Supporting Information

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1 Supporting Information Laminated and Two-Dimensional Carbon-Supported Microwave Absorbers Derived from MXenes Meikang Han, Xiaowei Yin,*, Xinliang Li, Babak Anasori, Litong Zhang, Laifei Cheng, and Yury Gogotsi Science and Technology on Thermostructural Composite Materials Laboratory, Northwestern Polytechnical University, Xi an, Shaanxi , China A. J. Drexel Nanomaterials Institute and Department of Materials Science and Engineering, Drexel University, Philadelphia, Pennsylvania 19104, United States *Corresponding author: S-1

2 Figure S1. Photograph of the as-prepared samples of C/TiO 2 hybrids in the paraffin matrix for dielectric measurement. The reflection coefficient (RC) was calculated using the measured complex permittivity at a given layer thickness and frequency by the following equations: RC db = 20log10 Zin -1 Z in +1 (1) Z in = tanh j2 fd c where Z in is the normalized input impendence of the microwave absorption layer, ε and μ are the relative permittivity and permeability of the samples, f is the EM wave frequency, d is the matching thickness, c is the light velocity in vacuum. RC value is < -10 db (denoted effective absorption), more than 90% of the EM wave is absorbed. The corresponding frequency range (RC < -10 db) is defined as the effective absorption bandwidth. (2) Figure S2. (a) Nitrogen adsorption desorption isotherms for Ti 3 C 2 T x, TiO 2 and C/TiO 2 hybrids (S-800); (b) The TG-DSC curves of the as-prepared C/TiO 2 hybrids in an air atmosphere at the temperature ranging from 30 to 800 C. S-2

3 The N 2 adsorption desorption isotherms (Figure S2a) show an increase in the specific surface area (SSA) from Ti 3 C 2 T x to C/TiO 2 hybrids. The SSA of C/TiO 2 hybrids estimated using the BET equations was found to be ~31.4 m 2 /g, a factor of 4 greater than that of Ti 3 C 2 T x, which had a SSA of 8.1 m 2 /g. In particular, to evaluate the SSA of carbon layers derived from MXene, pure TiO 2 was obtained by oxidation of the as-synthesized C/TiO 2 hybrids at 800 C in air, and its SSA was ~8.5 m 2 /g. The weight ratio of carbon to TiO 2 is about 1:24, as shown in the TG-DSC curves of C/TiO 2 hybrids in air atmosphere (Figure S2b). The SSA of carbon derived from MXene which was estimated from the above data was ~584 m 2 /g. In addition, based on the ratio of carbon in C/TiO 2 hybrids (~3.98 wt.%), it can be calculated that the mass ratio of carbon in the sample with 45 wt.% filler loading is ~1.79 wt.% ( wt.%). Figure S3. Schematic of the structural evolution from Ti 3 C 2 T x to C/TiO 2 hybrids with the increasing temperature, and the corresponding SEM images. Figure S3 shows a schematic of the structural evolution from Ti 3 C 2 T x to C/TiO 2 hybrids, coupled with the corresponding SEM images. After annealing at 600 C, small crystalline TiO 2 nanoparticles and disorder carbon form on the surface of Ti 3 C 2 T x layers. At this stage, no visible morphological changes were observed, which is ascribed to localized oxidation of the external Ti layers terminated with hydroxyl groups, oxygen and fluorine. As the temperature increases, the smooth flakes become rough, and the interlayer spacing broadens obviously, which is related to the increasing density and size of anatase and rutile TiO 2 particles during the intensified oxidation process. A significant transformation occurs when Ti layers undergo the complete oxidation of Ti at the annealing temperature of 800 C. It leads to the exfoliation of the intermediated C layers. 2D disordered carbon layers support TiO 2 nanocrystals, which separate carbon sheets and prevent them from restacking. S-3

4 Figure S4. 3D plots of reflection coefficient (RC) versus frequency and thickness for the samples with mass ratios of (a) 35, (b) 40 and (c) 50 wt.% C/TiO 2 hybrids (S-800) in the paraffin matrix. Figure S5. (a) ε' and (b) ε" versus frequency for the composites of Ti 3 C 2 T x, S-600, S-700 and S-800 in the paraffin matrix with 45 wt.% filler mass ratio. As shown in Figure S5, both ε' and ε" of S-800 are higher than those of Ti 3 C 2 T x, S-600 and S-700, especially in the low frequency (lower than 10 GHz). The complete exfoliation of carbon layers from multi-layer Ti 3 C 2 T x makes a major contribution to the increased permittivity, because the pure TiO 2 has a relatively low ε". 1 The typical relaxation peaks appear after annealing treatment, while no obvious relaxation can be S-4

5 observed in Ti 3 C 2 T x. It is attributed to the enhanced orientation polarization, which arises from defects and the oxygen functional groups. It should be specifically noted that the response frequency of S-800 is different from that of S-600 and S-700. This is related to the increasing crystallization of carbon layers and the crystal transition of TiO 2 from anatase to rutile. Figure S6. 3D plots of reflection coefficient values versus frequency and thickness for the composites of (a) Ti 3 C 2 T x, (b) S-600, (c) S-700 and (d) S-800 in the paraffin matrix with 45 wt.% mass ratio. The calculated RC values of all the samples versus thickness and frequency are shown in Figure S6. Based on our calculations, there is no effective absorption by Ti 3 C 2 T x with a thickness from 1 to 5 mm, which can be ascribed to its extremely low dielectric loss (Figure S6a). As for S-600 and S-700, both of them present a narrow absorption bandwidth and thick absorption layer (Figure S6b and c). For example, the effective absorption bandwidth of S-700 is only 2.4 GHz (6.6-9 GHz), and the sample thickness is 3.2 mm, although the RC min value can reach -36 db (Figure S6c). S-5

6 RGO/magnetic materials RGO/nonma gnetic materials RGO/carb on Table S1. EM wave absorption properties of graphene-based materials in recent years The G Optimum RC Type Filler Matrix content min effective thickness Refs (db) bandwidth (wt.%) (mm) (GHz) This Laminated C/TiO 2 wax work RGO NBR Magnetic RGO epoxy ~1 3 RGO foam wax RGO foam/cnts PDMS < RGO/C spheres wax 8.8 ~-25 2 ~4 6 RGO/ZnO spheres wax RGO/ZnO wax RGO/MoS 2 wax 4.3 ~ RGO/silica textile PF ~ RGO/SiC nanowires SiOC GN/PANI wax ~4 12 RGO/γ-Fe 2 O 3 wax RGO/α-Fe 2 O 3 wax 3.75 ~ RGO/Fe 3 O 4 wax ~ RGO/ Fe 3 O 4 wax RGO/ Fe 3 O 4 wax ~3 17 RGO/ Fe 3 O 4 PANI 8.97 ~ RGO/ Fe 3 O 4 epoxy - ~ RGO/ Fe 3 O 4 wax ~ RGO/Fe 3 O 4 /SiO 2 /NiO wax RGO/Fe 3 O 4 /ZnO epoxy RGO/Fe 3 O 4 /CNTs wax RGO/Fe 3 O 4 /SiO 2 wax ~5 24 RGO/ Fe 3 O 4 /Fe/ ZnO wax ~ RGO/Fe 3 O 4 /C/PANI wax RGO/CuS wax RGO/MnFe 2 O 4 PVDF RGO/NiFe 2 O 4 wax RGO/NiFe 2 O 4 wax ~ ~2 30 RGO/ CoFe 2 O 4 wax ~ RGO/ ZnFe 2 O 4 wax RGO/BaFe 12 O 19 PANI G/Fe wax ~ RGO/Fe wax 1.4 ~ RGO/Fe/MnO 2 wax 2.4 ~ RGO/Co wax ~ ~5 37 RGO/Ni wax ~19 ~ ~ RGO/NiCoP wax ~3 39 References (1) Xia, T.; Zhang, C.; Oyler, N. A.; Chen, X. Hydrogenated TiO 2 Nanocrystals: A Novel Microwave Absorbing Material. Adv. Mater. 2013, 25, (2) Singh, V. K.; Shukla, A.; Patra, M. K.; Saini, L.; Jani, R. K.; Vadera, S. R.; Kumar, N. Microwave Absorbing Properties of a Thermally Reduced Graphene Oxide/Nitrile Butadiene Rubber Composite. Carbon 2012, 50, (3) Kowsari, E.; Mohammadi, M. Synthesis of Reduced and Functional Graphene Oxide with Magnetic Ionic Liquid and Its Application as an Electromagnetic-absorbing Coating. Compos. Sci. Technol. 2016, 126, S-6

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