Surface electronic state modulation promotes photoinduced aggregation and oxidation of trace CO for lossless purification of H2 stream

doi:10.1016/S1872-2067(23)64483-3

Abstract

Abstract:

Although photogenerated hydroxyl radicals can oxidize CO without H₂ consumption, the nonselective collision severely lowers photocatalytic photon utilization. We here demonstrate that electronic state modification of TiO₂ resulted from magnesium doping can promote hydroxyl radical generation by weakening the adsorption of oxygen species and facilitating semiconductor-cocatalyst interfacial electron transfer. Importantly, the partial deprivation of electronic cloud from cationic sites can strengthen σ-donation and π-backdonation that synergistically promote the electrostatic interaction for aggregating CO in the vicinity of semiconductor. The resulted photocatalyst thus exhibits growing superiority over common counterpart in target reaction as CO concentration lowers. By these merits, CO in H₂ stream can be reduced to < 1 × 10^-6 with efficient photon utilization.

Key words: Electronic states, Hydroxyl radical, Carbon monoxide oxidation, Hydrogen purification, Photocatalytic fixed bed reaction

Haifeng Liu, Xiang Huang, Jiazang Chen. Surface electronic state modulation promotes photoinduced aggregation and oxidation of trace CO for lossless purification of H₂ stream[J]. Chinese Journal of Catalysis, 2023, 51: 49-54.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64483-3

https://www.cjcatal.com/EN/Y2023/V51/I8/49

Figures/Tables 8

Fig. 1. (a-c) Comparison of minimum energy pathways for H2O dissociation on TiO2 (101) surface with and without Mg doping. (d) Adsorption free energies of *OH adsorbed on the Ti sites on perfect TiO2 (101), 5c@Mg, and 6c@Mg. The dashed line indicates the free energy of a free solvated ?OH. The light blue, green, red, and white balls represent Ti, Mg, O, and H atoms, respectively.

Fig. 2. X-ray diffraction patterns (a), electron microscopy images (b,c), high-angle annular dark field (haadf) and elementary mapping images (d), UV-vis absorption spectra (e), and Ti 2p (f), O 1s (g), and Mg 1s (h) X-ray photoelectron spectra of TiO2 (b) and Mg-TiO2 (c,d,h). Although the phase (a), size (b,c), and light absorption behaviors (e) do not change, together with the elementary analysis (d,h), the blueshift of Ti 2p peaks (f) and the redshift of O 1s peak (g) suggest that modification of electronic states occurs after magnesium doping. The length of scale bars shown in haadf and elementary mapping images is 100 nm (d).

Fig. 3. Photoinduced anodic behaviors of TiO2 and Mg-TiO2 on the glassy carbon disk and the related cathodic current occurring on the platinum ring of a rotating ring-disk electrode. The ring is biased at 0 V (vs. Ag/AgCl), which is more positive than the potentials for hydrogen evolution in the solution (1 mol/L Na2SO4). The cathodic signal can reflect the reduction of hydroxyl radicals generated on the disk electrode.

Fig. 4. Photoinduced generation of hydroxyl radicals over TiO2 and Mg-TiO2 in 2 mmol/L NaOH solution containing 0.5 mmol/L terephthalic acid (TA) trapping agent. The generation of hydroxyl radicals can be partially reflected by the formation of 2-hydroxyterephthalic acid (HTA), which formed by reacting TA with the captured hydroxyl radicals. The formation rates of HTA estimated from the fluorescence spectra (a,b) are respectively 0.129 and 0.230 μmol/h for TiO2 and Mg-TiO2 (c). Since the concentration of HTA is far lower than that of TA even after reaction (60 min), it can safely conclude that the formation rate of hydroxyl radicals over Mg-TiO2 is 0.78 times higher than that of TiO2.

Fig. 5. Time constants for leakage of electrons from TiO2 and Mg-TiO2 to the solution and for interfacial transfer of electrons from TiO2 and Mg-TiO2 to copper (a). The percentage of electrons transferred to copper (b) can be estimated from time constants (a), which can be obtained by monitoring the open-circuit potential decay from photoinduced potential (Fig. S2).

Fig. 6. Photoinduced CO oxidation over TiO2|Cu and Mg-TiO2|Cu photocatalyst. CO2 generation rate (a) and the rate ratio (b) can be evaluated by monitoring the effluent gas (Fig. S5). The concentration of CO in the feeding stream (30 mL/min) is 100 vol%, 10 vol%, 1 vol%, and 0.1 vol%.

Fig. 7. The infrared absorption behaviors of CO over TiO2 and Mg-TiO2 in dark and under irradiation.

Fig. 8. Photoinduced oxidation of CO (10 × 10-6) in H2 stream (1 L/min). With increase in the number of reaction chambers (a), the concentration of CO in the effluent H2 stream decreases (b). According to the simulated CO concentration (solid line), the predicted behavior (extended dish line) suggests that TiO2|Cu photocatalyst needs at least 4 reaction chambers (open squares) to reduce CO to < 1 × 10-6 in the effluent H2 stream (b). The long-term operation shows that by connecting two reaction chambers, the Mg-TiO2|Cu photocatalyst can reduce the concentration of CO to < 1 × 10-6 (0.7-0.9 × 10-6) in effluent H2 stream after 1 h of initialization (c). For the case of TiO2|Cu photocatalyst, CO in the effluent gas is ~4 × 10-6 (c). In each reaction chamber, the irradiation (UVC, 254 nm) provided by a 320-W amalgam lamp is 105 W (a). The moisture (~10000 × 10-6 H2O) is provided by injecting water, which can be readily vaporized in the reaction chamber that kept at 90 °C. Compared with the highest level of PROX [24], methanation [25], and photocatalytic radical reaction [4], our work highlights an important strategy for hydrogen purification (d,e). The schematic diagram (a) is adapted from ref [4]. Copyright 2022, American Chemical Society

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Surface electronic state modulation promotes photoinduced aggregation and oxidation of trace CO for lossless purification of H₂ stream

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