Heterostructuring 2D TiO2 nanosheets in situ grown on Ti3C2Tx MXene to improve the electrocatalytic nitrogen reduction

doi:10.1016/S1872-2067(21)64020-2

Abstract

Abstract:

In this study, TiO₂ nanosheets (NSs) grown in situ on extremely conductive Ti₃C₂T_x MXene to form TiO₂/Ti₃C₂T_x MXene composites with abundant active sites are proposed to effectively achieve electrocatalytic NH₃ synthesis. Electron transfer can be promoted by Ti₃C₂T_x MXene with high conductivity. Meanwhile, the TiO₂ NSs in-situ formation can not only avoid Ti₃C₂T_x MXene microstacking but also enhance the surface specific area of Ti₃C₂T_x MXene. The TiO₂/Ti₃C₂T_x MXene catalyst reaches a high Faradaic efficiency (FE) of 44.68% at -0.75 V vs. RHE and a large NH₃ yield of 44.17 µg h^-1 mg^-1_cat. at -0.95 V, with strong electrochemical durability. ¹⁵N isotopic labeling experiments imply that the N in the produced NH₃ originated from the N₂ of the electrolyte. DFT calculations were conducted to determine the possible NRR reaction pathways for TiO₂/Ti₃C₂T_x MXene composites. MXene catalysts combined with other materials have been rationally designed for efficient ammonia production under ambient conditions.

Key words: Electrocatalyst, N₂ reduction reaction, TiO₂ nanosheet, Ti₃C₂T_x MXene, In-situ growth

Xiu Qian, Yanjiao Wei, Mengjie Sun, Ye Han, Xiaoli Zhang, Jian Tian, Minhua Shao. Heterostructuring 2D TiO₂ nanosheets in situ grown on Ti₃C₂T_x MXene to improve the electrocatalytic nitrogen reduction[J]. Chinese Journal of Catalysis, 2022, 43(7): 1937-1944.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64020-2

https://www.cjcatal.com/EN/Y2022/V43/I7/1937

Figures/Tables 7

Scheme 1. Schematic illustration of the synthesis of TiO2/Ti3C2Tx MXene composites.

Fig. 1. XRD patterns of Ti3AlC2, Ti3C2Tx MXene, and TiO2/Ti3C2Tx MXene composites.

Fig. 2. Fully scanned (a), Ti 2p (b), C 1s (c), and O 1s (d) XPS spectra of TiO2/Ti3C2Tx MXene composites.

Fig. 3. (a) SEM images of Ti3C2Tx MXene; SEM (b), TEM (c), and HRTEM (d) images of TiO2/Ti3C2Tx MXene. (e) Elemental mapping images of C, Ti, and O in TiO2/Ti3C2Tx MXene composites.

Fig. 4. (a) The dependence of current density on time for TiO2/Ti3C2Tx MXene. (b) Average NH3 yields and FEs. (c) UV-Vis spectra of TiO2/Ti3C2Tx MXene composites as a catalyst at different potentials. (d) NH3 yields rate and FEs at the applied potentials on TiO2/Ti3C2Tx MXene, Ti3C2Tx MXene, and pure TiO2 NSs. The error bars represent the standard deviation of three independent experiments. The specific error values of the NH3 yields are shown in Table S2.

Fig. 5. (a) NH3 yields and FEs at -0.95 V during six consecutive cycling tests. (b) Chronoamperometry curve of TiO2/Ti3C2Tx MXene composites after electrolysis at -0.95 V for 12 h. (c) NH3 yields and FEs of TiO2/Ti3C2Tx MXene composites under different N2 flow rates. (d) 1H NMR spectra of 14NH4+ and 15NH4+ yielded from NRR tests (at -0.95 V) using 14N2 and 15N2 as the N2 source, respectively.

Fig. 6. (a) The adsorption geometries of *NN, *NNH, *NHNH, *NHNH2, *NH2NH2, and *NH2 intermediates on TiO2/Ti3C2Tx MXene composites surface along the alternating pathway. An asterisk (*) denotes the adsorption site. Cyan, navy blue, brown, red, and white spheres represent Ti, N, C, O, and H atoms, respectively. (b) Reaction free energy pathways of NRR on TiO2/Ti3C2Tx MXene composites. (c) Free energy diagram of the NRR along the alternating pathway on TiO2/Ti3C2Tx MXene composites and pure TiO2, respectively.

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Heterostructuring 2D TiO₂ nanosheets in situ grown on Ti₃C₂T_x MXene to improve the electrocatalytic nitrogen reduction

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