Reduced graphene oxide aerogel decorated with Mo₂C nanoparticles toward multifunctional properties of hydrophobicity, thermal insulation and microwave absorption

Abstract

Reduced graphene oxide (rGO) aerogels are emerging as very attractive scaffolds for high-performance electromagnetic wave absorption materials (EWAMs) due to their intrinsic conductive networks and intricate interior microstructure, as well as good compatibility with other electromagnetic (EM) components. Herein, we realized the decoration of rGO aerogel with Mo₂C nanoparticles by sequential hydrothermal assembly, freeze-drying, and high-temperature pyrolysis. Results show that Mo₂C nanoparticle loading can be easily controlled by the ammonium molybdate to glucose molar ratio. The hydrophobicity and thermal insulation of the rGO aerogel are effectively improved upon the introduction of Mo₂C nanoparticles, and more importantly, these nanoparticles regulate the EM properties of the rGO aerogel to a large extent. Although more Mo₂C nanoparticles may decrease the overall attenuation ability of the rGO aerogel, they bring much better impedance matching. At a molar ratio of 1:1, a desirable balance between attenuation ability and impedance matching is observed. In this context, the Mo₂C/rGO aerogel displays strong reflection loss and broad response bandwidth, even with a small applied thickness (1.7 mm) and low filler loading (9.0wt%). The positive effects of Mo₂C nanoparticles on multifunctional properties may render Mo₂C/rGO aerogels promising candidates for high-performance EWAMs under harsh conditions.

Keywords

Mo₂C/reduced graphene oxide aerogel / microwave absorption / dielectric loss / hydrophobicity / thermal insulation

References

[1] Pierre AC, Pajonk GM. Chemistry of aerogels and their applications. Chem. Rev., 2002, 102(11): 4243.

[2] Hu H, Zhao ZB, Wan WB, Gogotsi Y, Qiu JS. Ultralight and highly compressible graphene aerogels. Adv. Mater., 2013, 25(15): 2219.

[3] Lee I, Kang SM, Jang SC, et al. One-pot gamma ray-induced green synthesis of a Prussian blue-laden polyvinylpyrrolidone/reduced graphene oxide aerogel for the removal of hazardous pollutants. J. Mater. Chem. A, 2019, 7(4): 1737.

[4] Y. Wang, D.Z. Kong, W.H. Shi, et al., Ice templated free-standing hierarchically WS₂/CNT-rGO aerogel for high-performance rechargeable lithium and sodium ion batteries, Adv. Energy Mater., 6(2016), No. 21, art. No. 1601057.

[5] Xi SB, Wang LL, Xie HQ, Yu W. Superhydrophilic modified elastomeric RGO aerogel based hydrated salt phase change materials for effective solar thermal conversion and storage. ACS Nano, 2022, 16(3): 3843.

[6] Zhang QC, Du ZJ, Hou MM, et al. Ultralight, anisotropic, and self-supported graphene/MWCNT aerogel with high-performance microwave absorption. Carbon, 2022, 188, 442.

[7] Rui XH, Tan HT, Yan QY. Nanostructured metal sulfides for energy storage. Nanoscale, 2014, 6(17): 9889.

[8] M.M. Zhang, Z.Y. Jiang, X.Y. Lv, et al., Microwave absorption performance of reduced graphene oxide with negative imaginary permeability, J. Phys. D: Appl. Phys., 53(2020), No. 2, art. No. 02LT01.

[9] A. Plyushch, T.L. Zhai, H.S. Xia, et al., Ultra-light reduced graphene oxide based aerogel/foam absorber of microwave radiation, Materials, 12(2019), No. 2, art. No. 213.

[10] F. Ye, Q. Song, Z.C. Zhang, et al., Direct growth of edge-rich graphene with tunable dielectric properties in porous Si₃N₄ ceramic for broadband high-performance microwave absorption, Adv. Funct. Mater., 28(2018), No. 17, art. No. 1707205.

[11] Zhao HB, Cheng JB, Zhu JY, Wang YZ. Ultralight CoNi/rGO aerogels toward excellent microwave absorption at ultrathin thickness. J. Mater. Chem. C, 2019, 7(2): 441.

[12] Wu PK, Feng YR, Xu J, Fang ZG, Liu QC, Kong XK. Ultralight N-doped platanus acerifolia biomass carbon microtubes/RGO composite aerogel with enhanced mechanical properties and high-performance microwave absorption. Carbon, 2023, 202, 194.

[13] Li JJ, Yang S, Jiao PZ, et al. Three-dimensional macroassembly of hybrid C@CoFe nanoparticles/reduced graphene oxide nanosheets towards multifunctional foam. Carbon, 2020, 157, 427.

[14] S.S. Wang, Y.C. Xu, R.R. Fu, et al., Rational construction of hierarchically porous Fe-Co/N-doped carbon/rGO composites for broadband microwave absorption, Nano-Micro Lett., 11(2019), No. 1, art. No. 76.

[15] Y.X. Li, Y.J. Liao, L.Z. Ji, et al., Quinary high-entropyalloy@graphite nanocapsules with tunable interfacial impedance matching for optimizing microwave absorption, Small, 18(2022), No. 4, art. No. 2107265.

[16] X.H. Liang, Z.M. Man, B. Quan, et al., Environment-stable Co_xNi_y encapsulation in stacked porous carbon nanosheets for enhanced microwave absorption, Nano-Micro Lett., 12(2020), No. 1, art. No. 102.

[17] Sun Y, Zhang JW, Zong Y, et al. Crystalline-amorphous Permalloy@iron oxide core-shell nanoparticles decorated on graphene as high-efficiency, lightweight, and hydrophobic microwave absorbents. ACS Appl. Mater. Interfaces, 2019, 11(6): 6374.

[18] H.H. Zhao, F.Y. Wang, L.R. Cui, X.Z. Xu, X.J. Han, and Y.C. Du, Composition optimization and microstructure design in MOFs-derived magnetic carbon-based microwave absorbers: A review, Nano-Micro Lett., 13(2021), No. 1, art. No. 208.

[19] Y.L. Lian, B.H. Han, D.W. Liu, et al., Solvent-free synthesis of ultrafine tungsten carbide nanoparticles-decorated carbon nanosheets for microwave absorption, Nano-Micro Lett., 12(2020), No. 1, art. No. 153.

[20] C. Wu, Z.F. Chen, M.L. Wang, et al., Confining tiny MoO₂ clusters into reduced graphene oxide for highly efficient low frequency microwave absorption, Small, 16(2020), No. 30, art. No. 2001686.

[21] Y. Li, F.B. Meng, Y. Mei, et al., Electrospun generation of Ti₃C₂T_x MXene@graphene oxide hybrid aerogel microspheres for tunable high-performance microwave absorption, Chem. Eng. J., 391(2020), art. No. 123512.

[22] Tong Y, He M, Zhou YM, et al. Three-dimensional hierarchical architecture of the TiO₂/Ti₃C₂T_x/RGO ternary composite aerogel for enhanced electromagnetic wave absorption. ACS Sustainable Chem. Eng., 2018, 6(7): 8212.

[23] Cheng YH, Tan MY, Hu P, et al. Strong and thermostable SiC nanowires/graphene aerogel with enhanced hydrophobicity and electromagnetic wave absorption property. Appl. Surf. Sci., 2018, 448, 138.

[24] Chen JP, Jia H, Liu Z, et al. Construction of C-Si heterojunction interface in SiC whisker/reduced graphene oxide aerogels for improving microwave absorption. Carbon, 2020, 164, 59.

[25] Dong S, Zhang WZ, Zhang XH, Hu P, Han JC. Designable synthesis of core-shell SiCw@C heterostructures with thickness-dependent electromagnetic wave absorption between the whole X-band and Ku-band. Chem. Eng. J., 2018, 354, 767.

[26] Xiao SS, Mei H, Han DY, Dassios KG, Cheng LF. Ultralight lamellar amorphous carbon foam nanostructured by SiC nanowires for tunable electromagnetic wave absorption. Carbon, 2017, 122, 718.

[27] Y.Q. Wang, H.B. Zhao, J.B. Cheng, B.W. Liu, Q. Fu, and Y.Z. Wang, Hierarchical Ti₃C₂T_x@ZnO hollow spheres with excellent microwave absorption inspired by the visual phenomenon of eyeless urchins, Nano-Micro Lett., 14(2022), No. 1, art. No. 76.

[28] Wang YH, Li CL, Han XJ, et al. Ultrasmall Mo₂C nanoparticle-decorated carbon polyhedrons for enhanced microwave absorption. ACS Appl. Nano Mater., 2018, 1(9): 5366.

[29] Wang YH, Han XJ, Xu P, et al. Synthesis of pomegranatelike Mo₂C@C nanospheres for highly efficient microwave absorption. Chem. Eng. J., 2019, 372, 312.

[30] Y.H. Wang, X.D. Li, X.J. Han, et al., Ternary Mo₂C/Co/C composites with enhanced electromagnetic waves absorption, Chem. Eng. J., 387(2020), art. No. 124159.

[31] Marcano DC, Kosynkin DV, Berlin JM, et al. Improved synthesis of graphene oxide. ACS Nano, 2010, 4(8): 4806.

[32] Sun XM, Li YD. Colloidal carbon spheres and their core/shell structures with noble-metal nanoparticles. Angew. Chem., 2004, 116(5): 607.

[33] Han BH, Chu WL, Han XJ, et al. Dual functions of glucose induced composition-controllable Co/C microspheres as high-performance microwave absorbing materials. Carbon, 2020, 168, 404.

[34] Krishnan D, Raidongia K, Shao JJ, Huang JX. Graphene oxide assisted hydrothermal carbonization of carbon hydrates. ACS Nano, 2014, 8(1): 449.

[35] Li JF, Zhang N, Zhao HT, Li ZG, Tian B, Du YC. Cornstalk-derived macroporous carbon materials with enhanced microwave absorption. J. Mater. Sci. Mater. Electron., 2021, 32(21): 25758.

[36] Zhang L, Zhang ZL, Lv YY, et al. Reduced graphene oxide aerogels with uniformly self-assembled polyaniline nanosheets for electromagnetic absorption. ACS Appl. Nano Mater., 2020, 3(6): 5978.

[37] Y. Li, X.F. Liu, X.Y. Nie, et al., Multifunctional organic-inorganic hybrid aerogel for self-cleaning, heat-insulating, and highly efficient microwave absorbing material, Adv. Funct. Mater., 29(2019), No. 10, art. No. 1807624.

[38] Cui LR, Wang YH, Han XJ, et al. Phenolic resin reinforcement: A new strategy for hollow NiCo@C microboxes against electromagnetic pollution. Carbon, 2021, 174, 673.

[39] X.Y. Wang, Y.K. Lu, T. Zhu, S.C. Chang, and W. Wang, CoFe₂O₄/N-doped reduced graphene oxide aerogels for highperformance microwave absorption, Chem. Eng. J., 388(2020), art. No. 124317.

[40] B. Yu, D.X. Yang, Y. Hu, J.R. He, Y.F. Chen, and W.D. He, Mo₂C nanodots anchored on N-doped porous CNT microspheres as electrode for efficient Li-ion storage, Small Methods, 3(2019), No. 2, art. No. 1800287.

[41] Zhang XJ, Wang GS, Cao WQ, et al. Enhanced microwave absorption property of reduced graphene oxide (RGO)-MnFe₂O₄ nanocomposites and polyvinylidene fluoride. ACS Appl. Mater. Interfaces, 2014, 6(10): 7471.

[42] Wu NN, Liu C, Xu DM, et al. Enhanced electromagnetic wave absorption of three-dimensional porous Fe₃O₄/C composite flowers. ACS Sustainable Chem. Eng., 2018, 6(9): 12471.

[43] Qiu Y, Yang HB, Wen B, Ma L, Lin Y. Facile synthesis of nickel/carbon nanotubes hybrid derived from metal organic framework as a lightweight, strong and efficient microwave absorber. J. Colloid Interface Sci., 2021, 590, 561.

[44] W.J. Zhu F. Ye, M.H. Li, et al., In-situ growth of wafer-like Ti₃C₂/carbon nanoparticle hybrids with excellent tunable electromagnetic absorption performance, Composites Part B, 202(2020), art. No. 108408.

[45] F.Y. Wang, Y.L. Liu, H.H. Zhao, et al., Controllable seeding of nitrogen-doped carbon nanotubes on three-dimensional Co/C foam for enhanced dielectric loss and microwave absorption characteristics, Chem. Eng. J., 450(2022), art. No. 138160.

[46] Ye XL, Chen ZF, Li M, et al. Microstructure and microwave absorption performance variation of SiC/C foam at different elevated-temperature heat treatment. ACS Sustainable Chem. Eng., 2019, 7(22): 18395.

[47] Xu HL, Yin XW, Fan XM, et al. Constructing a tunable heterogeneous interface in bimetallic metal-organic frameworks derived porous carbon for excellent microwave absorption performance. Carbon, 2019, 148, 421.

[48] Chen YY, Zhang Y, Jiang WJ, et al. Pomegranate-like N,P-doped Mo₂C@C nanospheres as highly active electrocatalysts for alkaline hydrogen evolution. ACS Nano, 2016, 10(9): 8851.

[49] Chen YA, Pötschke P, Pionteck J, Voit B, Qi HS. Multifunctional cellulose/rGO/Fe₃O₄ composite aerogels for electromagnetic interference shielding. ACS Appl. Mater. Interfaces, 2020, 12(19): 22088.

[50] Gu WH, Tan JW, Chen JB, et al. Multifunctional bulk hybrid foam for infrared stealth, thermal insulation, and microwave absorption. ACS Appl. Mater. Interfaces, 2020, 12(25): 28727.

[51] Chu K, Wang F, Li YB, Wang XH, Huang DJ, Geng ZR. Interface and mechanical/thermal properties of graphene/copper composite with Mo₂C nanoparticles grown on graphene. Composites Part A, 2018, 109, 267.

[52] Ma SD, Zhao NQ, Shi CS, et al. Mo₂C coating on diamond: Different effects on thermal conductivity of diamond/Al and diamond/Cu composites. Appl. Surf. Sci., 2017, 402, 372.

[53] Sheng A, Yang YQ, Yan DX, et al. Self-assembled reduced graphene oxide/nickel nanofibers with hierarchical core-shell structure for enhanced electromagnetic wave absorption. Carbon, 2020, 167, 530.

[54] X.S. Deng, Y.H. Wang, L.F. Ma, et al., Construction of dualshell Mo₂C/C microsphere towards efficient electromagnetic wave absorption, Int. J. Mol. Sci., 23(2022), No. 23, art. No. 14502.

[55] Wang FY, Xu P, Shi N, et al. Polymer-bubbling for one-step synthesis of three-dimensional cobalt/carbon foams against electromagnetic pollution. J. Mater. Sci. Technol., 2021, 93, 7.

[56] Cheng Y, Meng W, Li ZY, et al. Towards outstanding dielectric consumption derived from designing one-dimensional mesoporous MoO₂/C hybrid heteronanowires. J. Mater. Chem. C, 2017, 5(35): 8981.

[57] Tian CH, Du YC, Xu P, et al. Constructing uniform core-shell PPy@PANI composites with tunable shell thickness toward enhancement in microwave absorption. ACS Appl. Mater. Interfaces, 2015, 7(36): 20090.

[58] He N, Yang XF, Shi LX, et al. Chemical conversion of Cu₂O/PPy core-shell nanowires (CSNWs): A surface/interface adjustment method for high-quality Cu/Fe/C and Cu/Fe₃O₄/C CSNWs with superior microwave absorption capabilities. Carbon, 2020, 166, 205.

[59] J.K. Liu, Z.R. Jia, W.H. Zhou, et al., Self-assembled MoS₂/magnetic ferrite CuFe₂O₄ nanocomposite for high-efficiency microwave absorption, Chem. Eng. J., 429(2022), art. No. 132253.

[60] Meng FB, Wang HG, Huang F, et al. Graphene-based microwave absorbing composites: A review and prospective. Composites Part B, 2018, 137, 260.

[61] Gai LX, Zhao HH, Wang FY, et al. Advances in core-shell engineering of carbon-based composites for electromagnetic wave absorption. Nano Res., 2022, 15(10): 9410.

[62] Lu Z, Wang Y, Di XC, Wang N, Cheng RR, Yang LQ. Heterostructure design of carbon fiber@graphene@layered double hydroxides synergistic microstructure for lightweight and flexible microwave absorption. Carbon, 2022, 197, 466.

[63] Cheng JB, Liu BW, Wang YQ, Zhao HB, Wang YZ. Growing CoNi nanoalloy@N-doped carbon nanotubes on MXene sheets for excellent microwave absorption. J. Mater. Sci. Technol., 2022, 130, 157.

[64] Zhang X, Cheng J, Xiang Z, Cai L, Lu W. A hierarchical Co@mesoporous C/macroporous C sheet composite derived from bimetallic MOF and oroxylum indicum for enhanced microwave absorption. Carbon, 2022, 187, 477.

[65] Feng J, Zong Y, Sun Y, et al. Optimization of porous FeNi₃/N-GN composites with superior microwave absorption performance. Chem. Eng. J., 2018, 345, 441.

[66] Zhang GY, Shu RW, Xie Y, et al. Cubic MnFe₂O₄ particles decorated reduced graphene oxide with excellent microwave absorption properties. Mater. Lett., 2018, 231, 209.

[67] Yang YN, Xia L, Zhang T, et al. Fe₃O₄@LAS/RGO composites with a multiple transmission-absorption mechanism and enhanced electromagnetic wave absorption performance. Chem. Eng. J., 2018, 352, 510.

[68] Wu Y, Shu RW, Li ZY, et al. Design and electromagnetic wave absorption properties of reduced graphene oxide/multi-walled carbon nanotubes/nickel ferrite ternary nanocomposites. J. Alloys Compd., 2019, 784, 887.

[69] M.L. Ma, W.T. Li, Z.Y. Tong, et al., 1D flower-like Fe₃O₄@SiO₂@MnO₂ nanochains inducing RGO self-assembly into aerogels for high-efficient microwave absorption, Mater. Des., 188(2020), art. No. 108462.

[70] Huang Y, Zhang N, Wang MY, Liu XD, Zong M, Liu PB. Facile synthesis of hollow Zn_xFe_3−xO₄@porous MnO₂/rGO conductive network composites for tunable electromagnetic wave absorption. Ind. Eng. Chem. Res., 2018, 57(44): 14878.

[71] Cheng JB, Wang YQ, Zhang AN, Zhao HB, Wang YZ. Growing MoO₃-doped WO₃ nanoflakes on rGO aerogel sheets towards superior microwave absorption. Carbon, 2021, 183, 205.

[72] Liu Y, Wu WW, Liu LN, Xing ZJ, Chen XM, Liu P. Heterointerface engineering of lightweight, worm-like SiC/B₄C hybrid nanowires as excellent microwave absorbers. J. Mater. Chem. C, 2019, 7(32): 9892.

[73] Liu PB, Gao S, Wang Y, Huang Y, Wang Y, Luo JH. Core-shell CoNi@graphitic carbon decorated on B,N-codoped hollow carbon polyhedrons toward lightweight and high-efficiency microwave attenuation. ACS Appl. Mater. Interfaces, 2019, 11(28): 25624.

[74] Liu DW, Du YC, Xu P, et al. Waxberry-like hierarchical Ni@C microspheres with high-performance microwave absorption. J. Mater. Chem. C, 2019, 7(17): 5037.

[75] Xu XQ, Ran FT, Fan ZM, et al. Bimetallic metal-organic framework-derived pomegranate-like nanoclusters coupled with CoNi-doped graphene for strong wideband microwave absorption. ACS Appl. Mater. Interfaces, 2020, 12(15): 17870.

[76] H.H. Zhao, X.Z. Xu, Y.H. Wang, et al., Heterogeneous interface induced the formation of hierarchically hollow carbon microcubes against electromagnetic pollution, Small, 16(2020), No. 43, art. No. 2003407.