以材料發展為例談如何發展學術研究與應用及拉近產業與學術的距離New Nanomaterials for the Electrochemical Biosensing and Energy Applications; From Academic Research to Industrial Applications

Shen-Ming Chen陳生明

National Taipei University of Technology台北科技大學

CV

Materials and Methods

Materials

Working electrode

Reference electrode

Auxilliary electrode

Technique

Target analyte

Methods

2

The Analytes…

• Dopamine

• Melatonin

• Glucose

3

Electrochemical Techniques

Cyclic voltammetry

(CV)

Different Pulse Voltammetry

(DPV)

Amperometry

(i-t)

11

Contd.,

Cyclic Voltammetry• Reversible irreversible

Spectroelectrochemistry CV

Cyclic VoltammetryReversible irreversibleSpectroelectrochemistry CV (NFPMo)

Carbon nanomaterials in

sensor and biosensor application

9

0 Dimensional

2 Dimensional

Carbon

allotropes

Supporting Materials for Electrode

• Onion Like Carbon• Carbon Dot• Fullerene• Nano Diamond• Graphene Dot

• Single Walled CarbonNanotube• Multi Walled Carbon Nanotube• Carbon Nanohorons

• Multilayered Graphitic Sheets• Graphene• Graphene Oxide

• Graphite• Diamond

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Graphite

1. NaNO3

2. Conc. H2SO4

3. KMnO4

4. 30% H2O2

Graphene OxideUltrasonication

Synthesis of Graphene oxide (GO)

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DOI: 10.1039/c9nr09148c Nanoscale (2020)

Preparation of Graphene

Metal Oxides

✓ Recently, the nanostructures

binary transition metal oxides

(BTMOs) has been a potential

candidate for electrochemical

sensor applications.

✓ Low cost, high electrochemical

activity, good electrical

conductivity, stability, and high

theoretical capacitance etc.

13ISBN 978-953-307-1992

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➢ Tetraphenylporphyrin (TPP) as an important class of

conjugated macrocyclic compounds, contain methine bridges

(=CH–) and plays an important role in essential for life.

➢ The compound is a dark purple solid that dissolves in

non-polar organic solvents such as chloroform and

benzene.➢ Porphyrin has a delocalized system involving 26 π electrons and satisfies

Huckel’s rule for aromaticity (4n + 2p electrons).

➢ The π electrons of porphyrin lead to their unique optical,

electronic, magnetic, redox, catalytic, Self-assembly, and other

properties.

➢ These excellent physicochemical properties of porphyrin

used for fabrication of sensing and electro catalyst nano

architecture.

Tetraphenyl porphyrin

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Graphene–glucose oxidase biocomposite

Biosensors and Bioelectronics 39 (2013) 70–75 (Total cites: 122)

D nanomaterials

16

(A)(B)

(C)

(A)

(B)

(C)

Sensors

Capacitors Batteries

Solar Cells

17

2D chalcogenides and

their application

Classification of perovskites

Perovskite structure

Inorganic oxides

perovskitesHalide perovskites

Intrinsic

Perovskites

Doped

Perovskites

Alkali Halide

Perovskites

Organometal

Halide

Perovskites

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21

22

23

Prussian blue structure materials and application

Prussian blue structure materials and application

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25

Prussian blue structure materials and application

Electrochemical synthesisElectrochemical deposition

26

Thin GO sheets wrapped uniformlyabove the tubular network ofMWCNTs via non-covalent π- π*interactions to form a stable hybridmaterial.

• Reduction peak at -1.5Vcorresponds to reduction of oxygenfunctional groups.•The onset potential of thecomposite (-0.3 V) is much lowerthan that of pristine GO (-0.7 V).• Incorporation of MWCNT greatlyenhances the reduction of GO.

FESEM image of ERGO-MWCNT

Electrochemical reduction of GO-MWCNT

Biosensors and Bioelectronics, (2012)

Electrochemistry Communications, 17 (2012)

Electrochemical synthesis for Electrochemical Sensing

28

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30

Water oxidation catalysis(WOC)Oxygen Evolution Reaction(OER)

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32

DNA RNA bases determination

33

12

Synthesis and Fabirication of Binary Nanosheets (Bi2Te3@g-C3N4) Modified Electrode as Rapid

Electrochemical Sensor of Ractopamine

g-C3N4

Bi2Te3

g-C3N4

S

P

C

E

Binary nanosheets (Bi2Te3/g-c3N4)

Ractopamine

Electrochemical Sensor of

Ractopamine

29

23

Cu2O @ g-C3N4

Blood sample+8-oxo-dG

Urine sample+8-oxo-dG

DNA Damage Biomarker 8-hydroxy-2’-

deoxyguanosine

(8-HOG)

Schematic diagram of electrochemical sensor towards 8-HOG

ElectropolymerizationPreparation of PEDOT modified on GCE

Repeated CVs of PEDOT film growth in

aqueous solution containing 0.01 M

EDOT and 0.005 M HP-b-CD in 0.1M

LiClO4 pH (6.8) aqueous solution. Scan

rate = 0.1 V/s, electrode = glassy carbon.

Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)PEDOT & PSS

EQCM measurements of PtAu hybrid film, platinum

and nanoAu particles

• (A) Repeated cyclic voltammograms of

gold electrode modified with PtAu

hybrid film from 0.5M H2SO4

containing 1×10−3 M KAuCl4·3H2O and

1×10−3M K2PtCl6 with 100µM L-

Cysteine.

• (B) The change in EQCM frequency

was recorded concurrently with the first

seven consecutive cyclic

• voltammograms between −0.15 and

1.5V. The inset shows total frequency

change ∆F vs. scan cycle.

SEM characterization of Pt particle, nanoAu and

PtAu hybrid film

• (A) SEM images of the Pt particles

deposited on ITO from 0.5M H2SO4

containing 1×10−3MK2PtCl6

(magnification 25 K, view angle 60◦)

• (B) NanoAu particles deposited on ITO

from 0.5M H2SO4 containing 1×10−3 M

KAuCl4·3H2O (magnification 25K, view

angle 60◦).

• (C) PtAu hybrid film deposited on ITO

from 0.5M H2SO4 containing 1×10−3 M

KAuCl4·3H2O and 1×10-3MK2PtCl6 (100µ

L-Cysteine, magnification 20K, 30 cycles).

• (D) PtAu hybrid film (magnification 20K,

60 cycles). (E) PtAu hybrid film

(magnification 20K, 30 cycles, 60◦). (F)

PtAu hybrid film (magnification 20K, 60

cycles and 60◦).

The particle size of Pt and nanoAu were

in the range of 200–300, 50–80 nm.

Schematic representation of the simultaneous

electro catalytic oxidation of DA, AA and

UA by PtAu hybrid film modified electrode.

• Explain electron mediating properties

PtAu hybrid film towards oxidation DA,

AA and UA.

• NanoAu exhibited one additional

oxidation peak potential about +1.2V.

• On addition AA, DA, UA or mixture,

oxidation peak current Au increased.

• Phenomenon attributed mediated

oxidation reaction oxidation state Au

towards DA, AA, UA or mixture.

Simultaneous catalytic oxidation of AA, DA and UA

• (A) CV of the PtAu hybrid film (pH 4.0) containing individual concentrations of AA, DA and UA mixture.

• [AA]: 0.0, 0.069, 0.346, 0.692, 1.038 and 1.384 mM.

• [DA]: 0.0, 0.022, 0.110, 0.220, 0.330 and 0.440 mM;

• [UA]: 0.0, 0.062, 0.312, 1.249, 1.874 and 2.499 mM.

• (a') bare GC [AA, DA, UA]: 1.384, 0.44 and 2.499 mM.

• (B) DPV of AA, DA and UA mixture at PtAu hybrid film at GC (pH 4.0) solution containing individual concentration of AA (from A to I): 0.0, 0.103, 0.206, 0.413, 0.619, 0.826, 1.03, 1.23, 1.44 and 1.65 mM;

• [DA] (from A to I): 0.0, 0.024, 0.048, 0.096, 0.144, 0.192, 0.240, 0.280, 0.336 and 0.384 mM;

• [UA] (from A to I): 0.0, 0.021, 0.042, 0.084, 0.126, 0.168, 0.210, 0.252, 0.294 and 0.336 mM.

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❑Stable under storage

conditions and

❑Immobilized

The component used to bind the target molecule must be

❑Highly specific

Electrode

Electrochemical Biosensors

Hemoglobin

44

Electrochemical Biosensors

Glucose

biosensors

H2O2 biosensor

Polymer based biosensor

Dove press 2015,4, 25—4647

Bio-anode preparation

MWCNT

ZnOZnO

ZnOZnO

ZnOZnO GOx

GOx

GOx

SENSOR ACTUAT B-CHEM, 166-167 (2012) 372-377

• S. M. Chen et. al., Sensors & Actuators: B. Chemical (2017)

Bi-enzymatic sensor

The direct regeneration of FAD at polyphenazine mediator

Analytica Chimica Acta 881 (2015) 1–23 50

CNT based biosensors

ImportantDirect Bioelectrochemistry

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Electrochemical sensor

photocatalysis

Photoelectrocatalysis

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A Study of Electrocatalytic and Photocatalytic Activity of Cerium Molybdate

Nanocubes Decorated Graphene Oxide for the Sensing and Degradation of

Antibiotic Drug Chloramphenicol

57

ACS Appl. Mater. Interfaces 2017, 9, 6547−6559

Electrocatalytic and Photocatalytic Applications

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Synthesis of CeM and CeM/GO composite

Synthesis of CeM nanocubes Synthesis of GO and CeM/GO composite

The synthesis route for CeM, CeM/GO composite and its application for electrochemical sensor and

photocatalytic activity.

58

Electrochemical sensor

Supercapacitor

and

Energy Storage Devices

59

Porous Activated Carbon and Hybrid Metal Oxidesfor High Performance of Electrochemical Sensors and

Supercapacitor Applications

多孔活性碳與金屬氧化物複合材料特性及其應用於電

化學感測器與超級電容器之研究

Why we need biomass derived ACs ???

61

(Hazardous explosion)

CH

NS

✓ Ultra-high surface area (1000-4000 m2g-1)✓ Modulated pore size✓ Natural presence of heteroatoms like N, B, and S✓ Various oxygen-containing functional groups ✓ Excellent thermal/electrical conductivity

Multiple applications of Biomass-derived ACs

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Fig.. Types of supercapacitors

Types of supercapacitors

EDLCs

Pseudocapacitors

Energy Environ. Sci., 2017, 10, 538--545

ASCs

Lignocellulosic Biomass-Derived, Graphene Sheet-likePorous Activated Carbon for Electrochemical

Supercapacitor and Catechin Sensing

64

Chapter-3

Scheme 1. Synthesis of graphene sheet-like activated carbon (GPAC) and their applicationsas an electrode material for supercapacitor and catechin sensor.

65

Scheme of work

Results-Supercapacitor

66

Fig. 3.6. (a) Ragone plot of the solid-state SC (GPAC/PVA/KOH/GPAC) device.(b) CV profiles for one cell, two cell and three cell device connected in series.(c) The GCD profiles for three cell device at different operating voltages.(d) Three cell assembled solid-state SC devices joined in series to instantaneously

light up red LED. Inset: Simultaneously light up the green LED.

Mitochondria

e- O2

Electron transport Chain

(ETC)

H2O

O2Reactive Oxygen Species (ROS)

O2 H2O2

Superoxide dismutase

(SOD)

Fe2

+

OH-

➢DNA Damage

➢Cell Mutation

➢Lipid Oxidation

➢Protein Dysfunctions

Formation of H2O2 in Human Body

Toxicity

DOI: 10.1039/c9nr09148c Nanoscale (2020)

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Electrocatalysis & Enzymatic catalysis

• Manganese Doped Molybdenum Diselenide for Effective Enzyme Immobilization: In-vitro and In-vivo Real Time Analysis for Hydrogen Peroxide Sensing

68

Sukanya Ramaraj, Mani Sakthivel, SMChen el. al,, ACS applies materials & interfaces, 2019Microchim Acta 2017. DOI 10.1007/s00604-017-2179-2

Electrocatalysis & Enzymatic catalysis

• Manganese Doped Molybdenum Diselenide for Effective Enzyme Immobilization: In-vitro and In-vivo Real Time Analysis for Hydrogen Peroxide Sensing

69Sukanya Ramaraj, Mani Sakthivel, SMChen el. al,, ACS applies materials & interfaces, 2019

Electrocatalysis & Enzymatic catalysis

• Facile solvothermal preparation of Mn2CuO4microspheres: Excellent electrocatalyst for real-time detection of H2O2 released from live cells

70P. Balasubramanian, M. Annalakshmi, Shen-Ming Chen et. al., ACS applies materials & interfaces, 2019

Electrochemical sensors & Biosensors• The Innovative Strategy for the Simultaneous

Determination of Anti-cancer Drug Flutamide and Environmental Pollutant 4-Nitrophenol Based on Novel Carbon black and β-Cyclodextrin Nanocomposite

S. Kubendhiran, R. Sakthivel, Shen-Ming Chen, et. al., Analytical Chemistry. 90 (2018) 6283−6291.

Active-site-rich CoMoSe2 Integrated Graphene Oxide

Nanocomposite as an Efficient Electrocatalyst for

Electrochemical Sensor and Energy Storage Applications

Graphical abstract

72Sukanya Ramaraj, Mani Sakthivel, Shen-Ming Chen*.., Analytical Chemistry,(2019)

Biofuel cell

A biofuel cell uses living organisms to produce electricity

Microbial fuel cellEnzymatic biofuel cell

Schematic illustration of the working principle of the ER-GO-CNT based

glucose/O2 biofuel cell. At the ER-GO-MWCNT/GOx/Nf bioanode, oxidation of

glucose to gluconolactone. At the GCE/Graphene-Pt composite biocathode,

Reduction of O2 to water.

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Photocatalytic Applications

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Thank you

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