Nanomaterials for Environmental and Energy

Applications

Jimmy C. Yu

The Chinese University of Hong Kong

 The Nanoscale
Carbon Influenza
nano-tube virus cell

molecule protein hair

atom transistor

0.1 1.0 10 100 1000 10000 100000 nm

1 10 100 m
 What is Nanotechnology?
The creation of functional materials, devices and
systems through control of matter at the scale of 1 to
100 nm, and the exploitation of novel properties and
phenomena at the same scale.
Two preparation approaches
 Top ⇨ Down:
Start with the bulk material and “cut away
material” to make what we want
(using nanolithography: e.g., e-beam writing, X-
ray or UV lithography)

 Bottom ⇨ Up:
Building what we want by assembling it from
building blocks (such as atoms and molecules)
based on chemistry.
 Scanning Tunneling Microscopy (STM)
A small STM tip (one atom thick) is brought within a few atomic
diameters (~ 0.1 nm) of the surface of interest.
A voltage (typically ~1 V) is then applied across the tip and the
sample. Under these conditions, a small current starts to flow (~1
nA) across the gap.

The tunneling current is sensitive

to height fluctuations on an atomic
scale and by scanning the tip across
the surface and continually measuring
the tunneling current an image can
be built up showing the position of
the individual atoms.
Nanosized particles exhibit different properties than
larger particles of the same substance

For example: melting point of a solid

Nano-sized particles melts at lower temperatures
because they have relatively more atoms on the
surface.
Surface atoms require less
energy to move because they are
in contact with fewer atoms of
the substance.

In contact with 3 atoms

In contact with 7 atoms

 Different Colors
• Bulk gold appears yellow in color
• Nanosized gold appears red in color
– The particles are so small that electrons are not free to move
about as in bulk gold
– Because this movement is restricted, the particles interact
differently with light

“Bulk” gold looks yellow 12 nanometer gold clusters of particles look red
 Party due to the large surface area, many nanomaterials are
active catalysts (e.g. nanosized titanium dioxide particles).
UV
O2
Conduction band
Strength of Common Oxidizing Agents
e¯
• O2¯ Oxidant Oxidation Potential

•OH Hydroxyl Radical •OH 2.8 V

Valence band
h+
Superoxide Radical •O2- 2.4 V
OH-
TiO2 Particle Ozone O3 2.0 V

Hydrogen Peroxide H2O2 1.8 V

Hypochlorite OCl- 1.5 V

Chlorine Cl2 1.3 V

Oxygen O2 1.2 V
 Photocatalytic Degradation of a Gaseous Organic Pollutant
Journal of Chemical Education 75, 750-751 (1998)

1. Coating of TiO2 on glass A B C D

2. Photocatalytic oxidation TiO2  x  x

CH2Cl2 + 4•OH  CO2 +2H2O +2HCl Sunlight   x x
 English Edition February 2002
始创于1845年，每月以英语、德语、波兰
语、法语、意大利语、日语、汉语、中文
二十多种语言在全球同步发行。

消除污染物的新法寶 這種常用的增白劑可以用來淨化空氣
【本文轉載自2002年4月號】 撰文╱王琳達（Linda Wang）翻譯／儲三陽

建築物、馬路和行人道將可以轉變成為對付空氣污染的設施。日本
和香港的研究人員在建材上塗上二氧化鈦，以測驗它抗污染的效果。
二氧化鈦是大家熟知的白色染料，也是白漆及牙膏的原料。它能清
淨空氣，因為它是個有效的光催化劑：加速陽光中的紫外線分解空
氣中水分子的速度，這個反應產生的羥基自由基，會攻擊空氣中的
有機或無機化合物，將它們變成無害的分子，而且下一場雨就可以
沖走了。但是把牙膏塗到人行道上卻發揮不了作用，因為其中的二
氧化鈦分子的結晶顆粒太大，其直徑大約是20~250奈米。想要去除
污染，要小到7奈米，這麼小的顆粒才能集合足夠大的表面積，發
揮光催化的本事。
1970年代早期，東京大學的研究人員報導了二氧化鈦的光催化能力。
從那時起，科學家就利用它消滅醫院各種表面上的細菌，與處理污
水，但用於戶外消除氮 氧化物卻是個新點子。在香港，水泥板上
塗了二氧化鈦，可以去除90%的氮氧化物。那些氮氧化物多是老舊
車輛、柴油卡車噴出的，也是造成煙霧、酸雨等環境污 染物的根 陽光照射到塗敷了二氧化
鈦的混凝土上，將氮氧化
源。香港中文大學的化學家余濟美說，用二氧化鈦塗敷層對付污染
物廢氣轉變成硝酸離子。
物，幾分鐘內就可以完成環境得花上幾個月的工作。此外，他補充 鹼性的混凝土會中和那些
說，二氧化鈦是催化劑，不是消耗品，可以一直發揮作用。 硝酸離子，然後雨水就可
以將它們沖走。
 光催化薄膜的自清潔效應

UV

Organic
pollutants CO2,
H2O

x
Mesoporous
TiO2
Conclusion: 1 m2 area could remove 0.1 g of NOx during a 12-hour day.
Maximum NO removal = 12%
NewScientist 7 Feb. 2004 p. 23
Incorporation of Photocatalysis in Urban Design
Technology Transfer
Indoor Air Purification
 Disinfection technology needed
A billion people on the planet don’t have access to clean drinking water

The 2010 cholera outbreak

in Haiti: death toll 4672
WHO guideline values for trihalomethanes (THMs)

CHCl3 200 g/L

CHCl2Br 60 g/L
CHClBr2 100 g/L
CHBr3 100 g/L
 2011 Germany E. coli O104:H4 outbreak
There were 3,785 cases and 45 deaths had been reported as of 27 July.
Seafood Restaurant Closed after Cholera Scare
Supermarket Closed after Cholera Scare 21 Sept. 2011
 Patents: US 6803077, ZL 02119304.5, AU 2003229253,
CA 2480736, DE 10392572, HK 1060257, WO 2003092886
 Modes of Microbe Killing Action
Control
Disinfection Method h OH O2-

UV (254 nm) 
UV

UV (254 nm) + TiO2   

UV + TiO2
Advanced inorganic photocatalysts were utilized to inactivate virus or bacteria,
which addresses the needs of providing safe water supplies through the
development of photocatalytic disinfection methods.

J. Mater. Chem., 2010, 20, 4529-4536

Antibacterial photocatalytic coatings would be helpful!
 Top energy-consuming countries (%)
100%

90% Others

80%
Energy consumption (Mtoe)

70% Former Soviet

Union
60% India
China
50% Japan

40%
European Union
30%

20%

10% United States

Source: BP, 2010
0%
1965 1970 1975 1980 1985 1990 1995 2000 2005

The rapid economic development in China is powered

by substantial increase in energy consumption which places her as
one of the largest energy consumption country in the world. 35
 CO2 emissions in China and the United States

Existing trend is simply

7000

6000
not sustainable and needs
United States to be rectified
CO2 emissions (Million metric tons)

5000

4000

3000
China

2000

1000

0
1980 1985 1990 1995 2000 2005

Data source: EIA, 2010

下面應該可以找到能源吧!
 Solar energy is abundant

Solar-Thermal
Solar-Electric
•Photovoltaic (solar
cells)
•Concentrating solar
power
Biomass

http://en.wikipedia.org/wiki/File:Available_Energy-4.png
真空熱導管式太陽能熱水器 Solar-Thermal
太陽能光伏技術 Solar-Electric (Photovoltaic)
 Photovoltaic Solar Cells

Silicon-based solar cells are too expensive

The $/kW must come down to ~1/5 of current price to
compete on the market with fossil fuels
Dye-sensitized cells
銅銦鎵硒薄膜太陽能電池
CIGS Thin-Film Solar Cells
 Roadmap of CIGS Solar Cell
18

16

14

12

10

8
Efficiency (%)

0
 2010-2012, upgrade technology and
equipment, construct enterprise
service platform

2009-2010：develop
technology

2011-2013：industrial equipment
and technology R&D

2008-2009, first generation

equipment R&D
Photocatalytic
Water Splitting
Our Planet Earth