New Nanomaterials for the Electrochemical …...Recently, the nanostructures binary transition metal...
Transcript of New Nanomaterials for the Electrochemical …...Recently, the nanostructures binary transition metal...
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
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The Analytes…
• Dopamine
• Melatonin
• Glucose
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Electrochemical Techniques
Cyclic voltammetry
(CV)
Different Pulse Voltammetry
(DPV)
Amperometry
(i-t)
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Contd.,
Cyclic Voltammetry• Reversible irreversible
Spectroelectrochemistry CV
Cyclic VoltammetryReversible irreversibleSpectroelectrochemistry CV (NFPMo)
Carbon nanomaterials in
sensor and biosensor application
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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
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(A)(B)
(C)
(A)
(B)
(C)
Sensors
Capacitors Batteries
Solar Cells
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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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Prussian blue structure materials and application
Prussian blue structure materials and application
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Prussian blue structure materials and application
Electrochemical synthesisElectrochemical deposition
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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
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Water oxidation catalysis(WOC)Oxygen Evolution Reaction(OER)
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DNA RNA bases determination
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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
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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
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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
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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.
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Electrochemical sensor
Supercapacitor
and
Energy Storage Devices
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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 ???
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(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
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Chapter-3
Scheme 1. Synthesis of graphene sheet-like activated carbon (GPAC) and their applicationsas an electrode material for supercapacitor and catechin sensor.
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Scheme of work
Results-Supercapacitor
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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
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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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