Photoelectrocatalytic reduction of CO2 catalyzed by TiO2/TiN nanotube heterojunction: Nitrogen assisted active hydrogen mechanism

doi:10.1016/S1872-2067(23)64395-5

Abstract

Abstract:

To address the over-emission of CO₂, the construction of new heterojunction materials is a promising approach for the photoelectrocatalytic (PEC) conversion of CO₂ into valuable chemicals. Herein, a series of heterojunctions of TiO₂/TiN nanotube arrays were designed and fabricated by anodic oxidation of titanium plates, followed by in situ partial oxidation to form heterojunctions. The surface of the heterojunction with nitrogen instead of oxygen contained more active Ti³⁺ species, and the oxygen vacancies were able to harvest solar light and showed excellent performance in the PEC reduction of CO₂. As a porous material, the TiO₂/TiN nanotube supports good adsorption of CO₂ as well as a confined space favoring C-C coupling. Operando Fourier transform infrared (FTIR) analysis revealed that the active species *COOH^̇ and *CHO were the major intermediates. Density functional theory (DFT) calculations revealed that the highly active hydrogen atoms could attach to the surface of the heterojunction to form Ti-H species with Ti³⁺, and the existence of nitrogen atoms could promote the migration of lattice oxygen to form new oxygen vacancies, which is conducive to the adsorption and coupling of CO₂ and intermediates. The vibration frequency of Ti-H predicted by DFT calculations matches well with the operando FTIR observations. The PEC cell of Pd/R-TiO₂/TiN-30|SCE|BiVO₄ efficiently produced carbon-based chemicals at a rate of 115.9 μmol L^-1 h^-1 cm^-2 with high selectivity for C₂ products. The total efficiency of the PEC cell approached 6.0%, exceeding that of the plant cell by 0.4%. Isotopic labeling experiments of ¹³CO₂ and H₂¹⁸O verified the elemental source and inferred the reaction pathway via highly active hydrogen.

Key words: Photoelectrocatalysis, CO₂ reduction, Heterojunction, Titanium nitride, Operando FTIR

Yan Wei, Ruizhi Duan, Qiaolan Zhang, Youzhi Cao, Jinyuan Wang, Bing Wang, Wenrui Wan, Chunyan Liu, Jiazang Chen, Hong Gao, Huanwang Jing. Photoelectrocatalytic reduction of CO₂ catalyzed by TiO₂/TiN nanotube heterojunction: Nitrogen assisted active hydrogen mechanism[J]. Chinese Journal of Catalysis, 2023, 47: 243-253.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64395-5

https://www.cjcatal.com/EN/Y2023/V47/I4/243

Figures/Tables 6

Fig. 1. (a) Schematic diagram for the fabrication procedure of Pd/R-TiO2/TiN. SEM and HRTEM images of TiO2 (b,e), TiN (c,f) and TiO2/TiN-30 (d,g). HRTEM image (h) and EDS elemental mappings (i) of Pd/R-TiO2/TiN-30. (j) XRD patterns of samples.

Fig. 2. High resolution XPS spectra of Ti 2p (a) and EPR spectra at ?163.15 °C (b) for TiN and TiO2/TiN-30; Ti K-edge XANES spectra (c), corresponding EXAFS spectra in R space (d) and wavelet transform (e) for Ti foil, TiO2 and TiO2/TiN-30.

Fig. 3. LSV curves (a), transient photocurrent responses (b) and Nyquist plots (c) of different photocathodes. (d) Mott-Schottky plot of Pd/R-TiO2/TiN-30 electrode.

Fig. 4. The formation rates, C2 selectivity and Φcell of Pd/R-TiO2/TiN-x at -1.0 V vs. SCE (a), Pd/R-TiO2/TiN-30 working electrode at various bias potentials (b), various photocathodes at -1.0 V vs. SCE and Pd/R-TiO2/TiN-30 working electrode under different conditions (c). Note: (1) PC: The photocathode and photoanode were connected by an external wire. (2) EC: the bias potential of -1.0 V vs. SCE was applied in dark conditions.

Fig. 5. Operando FTIR spectra of PEC reduction using Pd/R-TiO2/TiN-30 as photocathode at -1.0 V vs. SCE in CO2 saturated 0.1 mol L?1 KHCO3 aqueous electrolyte (a) and using TiO2/TiN-30 as photocathode at -0.5 V vs. SCE in Ar saturated 0.1 mol L?1 KHCO3 aqueous electrolyte (b).

Fig. 6. (a) Calculated reaction energy profile for CO2 reduction to HCOOH on TiO2/TiN and corresponding energetically favorable structures. (b) The optimized configurations of lattice oxygen migration process. (c) Proposed reaction pathways for PEC CO2 reduction on TiO2/TiN.

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Photoelectrocatalytic reduction of CO₂ catalyzed by TiO₂/TiN nanotube heterojunction: Nitrogen assisted active hydrogen mechanism

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