Chemical tuning of Coulomb blockade at room-temperature in ultra-small platinum nanoparticle self-assemblies

Trapping and electrical characterization of single core/shell iron-based nanoparticles in self-aligned nanogaps

Labra Muñoz, J.A.
Konstantinović, Z.
Balcells, L.
Pomar, A.
Zant, H.S.J van der
Dulić, D.

August 2019

We report on the fabrication and measurements of platinum-self-aligned nanogap devices containing cu...

Correlative pipette probe electrochemistry - electron microscopy studies of platinum nanoclusters

Mecking Ornelas, Isabel

December 2020

This thesis focuses on combining Scanning ElectroChemical Cell Microscopy (SECCM) and aberration-cor...

Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt27(CO)31]4- Displaying a Defective Structure

Cesari, Cristiana
Berti, Beatrice
Funaioli, Tiziana
Femoni, Cristina
Iapalucci, Maria Carmela
Pontiroli, Daniele
Magnani, Giacomo
Riccò, Mauro
Bortoluzzi, Marco
Vivaldi, Federico Maria
Zacchini, Stefano

January 2022

The molecular Pt nanocluster [Pt27(CO)31]4- (14-) was obtained by thermal decomposition of [Pt15(CO)...

Chemical tuning of Coulomb blockade at room-temperature in ultra-small platinum nanoparticle self-assemblies

Tricard, Simon
Said-Aizpuru, Olivier
Bouzouita, Donia
Usmani, Suhail
Gillet, Angélique
Tassé, Marine
Poteau, Romuald
Viau, G.
Demont, Phillipe
Carrey, Julian
Chaudret, Bruno

January 2017

International audienceThis work describes self-assemblies of ultra-small platinum nanoparticles, the...

Chemical tuning of Coulomb blockade at room-temperature in ultra-small platinum nanoparticle self-assemblies

Tricard, Simon
Said-Aizpuru, Olivier
Bouzouita, Donia
Usmani, Suhail
Gillet, Angélique
Tassé, Marine
Poteau, Romuald
Viau, G.
Demont, Phillipe
Carrey, Julian
Chaudret, Bruno

January 2017

International audienceThis work describes self-assemblies of ultra-small platinum nanoparticles, the...

Tuning Coulomb blockade in ultra-small metallic nanoparticle self-assemblies, at room-temperature

Tricard, Simon
Said-Aizpuru, Olivier
Bouzouita, Donia
Usmani, Suhail
Gillet, Angélique
Tassé, Marine
Poteau, Romuald
Viau, G.
Demont, Phillipe
Carrey, Julian
Chaudret, Bruno

October 2016

International audienceTuning Coulomb blockade at room temperature in nanoparticle self-assemblies ca...

Synthesis of nanoparticles (NPs) with well controlled characteristics is crucial to better understand the behaviour of the active phase during reaction and to better correlate it with its catalytic performance. Among other self-assembly methods, the di-block copolymer approach is well suited to obtain monodisperse supported NPs which can serve as supported metallic catalysts on both flat (model catalysts) and powder (realistic catalysts) supports. In this approach, an amphiphilic di-block copolymer dissolved in toluene yields a system of inverse micelles of which the core can be charged with metallic precursors to ultimately yield networks with well-controlled characteristics (size, composition, inter-distance). Important questions must be addressed, in particular in the case of bimetallic systems, concerning the formation of unique NPs at the cores from the initially pre-formed bimetallic seeds or the stability of the NPs networks with increasing temperature in presence of reactive gases. We have chosen to work with PS-b-P2VP di-block copolymer micelles that were functionalized with chloro-auric acid and palladium di-acetate precursors. The precursors selectively bind with N-functions in the P2VP cores to form (bi-)metallic seeds within the micelles’ cores as it was previously established in the case of PdAg alloys. We have used an Environmental TEM (Titan ETEM G2, FEI/TFS) operated at 300kV under gas pressures up to 20 mbar to gain insight on their evolution/stability during heating under oxygen and CO (for CO oxidation catalysis). Temperature variation was achieved with a WildFire sample holder with dedicated heating MEMS-microchips (DENS Solutions) capable of reaching temperatures up to 1300°C. Monolayers of controlled AuxPd1-x core-metallized PS-b-P2VP micellar solutions were deposited by spin-coating (2000/4000 rpm) on the microchips. Special care was taken to minimize/prevent any influence of the electron beam on the observed events.The Au-rich system (Au80Pd20) showed that, under oxygen, the (bi-)metallic seeds within the P2VP cores begin to sinter around 350° and unique NPs are eventually formed around 500°C which is consistent with the decomposition temperature range of the PS-b-P2VP copolymer associated with metallic nuclei. Further heating up shows that the NPs network is stable up to 900°C. Approaching the melting temperature of gold (1064°C) the NPs begin to shrink; concomitantly, smaller NPs (that grow even at 1100°C) form around the shrinking NPs. These smaller NPs are formed with Pd atoms from the initial bimetallic NPs.In the case of the Pd-rich system (Au20Pd80), under oxygen, the seeds begin to sinter around 300°C and at 450°C demixing of the NPs is observed leading to Janus NPs (Au-rich/PdO, cf. Figure); the latter are readily reduced and homogeneous NPs reform upon CO exposure (cf. Figure).The stability of the bimetallic NPs seems to be driven by the intrinsic properties of the metals composing them.Thanks are due to the METSA network for supporting this study and to CLYM for the access to the ETEM.

Cadete Santos Aires, F.J.
Ehret, E.
Vas, J.V.
Chatre, C.
Landrivon, E.
Duchamp, M.
Epicier, Thierry

May 2022

SSCI-VIDE+ING:MEME+FCA:EEH:ELA:TEPInternational audienceObservation of liquids within a transmission...

Synthesis of nanoparticles (NPs) with well controlled characteristics is crucial to better understand the behaviour of the active phase during reaction and to better correlate it with its catalytic performance. Among other self-assembly methods, the di-block copolymer approach is well suited to obtain monodisperse supported NPs which can serve as supported metallic catalysts on both flat (model catalysts) and powder (realistic catalysts) supports. In this approach, an amphiphilic di-block copolymer dissolved in toluene yields a system of inverse micelles of which the core can be charged with metallic precursors to ultimately yield networks with well-controlled characteristics (size, composition, inter-distance). Important questions must be addressed, in particular in the case of bimetallic systems, concerning the formation of unique NPs at the cores from the initially pre-formed bimetallic seeds or the stability of the NPs networks with increasing temperature in presence of reactive gases. We have chosen to work with PS-b-P2VP di-block copolymer micelles that were functionalized with chloro-auric acid and palladium di-acetate precursors. The precursors selectively bind with N-functions in the P2VP cores to form (bi-)metallic seeds within the micelles’ cores as it was previously established in the case of PdAg alloys. We have used an Environmental TEM (Titan ETEM G2, FEI/TFS) operated at 300kV under gas pressures up to 20 mbar to gain insight on their evolution/stability during heating under oxygen and CO (for CO oxidation catalysis). Temperature variation was achieved with a WildFire sample holder with dedicated heating MEMS-microchips (DENS Solutions) capable of reaching temperatures up to 1300°C. Monolayers of controlled AuxPd1-x core-metallized PS-b-P2VP micellar solutions were deposited by spin-coating (2000/4000 rpm) on the microchips. Special care was taken to minimize/prevent any influence of the electron beam on the observed events.The Au-rich system (Au80Pd20) showed that, under oxygen, the (bi-)metallic seeds within the P2VP cores begin to sinter around 350° and unique NPs are eventually formed around 500°C which is consistent with the decomposition temperature range of the PS-b-P2VP copolymer associated with metallic nuclei. Further heating up shows that the NPs network is stable up to 900°C. Approaching the melting temperature of gold (1064°C) the NPs begin to shrink; concomitantly, smaller NPs (that grow even at 1100°C) form around the shrinking NPs. These smaller NPs are formed with Pd atoms from the initial bimetallic NPs.In the case of the Pd-rich system (Au20Pd80), under oxygen, the seeds begin to sinter around 300°C and at 450°C demixing of the NPs is observed leading to Janus NPs (Au-rich/PdO, cf. Figure); the latter are readily reduced and homogeneous NPs reform upon CO exposure (cf. Figure).The stability of the bimetallic NPs seems to be driven by the intrinsic properties of the metals composing them.Thanks are due to the METSA network for supporting this study and to CLYM for the access to the ETEM.

Cadete Santos Aires, F.J.
Ehret, E.
Vas, J.V.
Chatre, C.
Landrivon, E.
Duchamp, M.
Epicier, Thierry

May 2022

SSCI-VIDE+ING:MEME+FCA:EEH:ELA:TEPInternational audienceObservation of liquids within a transmission...

Dynamic covalent nanoparticle building blocks

Kay, Euan Robert

July 2016

The author thanks the Royal Society of Edinburgh and Scottish Government for a personal research fel...

Synthesis, Electrochemical Characterization and Molecular Dynamics Studies of Surface Segregation of Platinum Nano-Alloy Electrocatalysts

Favry, E.
Wang, D.
Fatauzzi, D.
Anton, J.
Su, D.
Jacob, T.
Alonso-Vante, N.

May 2011

Alloy Pt–M (M = Co, Ni) nanocatalysts, supported on carbon Vulcan XC-72, were synthesized using the ...

Tuning the coalescence degree in the growth of Pt–Pd nanoalloys

Diana Nelli
Manuella Cerbelaud
Riccardo Ferrando
Chloé Minnai

December 2020

Coalescence is a phenomenon in which two or more nanoparticles merge to form a single larger aggrega...

Influence of gas environment and heating on atomic structures of platinum nanoparticle catalysts for proton-exchange membrane fuel cells

Yoshida, Kenta
Zhang, Xudong
Shimada, Yusuke
Nagai, Yasuyoshi
Hiroyama, Tomoki
Tanaka, Nobuo
Lari, Leonardo
Ward, Michael R.
Boyes, Edward D.
Gai, Pratibha L.

February 2019

Atomic-scale relaxations of platinum nanoparticles (Pt NPs) for fuel-cell catalysts are evaluated by...

Surface modification of small platinum nanoclusters with alkylamine and alkylthiol: An XPS study on the influence of organic ligands on the Pt 4f binding energies of small platinum nanoclusters

Fu, XY
Wang, Y
Wu, NZ
Gui, LL
Tang, YQ

January 2001

Platinum nanoclusters of average size 1.3 nm, modified with alkylamine, and alkylthiol, were prepare...

Self-Assembly of a Micrometers-Long One-Dimensional Network of Cemented Au Nanoparticles

Maheshwari, Vivek C.
Kane, Jennifer
Saraf, Ravi F.

January 2008

One-dimensional Au nanoparticles connected by ionic linkers self-assemble into a micrometer-scale ne...

Synthesis and characterization of size-selected platinum clusters through scanning transmission electron microscopy and electrochemical methods

Harrison, Patrick James

July 2020

Platinum nanoparticles have a key role in today's society as catalysts for pharmaceutical applicatio...

Trapping and electrical characterization of single core/shell iron-based nanoparticles in self-aligned nanogaps

Labra Muñoz, J.A.
Konstantinović, Z.
Balcells, L.
Pomar, A.
Zant, H.S.J van der
Dulić, D.

August 2019

We report on the fabrication and measurements of platinum-self-aligned nanogap devices containing cu...

Correlative pipette probe electrochemistry - electron microscopy studies of platinum nanoclusters

Mecking Ornelas, Isabel

December 2020

This thesis focuses on combining Scanning ElectroChemical Cell Microscopy (SECCM) and aberration-cor...

Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt27(CO)31]4- Displaying a Defective Structure

Cesari, Cristiana
Berti, Beatrice
Funaioli, Tiziana
Femoni, Cristina
Iapalucci, Maria Carmela
Pontiroli, Daniele
Magnani, Giacomo
Riccò, Mauro
Bortoluzzi, Marco
Vivaldi, Federico Maria
Zacchini, Stefano

January 2022

The molecular Pt nanocluster [Pt27(CO)31]4- (14-) was obtained by thermal decomposition of [Pt15(CO)...

Chemical tuning of Coulomb blockade at room-temperature in ultra-small platinum nanoparticle self-assemblies

Tricard, Simon
Said-Aizpuru, Olivier
Bouzouita, Donia
Usmani, Suhail
Gillet, Angélique
Tassé, Marine
Poteau, Romuald
Viau, G.
Demont, Phillipe
Carrey, Julian
Chaudret, Bruno

January 2017

International audienceThis work describes self-assemblies of ultra-small platinum nanoparticles, the...

Chemical tuning of Coulomb blockade at room-temperature in ultra-small platinum nanoparticle self-assemblies

Tricard, Simon
Said-Aizpuru, Olivier
Bouzouita, Donia
Usmani, Suhail
Gillet, Angélique
Tassé, Marine
Poteau, Romuald
Viau, G.
Demont, Phillipe
Carrey, Julian
Chaudret, Bruno

January 2017

International audienceThis work describes self-assemblies of ultra-small platinum nanoparticles, the...

Tuning Coulomb blockade in ultra-small metallic nanoparticle self-assemblies, at room-temperature

Tricard, Simon
Said-Aizpuru, Olivier
Bouzouita, Donia
Usmani, Suhail
Gillet, Angélique
Tassé, Marine
Poteau, Romuald
Viau, G.
Demont, Phillipe
Carrey, Julian
Chaudret, Bruno

October 2016

International audienceTuning Coulomb blockade at room temperature in nanoparticle self-assemblies ca...

Synthesis of nanoparticles (NPs) with well controlled characteristics is crucial to better understand the behaviour of the active phase during reaction and to better correlate it with its catalytic performance. Among other self-assembly methods, the di-block copolymer approach is well suited to obtain monodisperse supported NPs which can serve as supported metallic catalysts on both flat (model catalysts) and powder (realistic catalysts) supports. In this approach, an amphiphilic di-block copolymer dissolved in toluene yields a system of inverse micelles of which the core can be charged with metallic precursors to ultimately yield networks with well-controlled characteristics (size, composition, inter-distance). Important questions must be addressed, in particular in the case of bimetallic systems, concerning the formation of unique NPs at the cores from the initially pre-formed bimetallic seeds or the stability of the NPs networks with increasing temperature in presence of reactive gases. We have chosen to work with PS-b-P2VP di-block copolymer micelles that were functionalized with chloro-auric acid and palladium di-acetate precursors. The precursors selectively bind with N-functions in the P2VP cores to form (bi-)metallic seeds within the micelles’ cores as it was previously established in the case of PdAg alloys. We have used an Environmental TEM (Titan ETEM G2, FEI/TFS) operated at 300kV under gas pressures up to 20 mbar to gain insight on their evolution/stability during heating under oxygen and CO (for CO oxidation catalysis). Temperature variation was achieved with a WildFire sample holder with dedicated heating MEMS-microchips (DENS Solutions) capable of reaching temperatures up to 1300°C. Monolayers of controlled AuxPd1-x core-metallized PS-b-P2VP micellar solutions were deposited by spin-coating (2000/4000 rpm) on the microchips. Special care was taken to minimize/prevent any influence of the electron beam on the observed events.The Au-rich system (Au80Pd20) showed that, under oxygen, the (bi-)metallic seeds within the P2VP cores begin to sinter around 350° and unique NPs are eventually formed around 500°C which is consistent with the decomposition temperature range of the PS-b-P2VP copolymer associated with metallic nuclei. Further heating up shows that the NPs network is stable up to 900°C. Approaching the melting temperature of gold (1064°C) the NPs begin to shrink; concomitantly, smaller NPs (that grow even at 1100°C) form around the shrinking NPs. These smaller NPs are formed with Pd atoms from the initial bimetallic NPs.In the case of the Pd-rich system (Au20Pd80), under oxygen, the seeds begin to sinter around 300°C and at 450°C demixing of the NPs is observed leading to Janus NPs (Au-rich/PdO, cf. Figure); the latter are readily reduced and homogeneous NPs reform upon CO exposure (cf. Figure).The stability of the bimetallic NPs seems to be driven by the intrinsic properties of the metals composing them.Thanks are due to the METSA network for supporting this study and to CLYM for the access to the ETEM.

Cadete Santos Aires, F.J.
Ehret, E.
Vas, J.V.
Chatre, C.
Landrivon, E.
Duchamp, M.
Epicier, Thierry

May 2022

SSCI-VIDE+ING:MEME+FCA:EEH:ELA:TEPInternational audienceObservation of liquids within a transmission...

Synthesis of nanoparticles (NPs) with well controlled characteristics is crucial to better understand the behaviour of the active phase during reaction and to better correlate it with its catalytic performance. Among other self-assembly methods, the di-block copolymer approach is well suited to obtain monodisperse supported NPs which can serve as supported metallic catalysts on both flat (model catalysts) and powder (realistic catalysts) supports. In this approach, an amphiphilic di-block copolymer dissolved in toluene yields a system of inverse micelles of which the core can be charged with metallic precursors to ultimately yield networks with well-controlled characteristics (size, composition, inter-distance). Important questions must be addressed, in particular in the case of bimetallic systems, concerning the formation of unique NPs at the cores from the initially pre-formed bimetallic seeds or the stability of the NPs networks with increasing temperature in presence of reactive gases. We have chosen to work with PS-b-P2VP di-block copolymer micelles that were functionalized with chloro-auric acid and palladium di-acetate precursors. The precursors selectively bind with N-functions in the P2VP cores to form (bi-)metallic seeds within the micelles’ cores as it was previously established in the case of PdAg alloys. We have used an Environmental TEM (Titan ETEM G2, FEI/TFS) operated at 300kV under gas pressures up to 20 mbar to gain insight on their evolution/stability during heating under oxygen and CO (for CO oxidation catalysis). Temperature variation was achieved with a WildFire sample holder with dedicated heating MEMS-microchips (DENS Solutions) capable of reaching temperatures up to 1300°C. Monolayers of controlled AuxPd1-x core-metallized PS-b-P2VP micellar solutions were deposited by spin-coating (2000/4000 rpm) on the microchips. Special care was taken to minimize/prevent any influence of the electron beam on the observed events.The Au-rich system (Au80Pd20) showed that, under oxygen, the (bi-)metallic seeds within the P2VP cores begin to sinter around 350° and unique NPs are eventually formed around 500°C which is consistent with the decomposition temperature range of the PS-b-P2VP copolymer associated with metallic nuclei. Further heating up shows that the NPs network is stable up to 900°C. Approaching the melting temperature of gold (1064°C) the NPs begin to shrink; concomitantly, smaller NPs (that grow even at 1100°C) form around the shrinking NPs. These smaller NPs are formed with Pd atoms from the initial bimetallic NPs.In the case of the Pd-rich system (Au20Pd80), under oxygen, the seeds begin to sinter around 300°C and at 450°C demixing of the NPs is observed leading to Janus NPs (Au-rich/PdO, cf. Figure); the latter are readily reduced and homogeneous NPs reform upon CO exposure (cf. Figure).The stability of the bimetallic NPs seems to be driven by the intrinsic properties of the metals composing them.Thanks are due to the METSA network for supporting this study and to CLYM for the access to the ETEM.

Cadete Santos Aires, F.J.
Ehret, E.
Vas, J.V.
Chatre, C.
Landrivon, E.
Duchamp, M.
Epicier, Thierry

May 2022

SSCI-VIDE+ING:MEME+FCA:EEH:ELA:TEPInternational audienceObservation of liquids within a transmission...

Dynamic covalent nanoparticle building blocks

Kay, Euan Robert

July 2016

The author thanks the Royal Society of Edinburgh and Scottish Government for a personal research fel...

Synthesis, Electrochemical Characterization and Molecular Dynamics Studies of Surface Segregation of Platinum Nano-Alloy Electrocatalysts

Favry, E.
Wang, D.
Fatauzzi, D.
Anton, J.
Su, D.
Jacob, T.
Alonso-Vante, N.

May 2011

Alloy Pt–M (M = Co, Ni) nanocatalysts, supported on carbon Vulcan XC-72, were synthesized using the ...

Tuning the coalescence degree in the growth of Pt–Pd nanoalloys

Diana Nelli
Manuella Cerbelaud
Riccardo Ferrando
Chloé Minnai

December 2020

Coalescence is a phenomenon in which two or more nanoparticles merge to form a single larger aggrega...

Influence of gas environment and heating on atomic structures of platinum nanoparticle catalysts for proton-exchange membrane fuel cells

Yoshida, Kenta
Zhang, Xudong
Shimada, Yusuke
Nagai, Yasuyoshi
Hiroyama, Tomoki
Tanaka, Nobuo
Lari, Leonardo
Ward, Michael R.
Boyes, Edward D.
Gai, Pratibha L.

February 2019

Atomic-scale relaxations of platinum nanoparticles (Pt NPs) for fuel-cell catalysts are evaluated by...

Surface modification of small platinum nanoclusters with alkylamine and alkylthiol: An XPS study on the influence of organic ligands on the Pt 4f binding energies of small platinum nanoclusters

Fu, XY
Wang, Y
Wu, NZ
Gui, LL
Tang, YQ

January 2001

Platinum nanoclusters of average size 1.3 nm, modified with alkylamine, and alkylthiol, were prepare...

Self-Assembly of a Micrometers-Long One-Dimensional Network of Cemented Au Nanoparticles

Maheshwari, Vivek C.
Kane, Jennifer
Saraf, Ravi F.

January 2008

One-dimensional Au nanoparticles connected by ionic linkers self-assemble into a micrometer-scale ne...

Synthesis and characterization of size-selected platinum clusters through scanning transmission electron microscopy and electrochemical methods

Harrison, Patrick James

July 2020

Platinum nanoparticles have a key role in today's society as catalysts for pharmaceutical applicatio...

Trapping and electrical characterization of single core/shell iron-based nanoparticles in self-aligned nanogaps

Labra Muñoz, J.A.
Konstantinović, Z.
Balcells, L.
Pomar, A.
Zant, H.S.J van der
Dulić, D.

August 2019

We report on the fabrication and measurements of platinum-self-aligned nanogap devices containing cu...

Correlative pipette probe electrochemistry - electron microscopy studies of platinum nanoclusters

Mecking Ornelas, Isabel

December 2020

This thesis focuses on combining Scanning ElectroChemical Cell Microscopy (SECCM) and aberration-cor...

Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt27(CO)31]4- Displaying a Defective Structure

Cesari, Cristiana
Berti, Beatrice
Funaioli, Tiziana
Femoni, Cristina
Iapalucci, Maria Carmela
Pontiroli, Daniele
Magnani, Giacomo
Riccò, Mauro
Bortoluzzi, Marco
Vivaldi, Federico Maria
Zacchini, Stefano

January 2022

The molecular Pt nanocluster [Pt27(CO)31]4- (14-) was obtained by thermal decomposition of [Pt15(CO)...

Chemical tuning of Coulomb blockade at room-temperature in ultra-small platinum nanoparticle self-assemblies

Abstract

Extracted data

Chemical tuning of Coulomb blockade at room-temperature in ultra-small platinum nanoparticle self-assemblies

Abstract

Extracted data

Related items

Related items