Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation

Kaline N. da Silva; Shwetha Shetty; Sam Sullivan−Allsop; Rongsheng Cai; Shiqi Wang; Jhon Quiroz; Mykhailo Chundak; Hugo L.S. dos Santos; Ibrahi M. Abdelsalam; Freddy E. Oropeza; Víctor A. de la Peña O’Shea; Niko Heikkinen; Elton Sitta; Tiago V. Alves; Mikko Ritala; Wenyi Huo; Thomas J.A. Slater; Sarah J. Haigh; Pedro H.C. Camargo

doi:10.1021/acsnano.4c07076

Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation

Kaline N. da Silva
, Shwetha Shetty
, Sam Sullivan−Allsop
, Rongsheng Cai
, Shiqi Wang
, Jhon Quiroz
, Mykhailo Chundak
, Hugo L.S. dos Santos
, Ibrahi M. Abdelsalam
, Freddy E. Oropeza
, Víctor A. de la Peña O’Shea
, Niko Heikkinen
, Elton Sitta
, Tiago V. Alves
, Mikko Ritala
, Wenyi Huo^*
, Thomas J.A. Slater
, Sarah J. Haigh^*
, Pedro H.C. Camargo^*

^*Corresponding author for this work

BA5208 Catalytic processes

Research output: Contribution to journal › Article › Scientific › peer-review

17 Citations (Scopus)

Abstract

Plasmonic catalysis has been employed to enhance molecular transformations under visible light excitation, leveraging the localized surface plasmon resonance (LSPR) in plasmonic nanoparticles. While plasmonic catalysis has been employed for accelerating reaction rates, achieving control over the reaction selectivity has remained a challenge. In addition, the incorporation of catalytic components into traditional plasmonic-catalytic antenna-reactor nanoparticles often leads to a decrease in optical absorption. To address these issues, this study focuses on the synthesis of bimetallic core@shell Au@AuPd nanoparticles (NPs) with ultralow loadings of palladium (Pd) into gold (Au) NPs. The goal is to achieve NPs with an Au core and a dilute alloyed shell containing both Au and Pd, with a low Pd content of around 10 atom %. By employing the (photo)electrocatalytic nitrite reduction reaction (NO2RR) as a model transformation, experimental and theoretical analyses show that this design enables enhanced catalytic activity and selectivity under visible light illumination. We found that the optimized Pd distribution in the alloyed shell allowed for stronger interaction with key adsorbed species, leading to improved catalytic activity and selectivity, both under no illumination and under visible light excitation conditions. The findings provide valuable insights for the rational design of antenna-reactor plasmonic-catalytic NPs with controlled activities and selectivity under visible light irradiation, addressing critical challenges to enable sustainable molecular transformations.

Original language	English
Pages (from-to)	24391-24403
Number of pages	13
Journal	ACS Nano
Volume	18
Issue number	35
DOIs	https://doi.org/10.1021/acsnano.4c07076
Publication status	Published - 3 Sept 2024
MoE publication type	A1 Journal article-refereed

Funding

This work was supported by the Jane and Aatos Erkko Foundation and the Academy of Finland (decision no. 334826). S.J.H. acknowledges funding from EPSRC (EP/P009050/1) and the European Research Council under the Horizon 2020 program for the ERC Starter Grant EvoluTEM (715502). TEM access for this work was supported by the Henry Royce Institute for Advanced Materials, funded through EPSRC grants EP/R00661X/1, EP/S019367/1, EP/P025021/1, and EP/P025498/1. ES thanks the Sao Paulo Research Foundation (FAPESP, #2013/07296-2, #2017/11986-5) and Brazilian Council for Scientific and Technological Development (CNPq, 405752/2022-9) for financial support (310550/2022-0). K.N.d.S. thanks the National Council for the Improvement of Higher Education for the scholarship (Capes\u2500PrInt 88887.464913/2019-00). EU/Interreg Aurora/Sustainable Hydrogen project is also acknowledged for its financial support. This work was partly supported by the European Union Horizon 2020 research and innovation program under the NOMATEN Teaming grant (857470) and the European Regional Development Fund via the Foundation for Polish Science International Research Agenda PLUS program grant (MAB PLUS/2018/8). The publication was created partly within the framework of the project of the Minister of Science and Higher Education \u201CSupport for the activities of Centres of Excellence established in Poland under Horizon 2020\u201D under contract no. MEiN/2023/DIR/3795. F.E.O. thanks the RYC2021-034254-I grant funded by MCIN/AEI/10.13039/501100011033 and by the \u201CEuropean Union NextGenerationEU/PRTR\u201D. Facilities of ALD center Finland research infrastructure were used for XPS characterization.

Keywords

Au@AuPd core−shell
bimetallic nanoparticles
nitrite reduction reaction (NORR)
plasmonic electrocatalysis
selectivity
ultralow loading
visible light irradiation

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10.1021/acsnano.4c07076

Cite this

da Silva, K. N., Shetty, S., Sullivan−Allsop, S., Cai, R., Wang, S., Quiroz, J., Chundak, M., dos Santos, H. L. S., Abdelsalam, I. M., Oropeza, F. E., de la Peña O’Shea, V. A., Heikkinen, N., Sitta, E., Alves, T. V., Ritala, M., Huo, W., Slater, T. J. A., Haigh, S. J., & Camargo, P. H. C. (2024). Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation. ACS Nano, 18(35), 24391-24403. https://doi.org/10.1021/acsnano.4c07076

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title = "Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation",

abstract = "Plasmonic catalysis has been employed to enhance molecular transformations under visible light excitation, leveraging the localized surface plasmon resonance (LSPR) in plasmonic nanoparticles. While plasmonic catalysis has been employed for accelerating reaction rates, achieving control over the reaction selectivity has remained a challenge. In addition, the incorporation of catalytic components into traditional plasmonic-catalytic antenna-reactor nanoparticles often leads to a decrease in optical absorption. To address these issues, this study focuses on the synthesis of bimetallic core@shell Au@AuPd nanoparticles (NPs) with ultralow loadings of palladium (Pd) into gold (Au) NPs. The goal is to achieve NPs with an Au core and a dilute alloyed shell containing both Au and Pd, with a low Pd content of around 10 atom \%. By employing the (photo)electrocatalytic nitrite reduction reaction (NO2RR) as a model transformation, experimental and theoretical analyses show that this design enables enhanced catalytic activity and selectivity under visible light illumination. We found that the optimized Pd distribution in the alloyed shell allowed for stronger interaction with key adsorbed species, leading to improved catalytic activity and selectivity, both under no illumination and under visible light excitation conditions. The findings provide valuable insights for the rational design of antenna-reactor plasmonic-catalytic NPs with controlled activities and selectivity under visible light irradiation, addressing critical challenges to enable sustainable molecular transformations.",

keywords = "Au@AuPd core−shell, bimetallic nanoparticles, nitrite reduction reaction (NORR), plasmonic electrocatalysis, selectivity, ultralow loading, visible light irradiation",

author = "\{da Silva\}, \{Kaline N.\} and Shwetha Shetty and Sam Sullivan−Allsop and Rongsheng Cai and Shiqi Wang and Jhon Quiroz and Mykhailo Chundak and \{dos Santos\}, \{Hugo L.S.\} and Abdelsalam, \{Ibrahi M.\} and Oropeza, \{Freddy E.\} and \{de la Pe{\~n}a O{\textquoteright}Shea\}, \{V{\'i}ctor A.\} and Niko Heikkinen and Elton Sitta and Alves, \{Tiago V.\} and Mikko Ritala and Wenyi Huo and Slater, \{Thomas J.A.\} and Haigh, \{Sarah J.\} and Camargo, \{Pedro H.C.\}",

year = "2024",

month = sep,

day = "3",

doi = "10.1021/acsnano.4c07076",

language = "English",

volume = "18",

pages = "24391--24403",

journal = "ACS Nano",

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da Silva, KN, Shetty, S, Sullivan−Allsop, S, Cai, R, Wang, S, Quiroz, J, Chundak, M, dos Santos, HLS, Abdelsalam, IM, Oropeza, FE, de la Peña O’Shea, VA, Heikkinen, N, Sitta, E, Alves, TV, Ritala, M, Huo, W, Slater, TJA, Haigh, SJ & Camargo, PHC 2024, 'Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation', ACS Nano, vol. 18, no. 35, pp. 24391-24403. https://doi.org/10.1021/acsnano.4c07076

TY - JOUR

T1 - Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation

AU - da Silva, Kaline N.

AU - Shetty, Shwetha

AU - Sullivan−Allsop, Sam

AU - Cai, Rongsheng

AU - Wang, Shiqi

AU - Quiroz, Jhon

AU - Chundak, Mykhailo

AU - dos Santos, Hugo L.S.

AU - Abdelsalam, Ibrahi M.

AU - Oropeza, Freddy E.

AU - de la Peña O’Shea, Víctor A.

AU - Heikkinen, Niko

AU - Sitta, Elton

AU - Alves, Tiago V.

AU - Ritala, Mikko

AU - Huo, Wenyi

AU - Slater, Thomas J.A.

AU - Haigh, Sarah J.

AU - Camargo, Pedro H.C.

PY - 2024/9/3

Y1 - 2024/9/3

N2 - Plasmonic catalysis has been employed to enhance molecular transformations under visible light excitation, leveraging the localized surface plasmon resonance (LSPR) in plasmonic nanoparticles. While plasmonic catalysis has been employed for accelerating reaction rates, achieving control over the reaction selectivity has remained a challenge. In addition, the incorporation of catalytic components into traditional plasmonic-catalytic antenna-reactor nanoparticles often leads to a decrease in optical absorption. To address these issues, this study focuses on the synthesis of bimetallic core@shell Au@AuPd nanoparticles (NPs) with ultralow loadings of palladium (Pd) into gold (Au) NPs. The goal is to achieve NPs with an Au core and a dilute alloyed shell containing both Au and Pd, with a low Pd content of around 10 atom %. By employing the (photo)electrocatalytic nitrite reduction reaction (NO2RR) as a model transformation, experimental and theoretical analyses show that this design enables enhanced catalytic activity and selectivity under visible light illumination. We found that the optimized Pd distribution in the alloyed shell allowed for stronger interaction with key adsorbed species, leading to improved catalytic activity and selectivity, both under no illumination and under visible light excitation conditions. The findings provide valuable insights for the rational design of antenna-reactor plasmonic-catalytic NPs with controlled activities and selectivity under visible light irradiation, addressing critical challenges to enable sustainable molecular transformations.

AB - Plasmonic catalysis has been employed to enhance molecular transformations under visible light excitation, leveraging the localized surface plasmon resonance (LSPR) in plasmonic nanoparticles. While plasmonic catalysis has been employed for accelerating reaction rates, achieving control over the reaction selectivity has remained a challenge. In addition, the incorporation of catalytic components into traditional plasmonic-catalytic antenna-reactor nanoparticles often leads to a decrease in optical absorption. To address these issues, this study focuses on the synthesis of bimetallic core@shell Au@AuPd nanoparticles (NPs) with ultralow loadings of palladium (Pd) into gold (Au) NPs. The goal is to achieve NPs with an Au core and a dilute alloyed shell containing both Au and Pd, with a low Pd content of around 10 atom %. By employing the (photo)electrocatalytic nitrite reduction reaction (NO2RR) as a model transformation, experimental and theoretical analyses show that this design enables enhanced catalytic activity and selectivity under visible light illumination. We found that the optimized Pd distribution in the alloyed shell allowed for stronger interaction with key adsorbed species, leading to improved catalytic activity and selectivity, both under no illumination and under visible light excitation conditions. The findings provide valuable insights for the rational design of antenna-reactor plasmonic-catalytic NPs with controlled activities and selectivity under visible light irradiation, addressing critical challenges to enable sustainable molecular transformations.

KW - Au@AuPd core−shell

KW - bimetallic nanoparticles

KW - nitrite reduction reaction (NORR)

KW - plasmonic electrocatalysis

KW - selectivity

KW - ultralow loading

KW - visible light irradiation

UR - https://www.scopus.com/pages/publications/85201671048

U2 - 10.1021/acsnano.4c07076

DO - 10.1021/acsnano.4c07076

M3 - Article

C2 - 39164202

AN - SCOPUS:85201671048

SN - 1936-0851

VL - 18

SP - 24391

EP - 24403

JO - ACS Nano

JF - ACS Nano

IS - 35

ER -

Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation

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