Graphical Abstract

Exploring advanced electromagnetic wave (EMW) absorbers is one of the most feasible ways to solve the increasing electromagnetic pollution in both military and civil fields. In this work, γ-graphyne (γ-GY) is synthesized by a mechanochemical route using CaC2 and hexabromobenzene (PhBr6). Then three-dimensional (3D) reduced graphene oxide/γ-GY (RGO/GY) heterostructures are prepared through facile solvothermal self-assembly and subsequent thermal reduction. The influences of calcination temperature and the content of γ-GY of the composite on EMW absorption performance are fully investigated. The minimum reflection loss (RL) value of the RGO/GY composite foam is −71.73 dB at 10.48 GHz with the matching thickness of 3.54 mm, and the effective absorption bandwidth (EAB) less than −10 dB is 7.36 GHz. Moreover, excellent terahertz (THz) absorption property is also obtained at 0.2–1.6 THz. The RL of 84.08 dB is acquired, and the EAB covers 100% of the entire measured bandwidth. In addition, the composite is also a promising anticorrosive EMW absorber. This work provides encouraging findings, which are also instructive for the potential advantages of graphyne-based materials as highly efficient EMW absorbers in both gigahertz and terahertz band ranges.
Gu, W. H.; Lv, J.; Quan, B.; Liang, X. H.; Zhang, B. S.; Ji, G. B. Achieving MOF-derived one-dimensional porous ZnO/C nanofiber with lightweight and enhanced microwave response by an electrospinning method. J. Alloys Compd. 2019, 806, 983–991.
Liang, L. Y.; Yang, R. S.; Han, G. J.; Feng, Y. Z.; Zhao, B.; Zhang, R.; Wang, Y. M.; Liu, C. T. Enhanced electromagnetic wave-absorbing performance of magnetic nanoparticles-anchored 2D Ti3C2Tx MXene. ACS Appl. Mater. Interfaces 2020, 12, 2644–2654.
Yang, N.; Luo, Z. X.; Zhu, G. R.; Chen, S. C.; Wang, X. L.; Wu, G.; Wang, Y. Z. Ultralight three-dimensional hierarchical cobalt nanocrystals/N-doped CNTs/carbon sponge composites with a hollow skeleton toward superior microwave absorption. ACS Appl. Mater. Interfaces 2019, 11, 35987–35998.
Qiu, Y.; Lin, Y.; Yang, H. B.; Wang, L.; Wang, M. Q.; Wen, B. Hollow Ni/C microspheres derived from Ni-metal organic framework for electromagnetic wave absorption. Chem. Eng. J. 2020, 383, 123207.
Li, J.; Miao, P.; Chen, K. J.; Cao, J. W.; Liang, J.; Tang, Y. S.; Kong, J. Highly effective electromagnetic wave absorbing prismatic Co/C nanocomposites derived from cubic metal–organic framework. Compos. Part B Eng. 2020, 182, 107613.
Wang, S. J.; Li, D. S.; Zhou, Y.; Jiang, L. Hierarchical Ti3C2Tx MXene/Ni chain/ZnO array hybrid nanostructures on cotton fabric for durable self-cleaning and enhanced microwave absorption. ACS Nano 2020, 14, 8634–8645.
Deng, B. W.; Xiang, Z.; Xiong, J.; Liu, Z. C.; Yu, L. Z.; Lu, W. Sandwich-like Fe&TiO2@C nanocomposites derived from MXene/Fe-MOFs hybrids for electromagnetic absorption. Nano-Micro Lett. 2020, 12, 55.
Chen, Q. L.; Li, L. Y.; Wang, Z. L.; Ge, Y. C.; Zhou, C. S.; Yi, J. H. Synthesis and enhanced microwave absorption performance of CIP@SiO2@Mn0.6Zn0.4Fe2O4 ferrite composites. J. Alloys Compd. 2019, 779, 720–727.
Liu, P. J.; Yao, Z. J.; Zhou, J. T.; Yang, Z. H.; Kong, L. B. Small magnetic Co-doped NiZn ferrite/graphene nanocomposites and their dual-region microwave absorption performance. J. Mater. Chem. C 2016, 4, 9738–9749.
Li, Z. J.; Hou, Z. L.; Song, W. L.; Liu, X. D.; Cao, W. Q.; Shao, X. H.; Cao, M. S. Unusual continuous dual absorption peaks in Ca-doped BiFeO3 nanostructures for broadened microwave absorption. Nanoscale 2016, 8, 10415–10424.
Jeon, S.; Kim, J.; Kim, K. H. Microwave absorption properties of graphene oxide capsulated carbonyl iron particles. Appl. Surf. Sci. 2019, 475, 1065–1069.
Zuo, Y. X.; Su, X. R.; Li, X. W.; Yao, Z. J.; Yu, T. T.; Zhou, J. T.; Li, J.; Lu, J.; Ding, J. Multimaterial 3D-printing of graphene/Li0.35Zn0.3Fe2.35O4 and graphene/carbonyl iron composites with superior microwave absorption properties and adjustable bandwidth. Carbon 2020, 167, 62–74.
Jiang, Y.; Chen, Y.; Liu, Y. J.; Sui, G. X. Lightweight spongy bone-like graphene@SiC aerogel composites for high-performance microwave absorption. Chem. Eng. J. 2018, 337, 522–531.
Shao, G.; Liang, J. F.; Zhao, W. Y.; Zhao, B.; Liu, W.; Wang, H. L.; Fan, B. B.; Xu, H. L.; Lu, H. X.; Wang, Y. G. et al. Co decorated polymer-derived SiCN ceramic aerogel composites with ultrabroad microwave absorption performance. J. Alloys Compd. 2020, 813, 152007.
Liu, Q. H.; Cao, Q.; Bi, H.; Liang, C. Y.; Yuan, K. P.; She, W.; Yang, Y. J.; Che, R. C. CoNi@SiO2@TiO2 and CoNi@Air@TiO2 microspheres with strong wideband microwave absorption. Adv. Mater. 2016, 28, 486–490.
Wang, Z. C.; Wei, R. B.; Gu, J. W.; Liu, H.; Liu, C. T.; Luo, C. J.; Kong, J.; Shao, Q.; Wang, N.; Guo, Z. et al. Ultralight, highly compressible and fire-retardant graphene aerogel with self-adjustable electromagnetic wave absorption. Carbon 2018, 139, 1126–1135.
Zhang, K. L.; Zhang, J. Y.; Hou, Z. L.; Bi, S.; Zhao, Q. L. Multifunctional broadband microwave absorption of flexible graphene composites. Carbon 2019, 141, 608–617.
Wang, H. G.; Meng, F. B.; Huang, F.; Jing, C. F.; Li, Y.; Wei, W.; Zhou, Z. W. Interface modulating CNTs@PANi hybrids by controlled unzipping of the walls of CNTs to achieve tunable high-performance microwave absorption. ACS Appl. Mater. Interfaces 2019, 11, 12142–12153.
Sun, H.; Che, R. C.; You, X.; Jiang, Y. S.; Yang, Z. B.; Deng, J.; Qiu, L. B.; Peng, H. S. Cross-stacking aligned carbon-nanotube films to tune microwave absorption frequencies and increase absorption intensities. Adv. Mater. 2014, 26, 8120–8125.
Li, W. X.; Qi, H. X.; Guo, F.; Du, Y. E.; Song, N. J.; Liu, Y. Y.; Chen, Y. Q. Co nanoparticles supported on cotton-based carbon fibers: A novel broadband microwave absorbent. J. Alloys Compd. 2019, 772, 760–769.
Liu, L. Y.; Yang, S.; Hu, H. Y.; Zhang, T. L.; Yuan, Y.; Li, Y. B.; He, X. D. Lightweight and efficient microwave-absorbing materials based on loofah-sponge-derived hierarchically porous carbons. ACS Sustainable Chem. Eng. 2019, 7, 1228–1238.
Baughman, R. H.; Eckhardt, H.; Kertesz, M. Structure property predictions for new planar forms of carbon: Layered phases containing sp2 and sp atoms. J. Chem. Phys. 1987, 87, 6687–6699.
Li, G. X.; Li, Y. L.; Liu, H. B.; Guo, Y. B.; Li, Y. J.; Zhu, D. B. Architecture of graphdiyne nanoscale films. Chem. Commun. 2010, 46, 3256–3258.
Gao, X.; Liu, H. B.; Wang, D.; Zhang, J. Graphdiyne: Synthesis, properties, and applications. Chem. Soc. Rev. 2019, 48, 908–936.
Li, Y. J.; Liu, Q. N.; Li, W. F.; Meng, H.; Lu, Y. Z.; Li, C. X. Synthesis and supercapacitor application of alkynyl carbon materials derived from CaC2 and polyhalogenated hydrocarbons by interfacial mechanochemical reactions. ACS Appl. Mater. Interfaces 2017, 9, 3895–3901.
Li, Q. D.; Yang, C. F.; Wu, L. L.; Wang, H.; Cui, X. L. Converting benzene into γ-graphyne and its enhanced electrochemical oxygen evolution performance. J. Mater. Chem. A 2019, 7, 5981–5990.
Yang, C. F.; Li, Y.; Chen, Y.; Li, Q. D.; Wu, L. L.; Cui, X. L. Mechanochemical synthesis of γ-graphyne with enhanced lithium storage performance. Small 2019, 15, 1804710.
Ding, W.; Sun, M. X.; Gao, B. W.; Liu, W. Z.; Ding, Z. P.; Anandan, S. A ball-milling synthesis of N-graphyne with controllable nitrogen doping sites for efficient electrocatalytic oxygen evolution and supercapacitors. Dalton Trans. 2020, 49, 10958–10969.
Zhang, S. C.; Yin, C.; Kang, Z.; Wu, P. W.; Wu, J.; Zhang, Z.; Liao, Q. L.; Zhang, J.; Zhang, Y. Graphdiyne nanowall for enhanced photoelectrochemical performance of Si heterojunction photoanode. ACS Appl. Mater. Interfaces 2019, 11, 2745–2749.
Wang, Y. Q.; Wang, H. G.; Ye, J. H.; Shi, L. Y.; Feng, X. Magnetic CoFe alloy@C nanocomposites derived from ZnCo-MOF for electromagnetic wave absorption. Chem. Eng. J. 2020, 383, 123096.
Liao, Q.; He, M.; Zhou, Y. M.; Nie, S. X.; Wang, Y. J.; Hu, S. C.; Yang, H. Y.; Li, H. F.; Tong, Y. Highly cuboid-shaped heterobimetallic metal–organic frameworks derived from porous Co/ZnO/C microrods with improved electromagnetic wave absorption capabilities. ACS Appl. Mater. Interfaces 2018, 10, 29136–29144.
Zuo, Z. C.; Shang, H.; Chen, Y. H.; Li, J. F.; Liu, H. B.; Li, Y. J.; Li, Y. L. A facile approach for graphdiyne preparation under atmosphere for an advanced battery anode. Chem. Commun. 2017, 53, 8074–8077.
Wu, N. N.; Liu, C.; Xu, D. M.; Liu, J. R.; Liu, W.; Shao, Q.; Guo, Z. H. Enhanced electromagnetic wave absorption of three-dimensional porous Fe3O4/C composite flowers. ACS Sustainable Chem. Eng. 2018, 6, 12471–12480.
Li, Y.; Liu, X. F.; Nie, X. Y.; Yang, W. W.; Wang, Y. D.; Yu, R. H.; Shui, J. L. Multifunctional organic–inorganic hybrid aerogel for self-cleaning, heat-insulating, and highly efficient microwave absorbing material. Adv. Funct. Mater. 2019, 29, 1807624.
Zeng, M.; Cao, Q.; Liu, J.; Guo, B. Y.; Hao, X. Z.; Liu, Q. W.; Liu, X. F.; Sun, X.; Zhang, X. X.; Yu, R. H. Hierarchical cobalt selenides as highly efficient microwave absorbers with tunable frequency response. ACS Appl. Mater. Interfaces 2020, 12, 1222–1231.
Che, R. C.; Peng, L. M.; Duan, X. F.; Chen, Q.; Liang, X. L. Microwave absorption enhancement and complex permittivity and permeability of Fe encapsulated within carbon nanotubes. Adv. Mater. 2004, 16, 401–405.
Zhou, C. L.; Wang, X. X.; Luo, H.; Deng, L. W.; Wang, S.; Wei, S.; Zheng, Y. W.; Jia, Q.; Liu, J. Q. Interfacial design of sandwich-like CoFe@Ti3C2Tx composites as high efficient microwave absorption materials. Appl. Surf. Sci. 2019, 494, 540–550.
Zhou, C. L.; Wang, X. X.; Luo, H.; Deng, L. W.; Wei, S.; Zheng, Y. W.; Jia, Q.; Liu, J. Q. Rapid and direct growth of bipyramid TiO2 from Ti3C2Tx MXene to prepare Ni/TiO2/C heterogeneous composites for high-performance microwave absorption. Chem. Eng. J. 2020, 383, 123095.
Wang, F. Y.; Sun, Y. Q.; Li, D. R.; Zhong, B.; Wu, Z. G.; Zuo, S. Y.; Yan, D.; Zhuo, R. F.; Feng, J. J.; Yan, P. X. Microwave absorption properties of 3D cross-linked Fe/C porous nanofibers prepared by electrospinning. Carbon 2018, 134, 264–273.
Wu, Y.; Shu, R. W.; Zhang, J. B.; Wan, Z. L.; Shi, J. J.; Liu, Y.; Zhao, G. M.; Zheng, M. D. Oxygen vacancies regulated microwave absorption properties of reduced graphene oxide/multi-walled carbon nanotubes/cerium oxide ternary nanocomposite. J. Alloys Compd. 2020, 819, 152944.
Shu, R. W.; Wan, Z. L.; Zhang, J. B.; Wu, Y.; Liu, Y.; Shi, J. J.; Zheng, M. D. Facile design of three-dimensional nitrogen-doped reduced graphene oxide/multi-walled carbon nanotube composite foams as lightweight and highly efficient microwave absorbers. ACS Appl. Mater. Interfaces 2020, 12, 4689–4698.
Liu, Y.; Jia, Z. R.; Zhan, Q. Q.; Dong, Y. H.; Xu, Q. M.; Wu, G. L. Magnetic manganese-based composites with multiple loss mechanisms towards broadband absorption. Nano Res. 2022, 15, 5590–5600.
Wang, G. Z.; Gao, Z.; Tang, S. W.; Chen, C. Q.; Duan, F. F.; Zhao, S. C.; Lin, S. W.; Feng, Y. H.; Zhou, L.; Qin, Y. Microwave absorption properties of carbon nanocoils coated with highly controlled magnetic materials by atomic layer deposition. ACS Nano 2012, 6, 11009–11017.
Tang, M.; Zhang, J. Y.; Bi, S.; Hou, Z. L.; Shao, X. H.; Zhan, K. T.; Cao, M. S. Ultrathin topological insulator absorber: Unique dielectric behavior of Bi2Te3 nanosheets based on conducting surface states. ACS Appl. Mater. Interfaces 2019, 11, 33285–33291.
Li, Z. N.; Han, X. J.; Ma, Y.; Liu, D. W.; Wang, Y. H.; Xu, P.; Li, C. L.; Du, Y. C. MOFs-derived hollow Co/C microspheres with enhanced microwave absorption performance. ACS Sustainable Chem. Eng. 2018, 6, 8904–8913.
Wang, R. L.; He, M.; Zhou, Y. M.; Nie, S. X.; Wang, Y. J.; Liu, W. Q.; He, Q.; Wu, W. T.; Bu, X. H.; Yang, X. M. Metal–organic frameworks self-templated cubic hollow Co/N/C@MnO2 composites for electromagnetic wave absorption. Carbon 2020, 156, 378–388.
Xu, Z. J.; He, M.; Zhou, Y. M.; Nie, S. X.; Wang, Y. J.; Huo, Y.; Kang, Y. F.; Wang, R. L.; Xu, R.; Peng, H. et al. Spider web-like carbonized bacterial cellulose/MoSe2 nanocomposite with enhanced microwave attenuation performance and tunable absorption bands. Nano Res. 2021, 14, 738–746.
Ur Rehman, S.; Wang, J. M.; Luo, Q. H.; Sun, M. Z.; Jiang, L.; Han, Q.; Liu, J. C.; Bi, H. Starfish-like C/CoNiO2 heterostructure derived from ZIF-67 with tunable microwave absorption properties. Chem. Eng. J. 2019, 373, 122–130.
Wang, S. Y.; Ke, X.; Zhong, S. T.; Lai, Y. R.; Qian, D. L.; Wang, Y. P.; Wang, Q. H.; Jiang, W. Bimetallic zeolitic imidazolate frameworks-derived porous carbon-based materials with efficient synergistic microwave absorption properties: The role of calcining temperature. RSC Adv. 2017, 7, 46436–46444.
Jiang, Y.; Xie, X.; Chen, Y.; Liu, Y. J.; Yang, R.; Sui, G. X. Hierarchically structured cellulose aerogels with interconnected MXene networks and their enhanced microwave absorption properties. J. Mater. Chem. C 2018, 6, 8679–8687.
Zhang, X.; Wang, H. H.; Hu, R.; Huang, C. Y.; Zhong, W. J.; Pan, L. M.; Feng, Y. B.; Qiu, T.; Zhang, C. F.; Yang, J. Novel solvothermal preparation and enhanced microwave absorption properties of Ti3C2Tx MXene modified by in situ coated Fe3O4 nanoparticles. Appl. Surf. Sci. 2019, 484, 383–391.
Bai, T. T.; Guo, Y.; Liu, H.; Song, G.; Zhang, D. B.; Wang, Y. M.; Mi, L. W.; Guo, Z. H.; Liu, C. T.; Shen, C. Y. Achieving enhanced electromagnetic shielding and absorption capacity of cellulose-derived carbon aerogels via tuning the carbonization temperature. J. Mater. Chem. C 2020, 8, 5191–5201.
Qiu, X.; Wang, L. X.; Zhu, H. L.; Guan, Y. K.; Zhang, Q. T. Lightweight and efficient microwave absorbing materials based on walnut shell-derived nano-porous carbon. Nanoscale 2017, 9, 7408–7418.
Huang, X. G.; Qiao, M.; Lu, X. C.; Li, Y. F.; Ma, Y. B.; Kang, B.; Quan, B.; Ji, G. B. Evolution of dielectric loss-dominated electromagnetic patterns in magnetic absorbers for enhanced microwave absorption performances. Nano Res. 2021, 14, 4006–4013.
Li, C.; Li, Z. H.; Qi, X. S.; Gong, X.; Chen, Y. L.; Peng, Q.; Deng, C. Y.; Jing, T.; Zhong, W. A generalizable strategy for constructing ultralight three-dimensional hierarchical network heterostructure as high-efficient microwave absorber. J. Colloid Interface Sci. 2022, 605, 13–22.
Zhang, J. J.; Li, Z. H.; Qi, X. S.; Gong, X.; Xie, R.; Deng, C. Y.; Zhong, W.; Du, Y. W. Constructing flower-like core@shell MoSe2-based nanocomposites as a novel and high-efficient microwave absorber. Compos. Part B Eng. 2021, 222, 109067.
Li, C.; Qi, X. S.; Gong, X.; Peng, Q.; Chen, Y. L.; Xie, R.; Zhong, W. Magnetic–dielectric synergy and interfacial engineering to design yolk–shell structured CoNi@void@C and CoNi@void@C@MoS2 nanocomposites with tunable and strong wideband microwave absorption. Nano Res. 2022, 15, 6761–6771.
Wu, Z. C.; Cheng, H. W.; Jin, C.; Yang, B. T.; Xu, C. Y.; Pei, K.; Zhang, H. B.; Yang, Z. Q.; Che, R. C. Dimensional design and core–shell engineering of nanomaterials for electromagnetic wave absorption. Adv. Mater. 2022, 34, 2107538.
Xue, W.; Yang, G.; Bi, S.; Zhang, J. Y.; Hou, Z. L. Construction of caterpillar-like hierarchically structured Co/MnO/CNTs derived from MnO2/ZIF-8@ZIF-67 for electromagnetic wave absorption. Carbon 2021, 173, 521–527.
Liu, P. B.; Zhang, Y. Q.; Yan, J.; Huang, Y.; Xia, L.; Guang, Z. X. Synthesis of lightweight N-doped graphene foams with open reticular structure for high-efficiency electromagnetic wave absorption. Chem. Eng. J. 2019, 368, 285–298.
Wang, N. N.; Wu, F.; Xie, A. M.; Dai, X. Q.; Sun, M. X.; Qiu, Y. Y.; Wang, Y.; Lv, X.; Wang, M. L. One-pot synthesis of biomass-derived carbonaceous spheres for excellent microwave absorption at the Ku band. RSC Adv. 2015, 5, 40531–40535.
Guo, L.; An, Q. D.; Xiao, Z. Y.; Zhai, S. R.; Cui, L.; Li, Z. C. Performance enhanced electromagnetic wave absorber from controllable modification of natural plant fiber. RSC Adv. 2019, 9, 16690–16700.
Ren, A. F.; Zahid, A.; Fan, D.; Yang, X. D.; Imran, M. A.; Alomainy, A.; Abbasi, Q. H. State-of-the-art in terahertz sensing for food and water security–A comprehensive review. Trends Food Sci. Technol. 2019, 85, 241–251.
Seo, M.; Park, H. R. THz biochemical sensors: Terahertz biochemical molecule-specific sensors (Advanced Optical Materials 3/2020). Adv. Opt. Mater. 2020, 8, 2070010.
Yang, X. X.; Vorobiev, A.; Generalov, A.; Andersson, M. A.; Stake, J. A flexible graphene terahertz detector. Appl. Phys. Lett. 2017, 111, 021102.
Zhang, Z. Y.; Zhong, C. Z.; Fan, F.; Liu, G. H.; Chang, S. J. Terahertz polarization and chirality sensing for amino acid solution based on chiral metasurface sensor. Sens. Actuators B Chem. 2021, 330, 129315.
Jung, G. B.; Myung, Y.; Cho, Y. J.; Sohn, Y. J.; Jang, D. M.; Kim, H. S.; Lee, C. W.; Park, J.; Maeng, I.; Son, J. H. et al. Terahertz spectroscopy of nanocrystal–carbon nanotube and -graphene oxide hybrid nanostructures. J. Phys. Chem. C 2010, 114, 11258–11265.
Yuan, T. Y.; Xiong, S. J.; Shen, X. H. Coordination of actinide single ions to deformed graphdiyne: Strategy on essential separation processes in nuclear fuel cycle. Angew. Chem., Int. Ed. 2020, 59, 17719–17725.