JOURNAL OF RARE EARTHS

Vol.25, Suppl., Jun. 2007, p.295

Advancement of Environmental Purification Material Modified by

Rare Earth Metals
Wu Qisheng (%%I&)’* , Yang Chunsheng (&&!&)’ , Chen Xi (I% &>’
( 1 . Jiangsu Key Laboratory for Ecological-Environment Materials , Yancheng Institute of Technology , Yancheng
224003 , China ; 2 . College of Resource and Environmental Science , Beijing University of Chemical Technology,
Beijing 100029 , China )

Abstract : It is necessary to study the materials modified by rare earth metals in the environment field deeply and systemat-
ically, this paper comprehensively described the development of materials modified by rare earth metals in the filed of en-
vironment purification such as photo catalyst, desulfurization , denitrification and purification of tail gas. It will be helpful
to solve the environment problems in our country.

Key words : rare earth metals ; environment, purification materials

CLC number: TG174.4 Document code : A Article ID: 1002 - 0721(2007) - 0295 - 06

There are 17 lanthanon including the lanthanide
series from the atomic number 57 to 71 and the other
two elements Sc and Y which have the similar chemi-
cal properties to the former. According to the physical
and chemical properties, lanthanon can be divided in-
to light rare earths, middle-weight rare earths and
heavy rare earths. Lanthanon have excellent physical,
chemical, optical and electrical properties because
they have unfilled 4f electrons. Environmental pollu-
tion has been the main factor which hinders the devel-
opment of economy in 21 century, so it is important to
work out high performance environmental purification
materials. Also it will be helpful to our country’s en-
vironmental protection to take full advantage of our
rich rare earth.
1 Photocatalyst
1.1 TiOt photocatalyst
Photocatalysis, which can use the energy from
the sun under room temperature, is a perfect produc-
tion technique of clean energy because of its unique
performance. Photocatalysis has wide application pros-
pect and great social and economic benefit in the field
of environmental protection, clean energy, medical
treatment, construction material, automotive industry,
and food preserving etc. Ti02 is widely used due to its
fine stability in photocatalysis system. However , the
photocatalysis activation of Ti02 falls quickly when the
wavelength of lamp-house is over 387 nm“] . Because
rare earths have complex level structure and spectral
characteristic, people dope some into TiO, so as to im-
prove its activation. Ren Min’s‘” experimentation on
Ti02’s activation analysis showed that absorption spec-
trum of photocatalyst became wider by doping La3+
and Y3+ . From Fig. 1, it can be seen that the absorp-
tion spectrum of Ti02 shows some shift by doping La.
When there are 0.5 % (mole fraction) La in TiO, , the
shift reaches the maximum (about 420 n m ) . While
doping much more, the movement falls. The move-
ment trend of absorption spectrum of Ti02 doped with
Y is similar to La.
By studying different photocatalysis activation of
Ti02 doping with different rare earth, Zhou VcT~yi‘~’
found that TiOz doping with 1. 25% (mass fraction)
Dy,03, CeOz , Gd203showed some photocatalysis acti-
vation to different substances , and analysed what the
mechanism of photocatalyst modified by rare earth
was. They thought that some rare earth ions jammed
into the crystal lattices of TiOz and replaced the posi-
tion of some Ti ions , leading to part deformation of lat-
tice. The stress field derived from this deformation
hindered the movement of grain boundary, and re-
strained the growth of the grains of TiO,; some other
rare earth ions covered the surface of Ti02 grains in the
form of RE203, they could effectively separate the
charge carriers , prolong the life of the carriers and

Received date: 2006 - 12 - 30; revised date: 2007 - 04 - 12

Foundation item : Project supported by Jiangsu Key Laboratory for Ecological-Environment Materials (XJS2005015)
Biography: Wu Qisheng ( 1965 - ) , Male, Doctor, Professor
* Corresponding author (E-mail : Qishengw @ ycit .cn )
296 JOURNAL OF RARE EARTHS, Vol. 2 5 , Suppl. , Jun . 2007

I .6
I
-T 1.2
.-
P
3 0.8
d

0.4

0
200 240 280 320 360 400 440 480 520 560 600
/nm
Fig. 1 Absorption spectrum of TiOl doped with La
( 1 ) Pure TiO,; (2) Doped with 0 . 5 % La; ( 3 ) Doped with 0.75% La; (4) Doped with 1.0% La

prevent reuniting of the electron hole pair so as to im-
prove the properties of photocatalysis reaction. By
studying the surface energy band structure of ( C e ,
Ag) /Ti02 nanometer photocatalysis material with STM/
STS technique, Liang J i n~ heng‘ ~found
’ that by doping
rare earth and (Ce ,Ag)/Ti02 into nanometer Ti02, its
energy gap fell from 2.9 to 2 . 4 e V , and added new
energy levels Ecb = - 1 . 0 eV , Evb= 0. 9 eV and
E , = 1 . 9 eV, which could do some photocatalysis un-
der visible light.
The photocatalysis modified by rare earth metals
now has been widely used in environmental purifica-
tion coating, inorganic antiseptic and wastewater tr-
eatment[5’6:.
1.2 Perovskite photocatalyst
Perovskite-type compound oxides are new inor-
ganic nonmetals with particular physical and chemical
properties. Because of their steady crystal structure,
unique electromagnetism performance and high activa-
tion of redox, hydrogenolysis , isomerization and elec-
trocatalysis , they have been widely used in the field of
optics, electrics , magnetics and catalysis. Perovskite-
type rare earth nanometer compound oxides have
unique electromagnetism property and redox activa-
tion, and its redox activation plays a big role while it
is used as photocatalysis. When soluble dyes is de-
graded by perovskite-type rare earth nanometer com-
pound oxides, the couple of electron hole is derived
from the surface of catalyst with illumination of proper
wavelength, furthermore, the holes will interact with
water and produce hydroxyl with high activation, play
redox reaction with the dyestuff molecules attaching to
the surface of catalyst, and degrade them into small
molecules. The property of perovskite-type compound
oxides varies with the atoms of A and B in A B 0 3 .
Generally, in compound oxides AB03, the 2P orbit of
oxygen is valence band, and the d orbit of atom B is
conduction band”’ .
Taking Gd203, Fe ( N 0 3 ) 3* 9 H 2 0 and HN03 as
raw material, Niu Xinshu and Li Honghua“’ made rare
earth compound oxides GdFe03 in citric acid, and did
some photocatalysis degradation research on the influ-
ence of illumination time and catalyst addition to pho-
tocatalysis activation. Fig. 2 shows the relationship be-
tween the decolor ratio D, of active turquoise blue
KGL and the illumination time, and Fig. 3 shows the
influence of GdFe03 added on to decolor ratio of active
turquoise blue KGL. They found that GdFe03 was a
good photocatalyst, when the addition of the catalyst
increased, the decolor ratio increased gradually too,
and the rising tendency became weaker and weaker.
Asako Kasahara‘” made LaTiOzN by replacing
the atom 0 in compound oxides, and studied its pho-
tocatalysis property. Fig. 4 shows the UV-vis DR spec-
tra of LaTi02 N , the spectral range of nitriding speci-
xo
60
4’ 40
20
‘0 20 40 60 XO 100 120
tlmin
Fig. 2 Influence of illumination on decolor ratio of active
turquoise blue KGL
( 1 ) Without GdFeO, and illumination ; (2) With GdFeO, but no
illumination; ( 3 ) With both GdFeO, and illumination
 Wu Q S et a1 . Advancement of Environmental Pun3cation Material Modified by RE 297

g
Q"

(5)k I - --
I

"0 20 40 60 80 100 120

300 400 500 600 700

rlmin WavclcngtWnm

Fig. 3 Influence of GdFeO3 added on decolor ratio of active Fig.4 UV-vis DR spectra of LaTi02N
turquoise blue KGL (1 ) LazTiz07, samples obtained by nitriding LazTiz07at 1123 K
(1) 50 mg; (2) 100 mg; (3) 150 mg; (4) 200 mg; after nitridation for (2) 22 h , (3) 48 h , and ( 4 ) 72 h , and sam-
(5) 250 mg ple obtained ( 5 ) by heating LaZTi2O7(72h of nitridation) in air at
573 K for 24 h

Table 1 Catalysis activation of degrading organic matter by perovskite-type oxides photocatalysis

Organic matter to Degradation
Photccatalyst Catalyst Preparation method
he degraded ratio/%

AB03 Active turquoise blue KGL SrFeO3 - 5 Sol-gel 78

SrFe03 Sol-gel > 95
GdFeO3 Sol-gel 74
LaFeO, Sol-gel (easy to degrade)
Acid red 3B SrFeO3 Sol-gel > 95
LaFeOs Sol-gel 74
LaFeOr Coprecipitation 65
LaFeO, Grinding 26
LaCo03 Sol-gel 98
LaFeO3 Sol-gel 71
LaMnO, Sol-gel 48
LaCrO3 Sol-gel 8
Weak acid blue 2BR SrFeO, Sol-gel > 95
Acid orange SrFeOs Sol-gel > 95
Reactive brilliant hule KGR GdFeO, Sol-gel 79
Reactive brilliant red X-B GdFe03 Sol-gel 96
Reactive orange K-N GdFe03 Sol-gel 98
Azo dyes NdFeO3 Sol-gelatin 82
Water soluble azo hlue LaNi03 Coprecipitation 90
AI - .Ac,B03 Methyl orange Lao. &o. zCo@ Sol-gela 97
Reactive brilliant red Lao.wPbo ~ M n 0 3 sol-gel 90
Acid red 3B La0.9&0 cnFeO3 Sol-gel 86
ABI -.Bc,O, Reactive brilliant ret Lac%. 3sFeo.05 0 3 Sol-gel 83
Acid black 10B LaCoo9Cuo. I 0 3 Sol-gel 99
Acid red 3B DyFeo zC%., 0 3 - s
, Sol-gel 92
Acid red 38 L~eo.~c~o.Olo3 Sol-gel 97

men increases from less than 320 nm to about 600

nm, and the energy gap falls from 3 . 9 to 2 . 1 eV, it
indicates that the photocatalysis property improves ef-
fectively by nitriding La2Ti207.
Table l [ l o l shows the report of different dyestuff
molecule degradation and mechanism by using perovs-
kite photocatalyst.
2 Desulfurization and Denitrification
SO2 and NO, coming from the gas of coal-burning
are the main cause of the problem of acid rain. The
method that improves the properties of desulfurizer and
denitrifier by doping rare earth oxides is an effective
298 JOURNAL OF RARE EARTHS, Vol. 2 5 , Suppl. , Jun . 2007

way to solve the environmental pollution. The tech-
nique of multi flue gas desulphurization ( FGD ) has
been made and put into industrialization, such as the
wet limestone-plaster technique. FGD is expensive be-
cause it will consume lots of absorbent generally and
produce a great deal of waste water and waste residue.
The dry-process desulphurization could recover sulfur
so as to greatly reduce the cost of production, and it
will not produce further pollution, so this method has
drawn much attention. A lot of researches have been
done in this field, such as perovskite oxides, cerium
oxides, zirconium oxides, Co-Ti-0 and La203.Further-
more, La203could deoxidize NO after it is activated.
Taking y-A1203 as the carrier, Hu Hui and Li
Jin[11l made some Ce02/y-A1203, La203/y-A1203and
CeO2-La2O3/y-Al2O3with certain concentration. There
would be 3 different catalysts by drying them for 24 h
at 24 "c after hydrolyzation. Figs. 5 and 6 show the
catalysis ability of SOz-converting. Generally speak-
ing, the process from start to activation state of all 3
catalysts has 3 stages: ( 1 ) absorption stage of SO?.
Due to the absorption of the catalyst, the converting
ratio of SO2 rises quickly in the initial phase of heating
and forms the first peak ; (2) desorption stage of SO2.
With the rising of temperature, some SO2 disengage
from the catalyst, and the converting ratio of SOz falls;
( 3 ) activation stage of SO2. The temperature rises a
lot at this stage, SO2 attaching to the catalyst interacts
100
$ 80
5
60
1 8
S 40
sl" 20
* Temperature/%
OY '
0 20 40 60 80 100
thin
with the active ingredient and CO and comes into ac-
tive state at last with the converting ratio's gradual ris-
ing. We also learn that the mixture of Ce02 and La203
has better activation than either.
Sun Fan and Wang studied the activa-
tion process of catalyst with the rare earth oxides as
their catalyst which accelerates the interaction among
SO2, NO and CO. They found that the activation of
rare earth oxides is closely bound up to its hydration
property. Fig. 7 is the comparison of denitrification ac-
tivation of perovskite with SO2, and Fig. 8 is the com-
parison of desulfurization activation of perovskite with
NO. Taking LaCo03 as catalyst, the converting ratio of
SO2 is over 99% at 600 "c , and the selectivity of ele-
ment S is over 99% too. Besides, it is possible to do
desulfurize and denitrification simultaneously, and the
converting ratio of SO2 and NO could be over 95% at
the same time.
0
600
TI "C
400 ?2 Fig. 7 Comparison of denitrification activation of perovskite
with SO2
+
C La203; LaCo03; A Lao.gCeo.ZC003; 0 La&eo & 0 0 3 ;
200 g2 x Lao.zCeo.&o03; 0 CeO2
120

Fig. 5 Catalyuic activation curve of CeOz/y-A1203

100
1001 600

80 ,o
'g
-
400 3
60
$Ei
E 40
200
E
g 0
tSO,/%
5r 20
* TemperatureK TIT

Or'
0
' 20
20~ 40 80
40'
thin
'120
120 . 160
160 2200
bO
0 Fig. 8

0 La2&;
Comparison of desulfurization activation of perovskite
with NO
+ h C 0 0 3 ; A ho.gCeo.2CO03; 0 h&eo.5Co03;
Fig. 6 Catalyuic activation curve of La~031y-Alz03 x L a o 2 C e d o 0 3 ; 0 CeOz
 Wu Q S et a1 . Advancement of Environmental Purification Material Modified by RE
3 Purification of Automobile Exhaust
Automobile exhaust from motorcycles and tractors
has been the main atmospheric pollutants in our coun-
try. The purifier for automobile exhaust develops fast.
The lanthanon, which is the most important component
element, has been playing its part from the second
generation catalyst, and the consumption of rare earth
will increase gradually with the development of auto-
mobile industry and the gradual advancement of envir-
onmental standard.
In order to take full advantage of all kinds of cat-
alysts and overcome their shortcomings, in recent
years, the development of composite material of solid
solution such as cerium oxide, zirconium oxide, lan-
thanum oxide and praseodymium oxide brings high
temperature catalyst coming into being as new genera-
tion. The solid solution of cerium-zirconium compound
oxide converts the application of rare earth oxide such
as Ce02 from alumina loaded to preformation powder
with high specific surface area and high thermal stabil-
ity[16’. And they show fine redox property, ability to
store ~ x y g e n “ ~ ’better
, thermal stability and perfect
low temperature catalysis performance“*’ . Generally
speaking, the automobile exhaust purifier has 3 main
functions. Firstly, It can improve the catalysis activa-
tion. The catalysis could be kept in good condition by
adding some rare earth, especially heavy metal. Sec-
ondly, It can store oxygen. The ratio of air to fuel is
hard to control during driving, and it always fluctuates
from “thin burning” to “condensing burning”. This
problem could be solved by adding some rare earth
substance which has the ability to store oxygen. Last,
it can improve the thermal stability and mechanical
strength of the metal carrier. For metal carrier purifi-
er, the carrier is easy to be broken due to the car
shake, washing and eroding of the high temperature
gas. So it is necessary to add some proper rare earth
into the metal carrier to improve its thermal stability
and mechanical strength, and it will also gain the
ability of anticorrosion and to oxide at high temp-
erature“’] .
Song Chonglin[mq2‘j studied the rare earth perovs-
kite LaBO, and analysed the mechanism of decomposi-
tion reaction of N 2 0 by TPR and XPS . It indicates that
with the rising of the average valence state of B , the
chemical potential of oxyanion boosts and the reaction
activation is improved. There are two kinds of oxygen
in LaB03, one is adsorption oxygen in low energy lev-
el, and the other is crystal lattice oxygen in high ener-
gy level. The adsorption oxygen on the surface of cata-
lyst blocks the decomposition of N 2 0 , while adding
299
some CH, that interacts with the adsorption oxygen on
the surface could accelerate the reaction; and the de-
composition of N 2 0 on the perovskite composition La-
B 0 3 is a surface catalysis process.
4 Prospects
Technology is indispensable to the development of
the application of rare earth, so does the rare earth to
the environmental protection. From the references we
know that there are much fundamental research of rare
earth both home and aboard which relates to environ-
mental protection. There will be great potential appli-
cation of rare earth in environmental protection. Nowa-
days, the application of materials modified by rare
earth is in the primary stage, the industrialized appli-
cation will relies on the development of rare earth sci-
ence. It is necessary to take deep researches on the
material modified by rare earth, which will not only
bring us comprehensive industry applied cost, bust al-
so be helpful to solve the deteriorating environmental
problem in our country.
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