Chemical Preparations of Metal Nanoparticle-Modified ... · Collaboration with Professor Kityk....

Chemical Preparations of

Metal Nanoparticle-Modified Electrodes

Munetaka Oyama

Associate Professor

Department of Material Chemistry

Graduate School of Engineering

Kyoto University, Japan

Graduate School of Engineering, Kyoto University, Japan

Kyoto in Japan

Capital:

794-1868

Top Universities for Chemistry

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3. University of California U. S.

4. Stanford University U. S.

5. Harvard University U. S.

6. University of Oxford U. K.

7. NUS Singapore

8. University of Tokyo Japan

16. Kyoto University Japan

QS World University Ranking 2018

http://www.topuniversities.com/......../chemistry

My Research History

1991 Dr. Sci. Kyoto University

Research Associate Nagoya University

Kyoto University

Spectroelectrochemistry in Organic Solvents

2001 Associate Professor Kyoto University

Nanomaterials Laboratory

Metal Nanoparticles Modified Electrodes

Graduate School of Engineering, Kyoto University

201720011989

Metal Nanoparticles

Time Cited and Number of Papers

AuNPs / ITOElectroanalysis

Our Research Progress since 2001

AuNPs / ITO

Seed-Mediate Growth

Noble Metal NPs / ITO

Commercially

Available NPs / ITO

Noble Metal NPs / Metals

AuNPs in Kimwipes

Chemical Preparations of

Various Nanostructures

Noble Metal NPs + grapheneAttachment of Seed NPs

Morocco

Malaysia

Electroanalysis

Nonlinear Optics

Sensing Devices

Poland

Saudi Arabia

ElectrocatalysisChina

Our Research Progress since 2001

Galvanic Replacement Reactions for

Preparing Noble Metal NPs / Metals

Metal NPs for Electrode Materials

Nanoparticle-

Attached ITO

ConductorSolution Metal

NanoparticlesGlass Indium Tin Oxides

Original of Seed-Mediated Growth Method

HAuCl4

Sodium Citrate

Seed Solution

Growth Solution

Cetyltrimethylammonium bromide

HAuCl4

Ascorbis Acid

Au nanospheres, diam. 4 nm

(CH2)15

J. Phys. Chem. B, 105, 4065 (2001). Adv. Mater. 15, 414 (2003).

Murphy and coworkers,

Our Seed-Mediated Growth Method

2 hoursHAuCl4

Sodium Citrate

24 hours

Seed Solution

Crystal Growth

Chemical Reduction

Growth Solution

HAuCl4

Ascorbis Acid

Substrate Indium Tin Oxide (ITO)

(CH2)15

Two-Step

Immersion

Au nanospheres, diam. 4 nm

Attachment of

Au Nano-seeds

Kambayashi, Zhang, Oyama, Cryst. Growth Des., 5, 81 (2005).

Attachment and Growth of AuNPs

Crystal growth of 60 - 80 nm of

Au Nanoparticles

Growth SolutionSeed Solution

for 2 hours for 24 hours

FE-SEM FE-SEM

Attachment and Growth of AuNPs

Crystal growth of 60 - 80 nm of

Au Nanoparticles

Growth SolutionSeed Solution

for 2 hours for 24 hours

FE-SEM FE-SEM

Attachment of Dispersed Au Nanoparticles

Zoom out

Time Course of Growth of AuNPs

Seed Solution

for 2 hours

Growth Solution

ca. 9 nm ca. 15 nm ca. 21 nm ca. 50 nm

24 hr.1 hr.1 min.

5 min.

Fabrication of Electrodes

Conducting Tape(Copper Tape)

AuNP-attached ITO substrate

diam. 2 mm

Non-Conducting Tape

Surface Images of AuNPs

Au Au Au

Growth Solution

for 24 hours

Growth Solution

for 24 hours

Crystal

Growth

Amorphous

0 1000 2000 3000 4000 5000 6000 7000

MPTMS/ITO

Au/ITOAu/MPTMS/ITO

Rct = 1044 cm2

Rct = 3074 cm2

Au Au Au

in 0.1 M PBS

(pH7.4)

containing

1 mM Fe(CN)64-

1 mM Fe(CN)63-.

Electrochemical Impedance

Zhang, Kambayashi, Oyama, Electrochem. Commun., 6, 683 (2004).

Dr. Jingdong Zhang

Professor

Huazhong University of Science and Technology

Wuhan, China

Oct. 2003 – Mar. 2005 in Kyoto

EIS, ascorbic acid, uric acid etc.

Electrochem. Commun., 6, 683 (2004). Times Cited: 104

Electroanalysis, 17, 408 (2005).

hemoglobin Electrochim. Acta, 50, 85 (2004). Times Cited: 118

myoglobin J. Electroanal. Chem., 577, 273 (2005). Times Cited: 97

NO detection Anal. Chim. Acta, 540, 299 (2005). Times Cited: 82

TiO2-AuNPs Electrochem. Solid-State Lett., 8, E49 (2005).

Dr. Jingdong Zhang’s Contributions

uric acid Indian J. Chem. A, 44, 945 (2005).

paracetamol Electrochem. Commun., 7, 803 (2005). Times Cited: 204

atenolol Electrochem. Commun., 8, 65 (2006). Times Cited: 169

nandrolone Talanta, 72, 3140 (2007).

methylprednisolone acetate J. Pharm. Biomed. Anal., 44, 1147 (2007).

Collaboration with Professor Goyal

Dr. Rajendra N. Goyal

Professor Emeritus

Indian Institute of Technology

Roorkee, India.

Goyal, Gupta, Oyama, Bachheti

Electrochem. Commun., 7, 803 (2005).

paracetamol

guanosine and GTP Anal. Chim. Acta, 581, 32 (2007).

adenosine and ATP Electroanalysis, 19, 575(2007) .

adenosine and guanosine Talanta, 71, 1110 (2007). Times Cited: 157

dopamine and serotonin Talanta, 72, 976 (2007). Times Cited: 196

salbutamol J. Electroanal. Chem., 611, 140 (2007).

5-hydroxytryptamine and 5-hydroxyindole

Sens. Actuators B, 134, 816 (2008). Times Cited: 179

prednisolone Bioelectrochemistry, 74, 272 (2009).

dopamine and ascorbic acid J. Electroanal. Chem., 631, 58 (2009).

norepinephrine Sens. Actuators B, 153, 232 (2011).

paracetamol and epinephirine Anal. Chim. Acta, 693, 35 (2011).

tryptophan Talanta, 85, 2626 (2011).

Dr. Gang Chang

Professor

Hubei University

Wuhan, China

Dr. Chang Gang’s Contributions

Dec. 2003 – Sep. 2006 in Kyoto

Silver Nanoparticle-Attached ITO

-0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7-100

E / V (vs.Ag/AgCl)1000 nm

200 nm

in 0.1 M PBS

Fe(CN)64-/Fe(CN)6

AgSP/ITO

AgNP/ITO

Chang, Oyama, Hirao, J. Phys. Chem. B, 109, 1204 (2005).

Palladium Nanoparticle-Attached ITO

-0.3 -0.2 -0.1 0.0 0.1 0.2

E / V (vs. Ag/AgCl)

Pd bulk

Pd nanoparticles

Platinum Nanoparticle-Attached ITO

0.1 0.2 0.3 0.4 0.5 0.6 0.7

E / V (vs. AgCl/Ag)

0.0 0.2 0.4 0.6 0.8 1.0

E / V (vs. AgCl/Ag)

PtNP/ITO

Methanol

Oxidation

Oxygen

Reduction

At Huazhong University of Science & Technology

Wuhan China, May 2017

Prof. Gang Chang

Hubei University, Wuhan, China

Prof. Jingdong Zhang

Huazhong University of Science &

Technology (HUST), Wuhan, China

Dr. Ali Umar’s Contributions

May 2004 – Mar. 2007 in Kyoto

Dr. Akrajas Ali Umar

Associate Professor

Institute of Micro-Engineering and

Nanoelectronics (IMEN)

Universiti Kebangsaan Malaysia (UKM)

Malaysia

Dr. Nouneh Khalid’s Contributions

Sep. 2007 – May. 2009 in Kyoto

Growth and optical features of AgNPs on ITO

Journal of Alloys Compounds, 509, 2631 (2011).

Synthesis and optical features of NiNPs on ITO

Dr. Khalid Nouneh

Assistant Professor

Universite Ibn Tofail

Morocco

Dr. Md. Abdul Aziz’s Contributions

Nov. 2009 – Oct. 2011 in Kyoto

Thermal-driven attachment of AuNPs on ITO

Journal of Nanoparticle Research, 15, 1618 (2013).

Preparation monodispersed carboxylate-functioalized AuNPs

Gold Bulletin, 47, 127 (2014).

Dr. Md Abdul Aziz

Research Scientist

King Faud University of

Petroleum and Minerals

Saudi Arabia

Dr. Xiaomei Chen’s Contributions

Dr. Xiaomei Chen

Professor

Jimei University

Reduction

+ Metal IonsGraphene

PdNPs+GO, H2O2 Electrochim. Acta, 97, 398 (2013).

PtNPs+RGO, Oxalic Acid Nanoscale, 5, 5779 (2013).

PtPdNCs+RGO, MeOH Carbon, 66, 387 (2014).

PtPdNPs+RGO, EtOH J. Mater. Chem. A, 2, 315 (2014).

PtPdNCs+RGO, Glucose Microchim. Acta, 181, 783 (2014).

AuPdNPs+RGO, 4-nitrophenol J. Mater. Chem. A, 2, 5668 (2014).

AuNPs+RGO, 3,3,5,5-TMB Dalton Trans., 43, 7449 (2014).

PtPdNDs+RGO, 3,3,5,5-TMB Sens. Actuators B, 201, 286 (2014).

PdNPs+RGO, 4-nitrophenol Chem. Lett., 43, 919 (2014).

Dr. Xiaomei Chen’s Contributions

Prof. Ivan Kityk

Czestochowa University

of Technology,

Poland

Physics, Non-linear Optics

Collaboration with Professor Kityk

Circularly polarized light-induced electrogyration

Physica E, 2005, 27, 420.

Acoustical circularly polarized gyration

Physica E, 2005, 28, 178.

Nonlinear optical properties

Nanotechnology, 2005, 16, 1687.

Control of the plasmon absorption with a two-color excitation

Journal of Applied Physics, 2005, 98, 084304.

Circular acoustogyration effect

Applied Optics, 2005, 44, 6905.

Kinetics of photoinduced changes

Philosophical Magazine Letters, 2005, 85, 549.

Non-linear optical properties

Physica E, 2006, 31, 38.

Luminescence of erbium doped AgNPs

Applied Surface Science, 253, 1626 (2006).

Acoustically induced nonlinear optics of PdNPs

Physica E, 35, 121 (2006).

Second order optical effects of PdNPs

Journal of Modern Optics, 55, 187 (2008).

Nonlinear optical properties of NiNPs

Optical & Laser Technology, 40, 499 (2008).

Nonlinear optical properties of AuNPs on ZnO

Nanotechnology, 19, 18709 (2008).

Journal of Nano Research, 2, 31 (2008).

Laser treatment of AgNPs

Materrals Chemistry and Physics, 113, 187 (2009).

Superlattices and Microstructures, 46, 637 (2009).

Optical features of AuNPs on ITO

Optical Communications, 284, 245 (2011).

Photoinduced absorption of AgNPs on ITO

Journal of Alloys Compounds, 509S, S424 (2011).

Picosecond laser treatment of AgNPs on ITO

Pump-probe third harmonic generation of AuNPs on ITO

Materials Letters, 74, 226 (2012).

Laser stimulated optical features of AuNPs on ITO

Physica E, 44, 1182 (2012).

Laser operated optoelectronic devices of AuNPs on FTO

J. Mater. Sci: Materials in Electronics, 24, 2422 (2013).

Second harmonic generation in LiB3O5 in AgNP/ITO

J. Mater. Sci: Materials in Electronics, 24, 4204 (2013).

AuNPs aggregation in laser induced anisotropy of ITO

Light reflection reduction of AgNPs attached Al-doped ZnO

Physica E, 56, 283 (2014).

Nonlinear optical features of BiB3O6/PVA on Al-doped ZnO

Physica E, 64, 1 (2014).

Third harmonic generation of AuNPs on Al-doped and Ga-doped ZnO

Physica E, 71, 91 (2015).

AuNPs/ITO prepared by Dr. Aziz

AuNP-Modified ITO Electrodes

Oyama, Fujita, Anal. Sci., 31, 597 (2015).

100 nm

5, 10, 20 nm

Competitive attachment of commercially available AuNPs

Oyama, Fujita, Anal. Sci., 31, 597 (2015).

100 nm

5, 10, 20 nm

Competitive attachment of commercially available AuNPs

Au Au Au

Failures in Modifications

Gold nanoparticles (AuNPs)

on indium doped tin oxides (ITO)

Progress since Oct. 2016

Failure of the preparations

Lower density

attachment

Strange islands of

linker molecules

Gathering

Progress since Oct. 2016

Jan. 2017 - Jun. 2017

As struggles of trials,

the effects of the kinds of ITO substrates and

the concentrations of linker molecules, APTMS.

Jul. 2017

As a final trial, we tried to change the source of AuNPs.

Gold Colloid Solutions

Previous Sigma

tannic acid capped (5, 10, 20 nm)

Present Sigma-Aldrich, but actually Cytodiagnostics (Canada)

stabilized suspension in citrate buffer

(5, 10, 15, 20, 30, 40, 50, 60, 80, 100 nm)

stabilized suspension in 0.1 mM PBS, reactant free

(5, 10, 15, 20, 30, 40, 50, 60, 80, 100, 150, 200,

250, 300, 400 nm)

stabilized suspension in citrate buffer stabilized suspension in 0.1 mM PBS,

reactant free

Jul. 2017

10 nm 15 nm

20 nm 30 nm

AuNPs: stabilized suspension in 0.1 mM PBS, reactant free

4% APTMSSep. 2017

An Important Point for Modification

Au Au Au

SSSSSSSSSS

small molecules

Brust et al., JCS Chem. Commun., 1994, 801.

citrate ions

Frens, Nature,

1973, 241, 20.

polymers

thiolssurfactants

10 nm 15 nm

20 nm 30 nm

4% APTMSOct. 2017

10 nm 15 nm

20 nm 30 nm

2% APTMSOct. 2017

Preparations for Professor Kityk

Various sized gold nanoparticles (AuNPs)

on fluorine doped tin oxides (FTO)

AuNP-Modified FTO Electrodes

10 nm 15 nm

20 nm 30 nm

2% APTMSOct. 2017Sigma-Aldrich

10 nm 50 nm

10 nm 15 nm

20 nm 30 nm

Preparations for Professor Laskowski

Silver nanoparticles (AgNPs)

on fluorine doped tin oxides (FTO)

Silver Colloid Solutions

Sigma-Aldrich (now Merch), but actually nanoComposix (USA)

0.02 mg/mL in aqueous buffer,

contains sodium citrate as stabilizer

(10, 20, 40, 60, 100 nm)

BBI solutions (previous, BB international Ltd.)

Silver nanoparticles (20, 40, 60, 80, 100 nm)

Cytodiagnostics

Sigma-Aldrich 15 nm

BBI solutions 30 nm

AgNPs: 20 nm

2% APTMSNov. 2017From Poland

AuNPs: 20 nm, stabilized suspension in 0.1 mM PBS, reactant free

Systematic Comparison of Modification

2% APTMSDec. 2017

FTO from Sigma-Aldrich FTO from Poland

AgNPs: 20 nm, 0.02 mg/mL in buffer, contains sodium citrate as stabilizer

2% APTMSDec. 2017

AgNPs: 20 nm, 0.02 mg/mL in buffer, contains sodium citrate as stabilizer

4% APTMSDec. 2017

Recent Development of

Metal Nanoparticle-Modified Electrodes

0 0.2 0.4 0.6E / V (vs. Ag|AgCl)

Ni Electrode

Au Electrode

100 nm

AuNP-Modified

Ni Electrode

Uemoto, Nakayama, Chen, Chang, Oyama,

Electroanalysis, 27, 964 (2015).

Electrode

AuNP-Modified Ni Electrode

Ni2+ + 2e- ⇄ Ni(s) E0 = -0.24 V

AuCl2- + e- ⇄ Au(s) + 2Cl- E0 = 1.15 V

AuCl4- + 2e- ⇄ AuCl2

- + 2Cl- E0 = 0.93 V

2AuCl4- + 3Ni(s) → 2Au(s) + 3Ni2+ + 8Cl-

Galvanic Replacement Reaction

During just immersing an electrode

in a solution containing only HAuCl4

Ni Electrode Treated with HAuCl4

with HAuCl4

Ni Wire Treated with HAuCl4

with HAuCl4

I/μA・

E / V vs. Ag / AgCl

1.0×10-3 M HAuCl4 Immersion Time 1 hour

50 m 10 m 5 m

1.0×10-4 M HAuCl4 Immersion Time 1 hour

50 m 10 m 5 m

1.0 mM ferrocyanideImmersion Time: 1 hour

HAuCl4

0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40-10

0.00 0.10 0.20 0.30 0.40

E / V vs. Ag / AgCl E / V vs. Ag / AgCl

I / µ

E / V vs. Ag / AgCl

1.0×10-5 M 1.0×10-6 M 1.0×10-7 M

0.00 0.20 0.40 0.60

E / V vs. Ag / AgCl E / V vs. Ag / AgCl

I / µ

E / V vs. Ag / AgCl

1.0 mM uric acidImmersion Time: 1 hour

HAuCl41.0×10-4 M 1.0×10-5 M 1.0×10-6 M

-0.50 0.00

I / µ

E / V vs. Ag / AgCl E / V vs. Ag / AgCl E / V vs. Ag / AgCl

10 mM glucoseImmersion Time: 1 hour

HAuCl41.0×10-4 M 1.0×10-5 M 1.0×10-6 M

Summary

Wet Chemical Synthesis of Metal Nanoparticles

Potentials for Nanostructuring

and Electrochemical Applications

Easy Synthesis in Aqueous Solution

at Room Temperature

At moment, we would like to focus the modification

of noble metal nanoparticles on Ni or Ti electrodes

The Ministry of Education, Culture, Sports, Science and

Technology, Japan

All collaborators, coauthors,

posdocs and students in my group.

Acknowledgements

Japan Society for the Promotion of Science (JSPS)

Chemical Preparations of Metal Nanoparticle-Modified ... · Collaboration with Professor Kityk....

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