Low Temperature Ammonia Synthesis from Atomic N and Water on Rutile TiO₂(110)^†

Shenzhen Key Laboratory of Energy Chemistry & Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China

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Corresponding author: E-mail: chenx37@sustech.edu.cn

摘要

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Abstract: We have investigated the formation of ammonia (NH₃) from atomic N and water (H₂O) on a rutile(R)-TiO₂(110) surface using the temperature-programed desorption method. The formation of NH₃ can be detected after coadsorption of atomic N and H₂O on the R-TiO₂(110) surface, desorbing from the 5-fold coordinated Ti⁴⁺ (Ti_5c) sites at about 400 K, demonstrating that the NH₃ formation on R-TiO₂(110) is feasible at low surface temperature. During the process, both hydroxyl groups at the bridging oxygen rows and H₂O on the Ti_5c sites contribute to the formation of NH₃, which are affected by H₂O coverage. At low H₂O coverage, the direct hopping of hydrogen atoms may be the dominant process for hydrogen transfer; while H₂O-assisted hydrogen atoms diffusion may be preferred at high H₂O coverage. Our result will be of significant help to get a deeper insight into the fundamental understandings of hydrogenation processes during the NH₃ synthesis.
- Ammonia /
- Hydrogen transfer /
- Temperature programmed desorption /
- R-TiO₂(110)
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Figure 1. Typical TPD spectra acquired at (a) m/z=17 (NH₃⁺, OH⁺) and (b) m/z=18 (H₂O⁺) after surfaces of R-TiO₂(110) were exposed to activated N for different sputtering times, followed by the dosing of 1 ML H₂O at 120 K. The contribution of H₂O in the TPD signal of m/z = 17 has been subtracted.

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Figure 2. The decay of H₂O (red circles) and the yield of NH₃ (blue squares) as a function of sputtering time, derived from FIG. 1. All the plotted lines are only drawn to guide the eye.

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Figure 3. Typical TPD spectra collected at (a) m/z = 18 (ND₂⁺, NDH₂⁺, OD⁺, H₂O⁺), (b) m/z = 19 (NHD₂⁺, HDO⁺) and (c) m/z = 20 (ND₃⁺, D₂O⁺) after surfaces of R-TiO₂(110) were exposed to activated N for 5 min, followed by the dosing of 1 ML D₂O at 120 K.

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Figure 4. Typical TPD spectra collected at (a) m/z = 30 (NO⁺) and (b) m/z = 44 (CO₂⁺, N₂O⁺) after the surface was exposed to activated N for 5 min, followed by dosing with different coverages of H₂O.

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Figure 5. Typical TPD spectra collected at (a) m/z = 17 (NH₃⁺, OH⁺) and (b) m/z = 18 (H₂O⁺) as a function of H₂O coverage. Before H₂O adsorption, R-TiO₂(110) surfaces were exposed to activated N for 5 min. The dash line in (b) represents the TPD spectrum collected after the clean R-TiO₂(110) surface was dosed with 1 ML H₂O.

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Figure 6. Schematic model of hydrogen atom diffusion in NH₃ formation. (a) Hydrogen diffusion along the O_b rows toward atomic N without the assistance of H₂O; (b) H₂O diffusion along the Ti_5c rows toward atomic N; (c) H₂O-assisted hydrogen diffusion across the O_b rows. Atoms are labeled as follows: Ti_5c³⁺ sites (open black circles), Ti_6c⁴⁺ sites (filled yellow circles), Ti_5c⁴⁺ sites (filled purple circles), bridge-bonded oxygen atoms (BBO, filled pink circles), atomic N (N_ads, filled green circles), H atoms (filled blue circles).

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