Unraveling the electro-oxidation steps of methanol on a single nanoparticle by in situ nanoplasmonic scattering spectroscopy

doi:10.1016/S1872-2067(23)64589-9

Chinese Journal of Catalysis ›› 2024, Vol. 57: 59-67.DOI: 10.1016/S1872-2067(23)64589-9

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Unraveling the electro-oxidation steps of methanol on a single nanoparticle by in situ nanoplasmonic scattering spectroscopy

Xiangqi Zhou^a^,^e^,¹, Lili Li^d^,¹, Jun-Gang Wang^b^,^*(), Zhanbo Li^c, Xiji Shao^f, Fupeng Cheng^a, Linjuan Zhang^a^,^h, Jian-Qiang Wang^a^,^h, Akhil Jain^g, Tao Lin^c^,^*(), Chao Jing^a^,^h^,^*()

^aKey Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China
^bSchool of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China
^cCollege of New Materials and New Energies, Shenzhen Technology University, Shenzhen 518118, Guangdong, China
^dState Key Laboratory of Crystal Materials and Institute of Crystal Materials, Shandong University, Jinan 250100, Shandong, China
^eKey Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education of China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, Hunan, China
^fDepartment of Physics, School of Intelligent Engineering, Shaoguan University, Shaoguan 512005, Guangdong, China
^gBioelectronics Laboratory, School of Pharmacy, Biodiscovery Institute, University of Nottingham, Nottingham NG7 2RD, UK
^hUniversity of Chinese Academy of Sciences, Beijing, 100049, China

Received:2023-11-22 Accepted:2023-12-21 Online:2024-02-18 Published:2024-02-10
Contact: * E-mail: jgwang@sit.edu.cn (J.-G. Wang), lintao@sztu.edu.cn (T. Lin), jingchao@sinap.ac.cn (C. Jing).
About author:¹ Contributed equally to this work.
Supported by:
“Transformational Technologies for Clean Energy and Demonstration,” Strategic Priority Research Program of the Chinese Academy of Sciences(XDA2100000);National Science Foundation of China(21802042);National Science Foundation of China(21902050);National Science Foundation of China(22374101);National Science Foundation of China(22209201);Shanghai Sailing Program(18YF1405700);Shanghai Sailing Program(21YF1456100);K. C. Wong Education Foundation(GJTD-2018-10);Youth Innovation Promotion Association, Chinese Academy of Sciences(Y201842);Youth Innovation Promotion Association, Chinese Academy of Sciences(2023270);DNL Cooperation Fund, CAS(DNL202008);Natural Science Foundation of Top Talent of SZTU(2019210);Startup Funding from Shaoguan University(440/9900064706);Engineering and Physical Sciences Research Council, UK (EP/R004072/1 to Dr Frankie Rawson which funded the post-doc position of Dr Akhil Jain)(EP/R004072/1)

Abstract

Abstract:

Understanding the mechanism of methanol oxidation reaction (MOR) remains a challenge in the development of direct methanol fuel cells. Large-scale investigations of the MOR encounter issues related to mass transfer and averaging effects. To address these limitations, exploring the MOR on the surfaces of individual nanocatalyst and precisely identifying the reaction steps can yield valuable insights into the underlying pathways. In this study, we employed in situ nanoplasmonic resonance scattering spectroscopy to dynamically monitor the MOR process on single gold nanorod particles (GNPs) and Pt-coated gold nanoparticles (Pt-GNPs). We observed the evolution of metal hydroxides, which was assumed as the active species. Notably, the dynamic behavior of the surface atomic layers revealed the rate-determining steps for both the GNPs and Pt-GNPs, indicating competitive adsorption of intermediates on the nanocatalyst surface. The resulting inherent reaction mechanism highlights the thermodynamics-dependent catalysts’ redox processes and their surface adsorptions, which holds significance for advancing highly active MOR catalysts.

Key words: Single nanoparticle detection, Dark-field microscopy, Plasmon resonance scattering, spectroscopy, Methanol oxidation reaction, Nano-electrochemistry

Xiangqi Zhou, Lili Li, Jun-Gang Wang, Zhanbo Li, Xiji Shao, Fupeng Cheng, Linjuan Zhang, Jian-Qiang Wang, Akhil Jain, Tao Lin, Chao Jing. Unraveling the electro-oxidation steps of methanol on a single nanoparticle by in situ nanoplasmonic scattering spectroscopy[J]. Chinese Journal of Catalysis, 2024, 57: 59-67.

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Figures/Tables 4

Fig. 1. Schematic representation of the plasmonic nanoantenna strategy to investigate MOR by PRS using dark field microscopy. (a) TEM (i) and HR-TEM (ii) images of GNPs. (b) TEM (i) and HR-TEM (ii) images of Pt-GNPs. Both the GNPs and Pt-GNPs exhibited the features of the (100) facet. (c,d) Schematic representation of MOR on GNPs and Pt-GNPs immobilized on ITO. (e) Diagrammatic representation of DFM setup utilized in this work. (f) Scattering spectra and dark-field images (insets) of a single GNP and Pt-GNP at open circuit potential, the scale bars in the insets are 1 μm.

Fig. 2. Scattering spectral changes during CV scanning of a single GNP in 0.5 mol/L KOH solution (a-d) and in 0.5 mol/L KOH + 0.5 mol/L MeOH solution (e-h). (a,e) Two-dimensional scattering spectral changes with an exposure time of 5 s. (b,f) CV curves, obtained in different solutions from -0.60 to 0.80 V vs Pt wire quasi-reference electrode at a scan rate of 10 mV/s. (c,g) Shifts in peak position, obtained from (a,e). (d,h) Corresponding spectral “CV” reconstructed from the first-order derivation of the peak shifts in (c) and (g) with time. The red dashed line in (h) is the same curve as in (d). The gray dashed lines in (a-h) indicate the potential sweep profile.

Fig. 3. Scattering spectral changes during CV scanning of a single Pt-GNP in 0.5 mol/L KOH solution (a-d) and 0.5 mol/L KOH + 0.5 mol/L MeOH solution (e-h). (a,e) Two-dimensional scattering spectral changes with an exposure time of 5 s. (b,f) CV curves in different solutions from -0.60 to 0.60 V vs. Pt wire quasi-reference electrode, obtained at a scan rate of 10 mV/s. (c,g) Shifts in peak position, obtained from (a) and (e). (d,h) Corresponding spectral "CV” reconstructed from the first-order derivation of the peak shifts in (c) and (g) with time. The red dashed line in (h) is the same curve in (d). The gray dashed lines in (a-h) indicate the potential sweep profile.

Fig. 4. Mechanism of the MOR process on single nanoparticle. MOR on GNP (a) and Pt-GNP surface (b). (c) Calculated Gibbs free energies of the MOR process on Au (100) through the HCOOH pathway. (d) Calculated Gibbs free energies of the MOR process on Pt (100) and Pt-Au (100) through the CO pathway.

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Unraveling the electro-oxidation steps of methanol on a single nanoparticle by in situ nanoplasmonic scattering spectroscopy

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