Zhongguo Kexue: Huaxue 2017, 47, 1045−1056. (25) Lv, Q.; Si, W. Y.; Yang, Z.; Wang, N.; Tu, Z. Y.; Yi, Y. P.; Huang, C. S.; Jiang, L.; Zhang, M. J.; He, J. J.; Long, Y. Z. Nitrogen-Doped Porous Graphdiyne: A Highly Efficient Metal-Free Electrocatalyst for Oxygen Reduction Reaction. ACS Appl. Mater. Interfaces 2017, 9, 29744−29752. (26) Xue, Y. R.; Li, J. F.; Xue, Z.; Li, Y. J.; Liu, H. B.; Li, D.; Yang, W. S.; Li, Y. L. Extraordinarily Durable Graphdiyne-Supported Electrocatalyst with High Activity for Hydrogen Production at All Values of pH. ACS Appl. Mater. Interfaces 2016, 8, 31083−31091. (27) Meng, Z.; Zhang, X.; Zhang, Y.; Gao, H.; Wang, Y.; Shi, Q.; Rao, D.; Liu, Y.; Deng, K.; Lu, R. Graphdiyne as a High-Efficiency Membrane for Separating Oxygen from Harmful Gases: A First-Principles Study. ACS Appl. Mater. Interfaces 2016, 8, 28166−28170. (28) Zuo, Z.; Shang, H.; Chen, Y.; Li, J.; Liu, H.; Li, Y.; Li, Y. A Facile Approach for Graphdiyne Preparation under Atmosphere for an Advanced Battery Anode. Chem. Commun. 2017, 53, 8074−8077.
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b01383. SEM images of the copper and nickel foams, typical morphology of a GDY-nanochain-modified copper foam, magnified SEM image of the nickel foam and the GDY nanochain on the framework, large-scale GDY nanochain in the voids of the nickel foam, oil/water separation test, and absorbent ability of the GDY foam on the copper foam (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected] (Z.Z.). *E-mail:
[email protected] (Y.L.). ORCID
Zicheng Zuo: 0000-0001-7002-9886 Yingjie Zhao: 0000-0002-2668-3722 Yuliang Li: 0000-0001-5279-0399 Author Contributions
The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS This work was supported by the National Nature Science Foundation of China (Grants 21790050 and 21790051), National Key Research and Development Project of China (Grant 2016YFA0200104), and Key Research Program of Frontier Sciences of Chinese Academy of Sciences (Grant QYZDY-SSW-SLH015).
■
REFERENCES
(1) Dai, L. Functionalization of Graphene for Efficient Energy Conversion and Storage. Acc. Chem. Res. 2013, 46, 31−42. (2) Wassei, J. K.; Kaner, R. B. Oh, the Places You’ll Go with Graphene. Acc. Chem. Res. 2013, 46, 2244−2253. (3) Yu, L.; Shearer, C.; Shapter, J. Recent Development of Carbon Nanotube Transparent Conductive Films. Chem. Rev. 2016, 116, 13413−13453. (4) Lebedeva, M. A.; Chamberlain, T. W.; Khlobystov, A. N. Harnessing the Synergistic and Complementary Properties of Fullerene and Transition-Metal Compounds for Nanomaterial Applications. Chem. Rev. 2015, 115, 11301−11351. (5) Chen, Z.; Ren, W.; Gao, L.; Liu, B.; Pei, S.; Cheng, H.-M. ThreeDimensional Flexible and Conductive Interconnected Graphene Networks Grown by Chemical Vapour Deposition. Nat. Mater. 2011, 10, 424−428. (6) Kang, L.; Zhang, S.; Li, Q.; Zhang, J. Growth of Horizontal Semiconducting SWNT Arrays with Density Higher than 100 tubes/μm using Ethanol/Methane Chemical Vapor Deposition. J. Am. Chem. Soc. 2016, 138, 6727−6730. (7) Georgakilas, V.; Perman, J. A.; Tucek, J.; Zboril, R. Broad Family of Carbon Nanoallotropes: Classification, Chemistry, and Applications of Fullerenes, Carbon Dots, Nanotubes, Graphene, Nanodiamonds, and Combined Superstructures. Chem. Rev. 2015, 115, 4744−4822. (8) Zhan, C.; Lu, J.; Jeremy Kropf, A.; Wu, T.; Jansen, A. N.; Sun, Y. K.; Qiu, X.; Amine, K. Mn(II) Deposition on Anodes and its Effects on Capacity Fade in Spinel Lithium Manganate-Carbon Systems. Nat. Commun. 2013, 4, 2437. H
DOI: 10.1021/acsami.8b01383 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Forum Article
ACS Applied Materials & Interfaces (29) Shang, H.; Zuo, Z.; Zheng, H.; Li, K.; Tu, Z.; Yi, Y.; Liu, H.; Li, Y.; Li, Y. N-Doped Graphdiyne for High-Performance Electrochemical Electrodes. Nano Energy 2018, 44, 144−154. (30) He, Z.; Liu, J.; Qiao, Y.; Li, C. M.; Tan, T. T. Y. Architecture Engineering of Hierarchically Porous Chitosan/Vacuum-Stripped Graphene Scaffold as Bioanode for High Performance Microbial Fuel Cell. Nano Lett. 2012, 12, 4738−4741. (31) Cabioc’h, T.; Jaouen, M.; Denanot, M. F.; Bechet, P. Influence of the Implantation Parameters on the Microstructure of Carbon Onions Produced by Carbon Ion Implantation. Appl. Phys. Lett. 1998, 73, 3096− 3098. (32) Butenko, Y. V.; Krishnamurthy, S.; Chakraborty, A. K.; Kuznetsov, V. L.; Dhanak, V. R.; Hunt, M. R. C.; Šiller, L. Photoemission Study of Onionlike Carbons Produced by Annealing Nanodiamonds. Phys. Rev. B: Condens. Matter Mater. Phys. 2005, 71, 075420. (33) Huang, C.; Zhang, S.; Liu, H.; Li, Y.; Cui, G.; Li, Y. Graphdiyne for High Capacity and Long-life Lithium Storage. Nano Energy 2015, 11, 481−489. (34) Wang, F.; Luo, H.; Wang, Q.; Wang, J.; Xu, J. Preparation of Superhydrophobic Polymeric Film on Aluminum Plates by Electrochemical Polymerization. Molecules 2009, 14, 4737−4746. (35) Tang, W.; Huang, Y.; Meng, W.; Qing, F.-L. Synthesis of Fluorinated Hyperbranched Polymers Capable as Highly Hydrophobic and Oleophobic Coating Materials. Eur. Polym. J. 2010, 46, 506−518. (36) Gao, X.; Zhou, J.; Du, R.; Xie, Z.; Deng, S.; Liu, R.; Liu, Z.; Zhang, J. Robust Superhydrophobic Foam: A Graphdiyne-Based Hierarchical Architecture for Oil/Water Separation. Adv. Mater. 2016, 28, 168−173. (37) Wang, S.; Liu, K.; Yao, X.; Jiang, L. Bioinspired Surfaces with Superwettability: New Insight on Theory, Design, and Applications. Chem. Rev. 2015, 115, 8230−8293. (38) Liang, H.-W.; Guan, Q.-F.; Chen, L.-F.; Zhu, Z.; Zhang, W.-J.; Yu, S.-H. Macroscopic-Scale Template Synthesis of Robust Carbonaceous Nanofiber Hydrogels and Aerogels and Their Applications. Angew. Chem., Int. Ed. 2012, 51, 5101−5105. (39) Niu, Z.; Chen, J.; Hng, H. H.; Ma, J.; Chen, X. A Leavening Strategy to Prepare Reduced Graphene Oxide Foams. Adv. Mater. 2012, 24, 4144−4150. (40) Gui, X.; Wei, J.; Wang, K.; Cao, A.; Zhu, H.; Jia, Y.; Shu, Q.; Wu, D. Carbon Nanotube Sponges. Adv. Mater. 2010, 22, 617−621. (41) Zhu, Y.; Murali, S.; Stoller, M. D.; Ganesh, K. J.; Cai, W.; Ferreira, P. J.; Pirkle, A.; Wallace, R. M.; Cychosz, K. A.; Thommes, M.; Su, D.; Stach, E. A.; Ruoff, R. S. Carbon-Based Supercapacitors Produced by Activation of Graphene. Science 2011, 332, 1537−1541. (42) Xu, Y.; Lin, Z.; Zhong, X.; Huang, X.; Weiss, N. O.; Huang, Y.; Duan, X. Holey Graphene Frameworks for Highly Efficient Capacitive Energy Storage. Nat. Commun. 2014, 5, 4554. (43) Zhao, Y.; Hu, C.; Hu, Y.; Cheng, H.; Shi, G.; Qu, L. A Versatile, Ultralight, Nitrogen-Doped Graphene Framework. Angew. Chem., Int. Ed. 2012, 51, 11174−11174. (44) Chen, J.; Sheng, K.; Luo, P.; Li, C.; Shi, G. Graphene Hydrogels Deposited in Nickel Foams for High-Rate Electrochemical Capacitors. Adv. Mater. 2012, 24, 4569−4573. (45) Niu, C.; Sichel, E. K.; Hoch, R.; Moy, D.; Tennent, H. High Power Electrochemical Capacitors Based on Carbon Nanotube Electrodes. Appl. Phys. Lett. 1997, 70, 1480−1482.
I
DOI: 10.1021/acsami.8b01383 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
