Clarifying sequential electron-transfer steps in single-nanoparticle electrochemical process for identifying the intrinsic activity of electrocatalyst

doi:10.1016/S1872-2067(24)60015-X

Abstract

Abstract:

Single-nanoparticle collision electrochemistry (SNCE) is an effective method for determining the intrinsic activity of electrocatalysts at the single-nanoparticle (NP) level. Despite fruitful advancements in the SNCE field, determining a quantitative relationship between the NP structure and its activity has remained difficult because of an unclear understanding of SNCE. In this study, we successfully uncovered the essential roles of the sequential electron-transfer steps in the SNCE system in regulating the apparent electrocatalytic activity of single NPs. By monitoring the oxygen reduction reaction of individual Pt NPs, significantly distinct apparent activities were observed at different electrodes owing to the rate-determining step-controlled electron transfer process. Furthermore, a new theoretical model is proposed for treating the electrochemical current, which involves NP-electrode electron transfer, heterogeneous electron transfer, and mass transfer in solution as sequential steps in the SNCE system. The combination of theoretical simulations and high-resolution electrochemical measurements allows for the corresponding parameters (contact resistance, heterogeneous kinetic constants, and adsorption possibility) of sequential electron-transfer steps to be quantified, resulting in the identification of a rate-determining step for improving the intrinsic activity of electrocatalysts. This work provides a clear picture for determining the intrinsic activity of single NPs in SNCE measurements and introduces a new conceptual route for the quantification of structure-activity relationships, which ultimately guide the rational design and optimization of electrocatalytic nanomaterials.

Key words: Single nanoparticle, Electrocatalyst, Electron transfer, Rate-determining step, Intrinsic activity

Zehui Sun, Zhuangzhuang Lai, Yingying Zhao, Jianfu Chen, Wei Ma. Clarifying sequential electron-transfer steps in single-nanoparticle electrochemical process for identifying the intrinsic activity of electrocatalyst[J]. Chinese Journal of Catalysis, 2024, 60: 262-271.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60015-X

https://www.cjcatal.com/EN/Y2024/V60/I5/262

Figures/Tables 6

Fig. 1. Schematic view of the sequential electron-transfer steps involved in the SNCE system, which result in the ORR of single Pt NP at the CNE electrode surface. Jcont, Jet, and Jdiff represent NP-electrode electron transfer, heterogeneous kinetic, and mass transfer controlled current densities, respectively.

Fig. 2. Microstructural characterization of CNE. SEM images of s-CNE (a) and r-CNE (b) etched using BOE and HF, respectively. EDX spectra of sN-CNE (c) and rN-CNE (d) after PE electrodeposition and thermal pyrolysis. (e) EDX mapping of a PE film modified r-CNE with C, O, Si, and N elements. (f) Raman spectra of r-CNE and rN-CNE. (g) High-resolution XPS N 1s spectra of an rN-CNE.

Fig. 3. Chronoamperometric curves and representative current traces of individual Pt NP collisions at -500 mV vs. An Ag/AgCl wire at a smooth CNE (a), rough CNE (b), smooth CNE doping with N atoms (c) and rough CNE doping with N atoms (d) immersed in an oxygen-saturated 20 mmol L-1 KOH solution containing 1 × 10-10 mol L-1 Pt NPs. The corresponding histograms show the distributions of the current amplitudes (ii) and durations (iii). Black curves show Gaussian fits. The data were obtained from a large population of electrocatalytic events of individual Pt NPs (more than 1000 events). The experimental error (±) indicates the value of a Gaussian fit of the current or duration ± one standard deviation.

Fig. 4. The theoretical model for nanocollision electrochemistry. (a) Illustration of a collision of a freely diffused NP with the electrode’s surface along with the catalysis of the ORR. (b) Duration of current traces as a function of k0/Pads. (c) Apparent current in a nanocollision system as function of k0/Rcont. (d) Expanded portion of simulated current traces on s-CNE, r-CNE, sN-CNE, and rN-CNE. Histograms of the duration (e) and amplitude (f) of the current spikes. The experimental error (±) indicates the value of a Gaussian fit of the current or duration ± one standard deviation.

Table 1 Electrochemical parameters of electron transfer for different electrode surfaces.

Electrode	R_cont (Ω)	k₀ (m/s)	P_ads
s-CNE	6.0 × 10⁹	3.2 × 10^-6	0.9850
r-CNE	1.2 × 10⁹	3.2 × 10^-6	0.9850
sN-CNE	6.0 × 10⁹	2.0 × 10^-3	0.9950
rN-CNE	1.2 × 10⁹	2.5 × 10^-3	0.9985

Fig. 5. (a) Reaction coordinates for the ORR processes of Pt (black line), Pt/C (blue line) and Pt/NC (red line) at U = 1.23 V. Projected density of states (PDOS) of Pt in Pt/C (b) and Pt/N-C (c). The d-band centers are labeled Ed and are shown in red, and the Fermi energy was subtracted to show EF at 0. (d) Differential charge density maps for Pt/C and Pt/N-C, respectively. The yellow and cyan colors denote charge accumulation and depletion, respectively. (e) ORR polarization curves of the Pt NPs in O2-saturated 20 mmol L?1 KOH at various stirring speeds ω: ω = 100, 200, 400, 800, 1600 r min?1; Scan rate = 5 mV s?1, and Pt loading = 14 μg cm?2. (f) The corresponding K-L plots for ORR at ?0.5 V.

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