Palladium-copper nanodot as novel H2-evolution cocatalyst: Optimizing interfacial hydrogen desorption for highly efficient photocatalytic activity

doi:10.1016/S1872-2067(21)63830-5

Abstract

Abstract:

Noble metal palladium (Pd) is well-known as excellent photocatalytic cocatalyst, but its strong adsorption to hydrogen causes its limited H₂-evolution activity. In this study, the transition metal Cu was successfully introduced into the metallic Pd to weaken its hydrogen-adsorption strength to improve its interfacial H₂-evolution rate via the Pd-Cu alloying effect. Herein, the ultrasmall Pd_100-_xCu_x alloy nanodots (2-5 nm) as a novel H₂-evolution cocatalyst were integrated with the TiO₂ through a simple NaH₂PO₂-mediated co-deposition route. The resulting Pd_100-_xCu_x/TiO₂ sample shows the significantly enhanced photocatalytic H₂-generation performance (269.2 μmol h ^-1), which is much higher than the bare TiO₂. Based on in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) and density functional theory (DFT) results, the as-formed Pd_100-_xCu_x alloy nanodots can effectively promote the separation of photo-generated charges and weak the adsorption strength for hydrogen to optimize the process of hydrogen-desorption process on Pd₇₅Cu₂₅ alloy, thus leading to high photocatalytic H₂-evolution activity. Herein, the weakened H adsorption of Pd₇₅Cu₂₅cocatalyst can be ascribed to the formation of electron-rich Pd after the introduction of weak electronegativity Cu. The present work about optimizing electronic structure for promoting interfacial reaction activity provides a new sight for the development of the highly efficient photocatalysts.

Key words: Photocatalytic H₂ evolution, TiO₂, Pd_100-xCu_xalloy, Electron-rich Pd, Hydrogen desorption

Jiachao Xu, Duoduo Gao, Huogen Yu, Ping Wang, Bichen Zhu, Linxi Wang, Jiajie Fan. Palladium-copper nanodot as novel H₂-evolution cocatalyst: Optimizing interfacial hydrogen desorption for highly efficient photocatalytic activity[J]. Chinese Journal of Catalysis, 2022, 43(2): 215-225.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63830-5

https://www.cjcatal.com/EN/Y2022/V43/I2/215

Figures/Tables 10

Fig. 1. Schematic diagram illustrating the controllable preparation for Pd100-xCux/TiO2 photocatalyst.

Fig. 2. XRD patterns (a) and the slow-scan patterns (b) of metal PdCu for various samples. (1) TiO2; (2) Pd95Cu5/TiO2; (3) Pd75Cu25/TiO2; (4) Pd55Cu45/TiO2.

Fig. 3. TEM (a,b) and HRTEM (c) images of Pd75Cu25/TiO2 photocatalyst; (d) HAADF-STEM and its EDS mapping images; (e) The corresponding line-scan results of single Pd75Cu25 nanodot.

Fig. 4. XPS survey spectra (a) and high-resolution XPS spectra of Pd 3d (b), Cu 2p (c) for TiO2 (1), Pd95Cu5/TiO2 (2), Pd75Cu25/TiO2 (3) and Pd55Cu45/TiO2 (4).

Fig. 5. UV-vis spectra for TiO2 (1), Pd100Cu0/TiO2 (2), Pd95Cu5/TiO2 (3), Pd75Cu25/TiO2 (4), and Pd55Cu45/TiO2 (5).

Fig. 6. (a) The photocatalytic H2-generation rate of various samples: (1) TiO2; (2) Pd100Cu0/TiO2; (3) Pd95Cu5/TiO2; (4) Pd75Cu25/TiO2; (5) Pd55Cu45/TiO2; (6) Pd37Cu63/TiO2; (7) Pd25Cu75/TiO2. (b) photocatalytic H2-generation cycling tests of Pd75Cu25/TiO2 sample; (c) Proposed photocatalytic H2-generation mechanism of the Pd100-xCux nanodot-modified TiO2 photocatalyst.

Fig. 7. ISI-XPS spectra of Ti 2p (a) and Pd 3d (b) for the Pd75Cu25/TiO2 sample; (c) Schematic diagrams for the electron transfer of the Pd75Cu25/TiO2.

Fig. 8. Theoretical calculations of the HER activation energy of the Pd75Cu25 alloy. (a) Atomic configurations of the water-dissociation step on the surface of the Pd75Cu25 alloy. Color codes: blue and deep orange represent Pd and Cu atoms, while red and green represent O and H atoms in a single H2O molecule, respectively; (b) Calculated water-dissociation barriers diagram; (c) Calculated Free energies of H adsorption diagram.

Fig. 9. Bulk model of Pd75Cu25 alloy (a) and corresponding charges transformation (b) obtained from Bader charge analysis; (c) XPS results of Pd element in the Pd100Cu0/TiO2 and Pd75Cu25/TiO2 samples.

Fig. 10. Transient-state photoluminescence spectra (a), linear sweep voltammetry curves (b), transient photocurrent responses (c) and electrochemical impedance spectra (d) for TiO2 (1), Pd100Cu0/TiO2 (2), and Pd75Cu25/TiO2 (3).

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Palladium-copper nanodot as novel H₂-evolution cocatalyst: Optimizing interfacial hydrogen desorption for highly efficient photocatalytic activity

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