Surface confinement of sub-1 nm Pt nanoclusters on 1D/2D NiO nanotubes/nanosheets as an effective electrocatalyst for urea-assisted energy-saving hydrogen production

doi:10.1016/S1872-2067(24)60203-2

Abstract

Abstract:

To address the high cost and limited electrochemical endurance of Pt-based electrocatalysts, the appropriate introduction of transition metal-based compounds as supports to disperse and anchor Pt species offers a promising approach for improving catalytic efficiency. In this study, sub-1 nm Pt nanoclusters were uniformly confined on NiO supports with a hierarchical nanotube/nanosheet structure (Pt/NiO/NF) through a combination of spatial domain confinement and annealing. The resulting catalyst exhibited excellent electrocatalytic activity and stability for hydrogen evolution (HER) and urea oxidation reactions (UOR) under alkaline conditions. Structural characterization and density functional theory calculations demonstrated that sub-1 nm Pt nanoclusters were immobilized on the NiO supports by Pt-O-Ni bonds at the interface. The strong metal-support interaction induced massive charge redistribution around the heterointerface, leading to the formation of multiple active sites. The Pt/NiO/NF catalyst only required an overpotential of 12 and 136 mV to actuate current densities of 10 and 100 mA cm^-2 for the HER, respectively, and maintained a voltage retention of 96% for 260 h of continuous operation at a current density of 500 mA cm^-2. Notably, in energy-efficient hydrogen production systems coupled with the HER and UOR, the catalyst required cell voltages of 1.37 and 1.53 V to drive current densities of 10 and 50 mA cm^-2, respectively—approximately 300 mV lower than conventional water electrolysis systems. This study presents a novel pathway for designing highly efficient and robust sub-nanometer metal cluster catalysts.

Key words: Metal-support interaction, Sub-nanometric cluster, Hydrogen evolution reaction, Size engineering, Urea oxidation reaction

Jiaxin Li, Yan Lv, Xueyan Wu, Xinyu Guo, Zhuojun Yang, Jixi Guo, Tianhua Zhou, Dianzeng Jia. Surface confinement of sub-1 nm Pt nanoclusters on 1D/2D NiO nanotubes/nanosheets as an effective electrocatalyst for urea-assisted energy-saving hydrogen production[J]. Chinese Journal of Catalysis, 2025, 69: 203-218.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60203-2

https://www.cjcatal.com/EN/Y2025/V69/I2/203

Figures/Tables 8

Scheme 1. Schematic overview of the fabrication of sub-1 nm Pt nanoclusters loaded on NiO nanotubes/nanosheets.

Fig. 1. (a) XRD patterns of Pt/NiO/NF and NiO/NF nanoarray. (b,c) SEM images of Pt/NiO/NF at different magnifications. (d) TEM images of Pt/NiO/NF (with Pt nanoclusters size distribution on NiO supports). High-resolution TEM images (e-g) and the SAED pattern (h) of the Pt/NiO/NF. (i) Dark field STEM and corresponding elemental mapping images of Pt/NiO/NF.

Fig. 2. (a) UPS analysis of Pt/C and NiO/NF. (b) Energy band profile of the metal Pt in contact with the semiconductor NiO. High-resolution spectra of Pt 4f (c), Ni 2p (d), and O 1s (e) for Pt/NiO/NF and NiO/NF, respectively. (f) Valence band spectra of Pt/NiO/NF and NiO/NF nanoarray.

Fig. 3. (a) HER polarization curve of Pt/NiO/NF in 1.0 mol L-1 KOH solution at a scan rate of 5 mV s-1. (b) Potential comparison of the catalysts for HER. (c) Tafel slopes of Pt/NiO/NF and NiO/NF, and Pt/C. (d) EIS of Pt/NiO/NF and NiO/NF, and Pt/C. (e) Cdl values of Pt/NiO/NF, NiO/NF and NF. (f) TOF and N values in 1.0 mol L-1 PBS solution (left: TOF value; right: number of active species). (g) The comparison of LSV curves of Pt/NiO/NF catalyst before and after 5000 cycles CV cycling test (inset shows multi-step chronopotentiometric curves without iR compensation). (h) Chronopotentiometry measurements of Pt/NiO/NF at 500 mA cm-2.

Fig. 4. (a) Top view of the DFT optimization model for the Pt/NiO/NF catalyst (Blue balls = Pt, dark grey = Ni, red balls = O). (b) Difference charge density analysis of Pt/NiO/NF (The yellow area stands for electron accumulation and the cyan area stands for electron depletion). (c) Calculated DOS of NiO/NF and Pt/NiO/NF. (d) PDOS of Ni-3d in Pt/NiO/NF and NiO/NF. (e) PDOS of O-2p in Pt/NiO/NF and NiO/NF. (f) PDOS of P-5d in Pt/NiO/NF and Pt. (g) Adsorption free energies of H* on the surface of the Pt/NiO/NF and NiO/NF catalysts, respectively. (h) Water dissociation energy comparison plot for Pt/NiO/NF and NiO/NF.

Fig. 5. (a) Polarization curves for the OER and UOR of Pt/NiO/NF in 1.0 mol L-1 KOH + 0.5 mol L-1 urea at a scan rate of 5 mV s-1. (b) Potential comparison for the Pt/NiO/NF during UOR and OER. UOR polarization curves (c), Tafel slopes (d), and EIS (e) of Pt/NiO/NF and NiO/NF, and RuO2/NF in 1.0 mol L-1 KOH and 0.5 mol L-1 urea (the inset in Fig. (e) illustrates the equivalent circuit diagram). (f) Cdl value of Pt/NiO/NF and NiO/NF. (g) Multi-step chronopotentiometric curve of Pt/NiO/NF without iR-compensation, with the inset illustrating UOR cycling stability of the Pt/NiO/NF in 1.0 mol L-1 KOH and 0.5 mol L-1 urea.

Fig. 6. (a) In situ attenuated total reflection (ATR)-FTIR spectra of Pt/NiO/NF catalysts at a constant potential (vs. RHE) of 1.50 V. (b) In situ Raman spectra of Pt/NiO/NF catalyst at different applied potentials in 1.0 mol L-1 KOH and 0.5 mol L-1 urea solution. (c) Calculated DOS of Pt/NiONF and NiO/NF. (d) Amplified in situ FTIR spectra of Pt/NiO/NF catalysts in the 1250-3750 cm-1 range. (e) In situ Raman spectra of Pt/NiO/NF catalyst at different applied potentials. (f) Proposed UOR pathway on the surface of Pt/NiO/NF. (g) Urea adsorption energies at different active sites. (h) DFT model of the clean surface of Pt/NiOOH/NF, as well as adsorption of urea molecules and *OCN2, *OCOH intermediates during the UOR reaction in solution. (i) Gibbs free energy calculations for UOR intermediates on the active sites of Pt/NiOOH/NF and NiOOH/NF catalysts.

Fig. 7. (a) Schematic of the HER and UOR coupled system using Pt/NiO/NF as a bifunctional electrode. (b) Polarization curves of the Pt/NiO/NF electrode. (c) Electrode voltage comparison plots. (d) Polarization curves of Pt/NiO/NF||Pt/NiO/NF, NiO/NF||NiO/NF, and Pt/C||RuO2 electrodes in the HER||UOR system. (e) Cell stability of Pt/NiO/NF electrodes in the HER||UOR system during a multi-step chronopotentiometric test. The inset shows an optical image of the test system, with visible H2 and N2 + CO2 bubbles on the Pt/NiO/NF cathode and anode, respectively. (f) Faradaic efficiency of H2 production in the HER||UOR system upon operation time.

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