MXenes induce epitaxial growth of size-controlled noble nanometals: A case study for surface enhanced Raman scattering (SERS)

doi:10.1016/j.jmst.2019.09.013

Abstract

Abstract:

Noble nanometals are of significance in both scientific interest and technological applications, which are usually obtained by conventional wet-chemical synthesis. Organic surfactants are always used in the synthesis to prevent unexpected overgrowth and aggregation of noble nanometals. However, the surfactants are hard to remove and may interfere with plasmonic and catalytic studies, remaining surfactant-free synthesis of noble nanometals a challenge. Herein, we report an approach to epitaxial growth of size-controlled noble nanometals on MXenes. As piloted by density functional theory calculations, along with work function experimental determination, kinetic and spectroscopic studies, epitaxial growth of noble nanometals is initiated via a mechanism that involves an in situ redox reaction. In the redox, MXenes as two-dimensional solid reductants whose work functions are compatible with the reduction potentials of noble metal cations, enable spontaneous donation of electrons from the MXenes to noble metal cations and reduce the cations into nanoscale metallic metals on the outmost surface of MXenes. Neither surfactants nor external reductants are used during the whole synthesis process, which addresses a long-standing interference issue of surfactant and external reductant in the conventional wet-chemical synthesis. Moreover, the MXenes induced noble nanometals are size-controlled. Impressively, noble nanometals firmly anchored on MXenes exhibit excellent performance towards surface enhanced Raman scattering. Our developed strategy will promote the nanostructure-controlled synthesis of noble nanometals, offering new opportunities to further improve advanced functional properties towards practical applications.

Key words: Two-dimensional materials, Mxene, In situ redox, Noble metal, SERS

Renfei Cheng, Tao Hu, Minmin Hu, Changji Li, Yan Liang, Zuohua Wang, Hui Zhang, Muchan Li, Hailong Wang, Hongxia Lu, Yunyi Fu, Hongwang Zhang, Quan-Hong Yang, Xiaohui Wang. MXenes induce epitaxial growth of size-controlled noble nanometals: A case study for surface enhanced Raman scattering (SERS)[J]. J. Mater. Sci. Technol., 2020, 40: 119-127.

Figures/Tables 7

Fig. 1. Schematic of electronic structure for termination-functionalized Ti3C2Tx MXenes. All the bands are aligned by the vacuum energy level. The black dash lines indicate the Fermi level (EF), showing the boundary of occupied states and unoccupied electronic states. The shaded areas are filled with electrons in the solid. As calculated theoretically, the work functions of Ti3C2(OH)2, Ti3C2O(OH), Ti3C2F2 and Ti3C2O2 are 2.0, 3.0, 4.79 and 6.57 eV, respectively. The work function of the free-standing Ti3C2Tx membrane is experimentally determined to be 4.36-4.47 eV, as marked by the red asterisk in the right panel. The energy of free electron is 4.5 eV on the hydrogen scale.

Fig. 2. Evolution of HAuCl4 solution droplet on Ti3C2Tx membrane. (a) optical photograph of droplet of HAuCl4 solution just dropped on Ti3C2Tx membrane; (b) optical image of Ti3C2Tx membrane and droplets after 3 min of dropwise addition of HAuCl4 solution. (c) optical image of Ti3C2Tx membrane and droplets after 15 min of dropwise addition of HAuCl4 solution, (d) optical photograph of Au@Ti3C2Tx membrane, (e) the cross-sectional microstructure of Au anchored on Ti3C2Tx membrane, (f) contour plot of 2D XRD patterns for operando XRD to reveal the interaction between the solution droplet of 10 μL HAuCl4 and the Ti3C2Tx membrane at room temperature. The positions of the Au (111) and Ti3C2Tx (004) reflection are marked, (g) contact angle and appearance of the droplet on Ti3C2Tx membrane in the course of time, (h) mass loss of HAuCl4 solution droplet on Ti3C2Tx membrane as a function of time. Inset shows the volume evolution of the sphere-cap-like droplet with time. Note that the complete evaporation of the droplet to dryness at room temperature approximately requires 50 min.

Fig. 3. Redox mechanism of HAuCl4 solution with Ti3C2Tx membrane. (a) XPS spectra of Ti 2p collected on pristine Ti3C2Tx membrane, (b) XPS spectra of Ti 2p collected on Au@Ti3C2Tx. The sample was prepared by placing a droplet of chloroauric acid (1.0 × 10-3 mol L-1) on Ti3C2Tx MXene membrane at room temperature and allowed to dryness. Note that the C-Ti-O composition increases in Au@Ti3C2Tx. The XPS spectra were recorded without Ar sputtering or with Ar sputtering for 120 s; (c) schematics of the redox mechanism of HAuCl4 solution with Ti3C2Tx MXene. It illustrates the redox reaction in which Au3+ as electron acceptor and MXene as donor, forming gold nanometal as chloroauric acid solution contacts MXene membrane.

Fig. 4. Morphological characterization of Au@Ti3C2Tx. (a-d) Au nanoparticles is prepared by 1.0 × 10-3 mol L-1 HAuCl4 solution droplet on Ti3C2Tx membrane; (e-f) Au@Ti3C2Tx prepared by 1.0 × 10-4 mol L-1 HAuCl4 solution droplet on Ti3C2Tx membrane; (a) SEM image of Au@Ti3C2Tx (Inset is a high magnification of (a)), (b, c) EDS elemental mapping of (b) Au, and (c) Ti, (d) size distribution of Au nanoparticles. The statistic size of Au nanoparticles is 124 nm (e) SEM image of Au@Ti3C2Tx (Inset is a high magnification of (e)). EDS elemental mapping of (f) Au, and (g) Ti. (h) Size distribution of Au nanoparticles. The statistic size of Au nanoparticles is 39 nm.

Fig. 5. Morphological characterization of Pd@Ti3C2Tx. (a-d) Pd nanoparticles is prepared by 1 × 10-3 mol L-1 H2PdCl4 solution droplet on Ti3C2Tx membrane; (e-h) Pd@Ti3C2Tx is prepared by 1 × 10-4 mol L-1 H2PdCl4 solution droplet on Ti3C2Tx membrane. (a) SEM image of Pd@Ti3C2Tx. EDS elemental mapping of (b) Pd, and (c) Ti. (d) Size distribution of Pd nanoparticles. The Pd particles distribute bimodally with two peaks at 102 nm and 306 nm. (e) SEM image of Pd@Ti3C2Tx. EDS elemental mapping of (f) Pd, and (g) Ti. (h) Size distribution of Pd nanoparticles. The statistic size of Pd nanoparticles is 58 nm.

Fig. 6. SERS effect of Au@Ti3C2Tx and Pd@Ti3C2Tx. (a) Typical Raman spectra of MB recorded from Au@Ti3C2Tx and Ti3C2Tx. Inset shows the optical photograph of Au@Ti3C2Tx membrane. For Au@Ti3C2Tx, the droplet imprint on the membrane is the area where Raman spectra are collected. (b) SERS spectra of MB collected from an area of 10 μm × 10 μm on Au@Ti3C2Tx. (c) Raman intensity mapping of the band centered at 1621 cm-1. (d) Typical Raman spectrum of MB recorded from Pd@Ti3C2Tx substrates. Inset shows the molecular structure of MB. (e) SERS spectra of MB collected from Pd@Ti3C2Tx. (f) Raman intensity mapping of the band centered at 1621 cm-1.

Fig. 7. Reproducibility and stability of SERS substrates. Raman intensity distribution of the band at 1621 cm-1 for (a) Au@Ti3C2Tx and (b) Pd@Ti3C2Tx substrates. Storage time dependence of Raman intensity of MB at 1621 cm-1 for (c) Au@Ti3C2Tx and (d) Pd@Ti3C2Tx substrates.

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